Environmental Science & Technology 1979 vol.13 no.2

H.P.: "Now that we're coming on-stream, Bill, we've got toshow compliance."Arrowsmith: "No problem, Hank, ERT also monitors air quality."

Arrowsmith sees his project through, using ERT every step of the way, fromsiting to compliance. ERT is the nation's largest full-service environmentalconsulting firm. For a free subscription to our informative Newsletter, writeto BJ. Miller, Environmental Research & Technology, Inc., 696 VirginiaRoad, Concord, Massachusetts 01742. For swift action on any environmentalproblem, call (617) 369-8910, Ext. 310. Our staff of nearly 800 is ready toserve your needs.

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132 Environmental Science & Technology

CONTENTSVolume 13, Number 2, February 1979

OUTLOOK

142Pollution control industry. A. D. Littlereport finds air, water and instrumentfirms in a growing business

144Regulations, Compliance with air andwater deadlines is highlight of ACS/AIChE session in Miami Beach, Fla.

146Hazardous substances. The federalInteragency Liaision RegulatoryGroup lists 24 materials of concern

149Pollutant analysis. The PittsburghConference has a full week of environmental papers next month

REGULATORY ALERT

155Economic penalties. ERT's Delandsummarizes the new enforcementpowers of the EPA and states in theClean Air Act Amendments

FEATURES

156Climate. Report on the Ist world climate conference this month in Geneva-F. Kenneth Hare, University ofToronto, Ontario, Canada

160Plant wastewaters. Textile industrycollects data on toxic pollutants-G.D. Rawlings, Monsanto ResearchCorp., Ohio and Max Samfield, EPA,Research Triangle Park, N.C.

year. Air freight rates per year available on request. Singlecopies: current issues, $5.00. Rates for back issues and volumesare available from Special Issues Sales Department. 1155 16th

;ti'll ~~~b~ ~~~~1~rI0s~';~;~~~~1~j\~:e'~f ~~~~~~r~~~g~of address to be received in the time specified: if claim is dated(a) North America: more than 90 days beyond issue date. (b)all other foreign: more than one year beyond issue date; or if thereason given is "missing from files." Hard copy claims arehandled at the ACS Columbus address.

SUBSCRIPTION SERVICE: Send alt new and renewalsubscriptions with payment to: Office of the Controller, 115516th St" N.W., Washington, D.C. 20036. All correspondenceand telephone calls regarding changes of address. claims formissing issues, subscription service, the status of records andaccounts, air mail and air freight rates should be directed to:Manager. Membership and Subscription Services. AmericanChemical Society. P.O. Boll. 3337. Columbus. Ohio 43210.Telephone (614) 421-7230. On ct!anges of address. include both

166Hazardous wastes. The Californiasuccess with recycling-C. G.Schwarzer, Dept. of Health Services,Berkeley

InRulemaking. Critique of proposed newsource performance standards forelectric utilities-R. W. Dunlap and B.J. Goldsmith, Environmental Research& Technology, Concord, Mass.

RESEARCH

179Sources and fates of aromatic compounds in urban stormwater runoff.Moira J. MacKenzie* and Joseph V.Hunter

A study aimed at characterization,identification of sources, and probablefate of aromatic sulfur compounds inpetroleum oils from stormwater runoffis presented.

184Design and evaluation of a new lowpressure impactor. 2. Susanne V.Hering, Sheldon K. Friedlander*,John J. Collins, and L. Willard Richards

The last two stages of a low-pressureimpactor described earlier have beencalibrated using a near monodisperseuranine aerosol.

189Evaluation of boron removal by adsorption on solids. Won- Wook Choiand Kenneth Y. Chen*

Adsorption was found to be moderately effective for the removal of lowlevels of boron from solution, depending on the pH of the suspension and theinitial boron concentration.

old and new addresses witt! ZI P code aiXompanied by a recentmailing label. Allow sill. weeks for change to become effective.

MICROFILM OR MICROFICHE. For information. writeto: Microform Program. ACS, 1155 16th St.. N.W., Washington, D.C. 20036. or call (202) 872-4554.

The American Chemical Society assumes no responsibilityfor the statements and opinions advanced by contributors to thepublications. Views expressed in the editorials are those of theauthor and do not necessarily represent the official position ofthe Society.

('redits: 140_ 143. 145, t:S& rs Julian Joscphson: 147.Chasc SlUdil>s. Ltd. (Wasnington, D.C.) (far left)_ andD. J. Hanson (remaining three): 15M, UN/FAO: 159.Lyle C. Axthclm. Bureau of Reclamation: 164, Wallace-Martin. Inc. (D.ayton. Ohio)

('ol'er: NOAA/Ken Dcwey

197Emissions from pressurized nuidizedbed combustion processes. Keshava S.,Murthy*, James E. Howes, HermanNaek, and Ronald C. Hoke

Results of the comprehensive analysis of emissions from a pressurizedOuidized-bed combustion unit arc described to illustrate the methodologyfor such comprehensive analysis.

205Free-radical oxidation of organicphosphonic acid salts in water usinghydrogen peroxide, oxygen, and ultraviolet light, Theodore Mill* andConstance W. Gould

Methylphosphonic acid and isopropyl methylphosphonic acid wereoxidized in water to phosphoric acid,CO2, and H20. Rapid and completeoxidation is possible with careful control.

209Acid precipitation in the New YorkMetropolitan Area: Its relationship tometeorological factors. George T.Wolff*, Paul J. Lioy, Howard Golub,and Jill S. Hawkins

A study of the spatial, meteorological, and seasonal factors associatedwith precipitation pH from 1975 to1977 is reported.

213Toxicity of copper to cutthroat trout(Sa/mo clarki) under different conditions of alkalinity, pH, and hardness.Charles Chakoumakos, Rosemarie C.Russo, and Robert V. Thurston*

For the soluble species CuH ,CuOH+, Cu(OHlz°, CU1(OH)2H,CuC03o, and Cu(C03lz1-, the acutetoxicity of Cu was inversely correlatedwith water hardness and alkalinity.

Editor: Russell F. ChristmanAssociate Editor: Charles R. O'McliaWASIIINCTON EDITORIAl. STAFf.'Managing Edilor: Stanton S. MillerAssociate Editor: Julian JosephsonAssociol(' Editor: Lois R. EmberMANUSCRIPT REVIEWINGManager: Katherine l. BiggsAssistan, Editor: Sheila M. KennedyEditorial Ani.uam: Rosalind M. BishMANUSCRIPT EDITINGAssociatt> Editor: Gloria L DinoteA.f.fociatt> Editor: Deborah A. WilsonGRAPHICS AND PRODUCfIONProdurtion Manager: Leroy L CorcoranDesigner: Alan Kahan Artist: Linda M. Mallingly

219Chemical speciation of heavy metals inpower plant ash pond leachate. ThomasL. Theis* and Richard O. Richter

Data from active Oy ash disposal sitemeasurements show that partitioningof heavy metals between solution andparticulate phases is most affected bypH, p(FeOOH), p(MnO,). andP(S041-).

224An approach to estimating probabilitiesof transportation-related spills ofhazardous materials. Charles A.Menzie

Spill probabilities are estimatedfrom equations based on the Poissondistribution. The precision of the estimates is expected to increase as thedata base is expanded.

NOTES

228On the degradation of 2,3,7,8-tetrachlorodibenzoparadioxin (TCDD) bymeans of a new class of chloroiodides.Claudio Botre*, Adriana Memoli, andFranco Alhaique

A new method for the decomposition of TCDD and other ethers is reported, using chloroiodides obtainedfrom quaternary ammonium salt surfactants.

231A comparison of time and timeweather models for predicting parathion disappearance under Californiaconditions. Herbert N. Nigg* and JonC. Allen

Advisory Boord: Robert J. Charlson. Charles Coutanl.Rudolr"B. Husar. Roger A. Minear. Francois M. M.Morel. Frank P. Sebastian. R. Rhodes Trussell. CharlesS. Tuesday. William E. Wilson. Jr.

Published by theAMERICAN CHEMICAL SOCIETY1155 16th Street. N.W,Washington. D.C. 20036(202) 872-4600

BOOKS AND JOURNALS DIVISIOND. H. Michael Bowen. DirectorCharles R. Bertsch. Head. Journals Departmen'Bacil Guiley. Head. Magazine and Production

Departmelllc

ESTHAG 13(2) 131-252 (1979)ISSN 0013-936X

The time-weather first-order disappearance model gave considerablybetter predictions than the time modelalone, for California Valencia foliage.

CORRESPONDENCE

234Ambient air hydrocarbon concentrations in Florida. Robert D. Sculley.Kenneth H. Ludlum and Bruce S.Bailey. William A. Lonneman andJoseph J. Bufalini

CORRECTION

239Chemical modeling of trace metals infresh waters: Role'of complexation andadsorption. Jasenka Vuceta * andJames J. Morgan

* To whom t:orrcspondcncc should Ix addrcl'o!>cd.

Thi:. issue cont,lins no parers for which there i:. ~ur'plcmcnlary nmlcrial in microform.

DEPARTME TS

135 Editorial

137 Currents

240 Industry trends

241 Products

242 Literature

243 Books

244 Meetings

245 Classified section

248 Consulting services

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Please send research manuscripts to ManuscriptReviewing.fealllre manuscripts to ManagingEditor.

For .luthor's guide i1nd editorial polil:)'. sec January1979 issue. page 51. or write Katherine I. Big!!s.Manuscript Reviewing Office I::S& T. A s;unplccopyright transfer form. whid Illay be cupied.appears on pa1:!e 110 of Ihe January 1979 issul.'.

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location Month DatesDenver.CO July 12-13Chicago, IL August 2-3Pittsburgh. PA September 6-7Boston. MA October 4-5Newark. NJ November 1-2Baltimore. MD December 6-7

For Full DetailsComplete information on the RAC-sponsored two-day seminars,including registration fees, will be furnished on request. For RESEARCH APPLIANCE COMPANYimmediate action, contact Mr. Wayne Baker, RAC's Director of Route 6, Gibsonia, PA 15044. 412-443-5935

Training, at the address or phone number listed. Environmental Instruments/Laboratory Products

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Tampa. FL January 11-12Atlanta. GA February 1-2Houston. TX March 1-2Dallas. TX April 5-6Los Angeles. CA May 10-11san Francisco. CA June 7-8

Two-Day Technical SeminarsConducted by Dale Lundgren, Professor of EnvironmentalEngineering Sciences, University of Florida, the RAC-sponsoredseminars cover all relevant parameters for accurate sampling ofgaseous and particulate emissions from all types of stationarysources. These comprehensive seminars describe the methods,procedures, and types of equipment required to sample stacks andexhaust systems in accordance with EPA Methods 1 through B.Each seminar is programmed to accommodate 20 participants on afirst-come, prior registration basis.

1979 ScheduleLocation Month Dates


GUEST EDITORIAL

Scientific questionsand the courts

In November 1978, a judge in a county court inwestern Pennsylvania issued an injunction banningfluoridation by the West View Water Authority afterlengthy hearings in a suit instituted by several residents. The most recent epidemiological and otherevidence showing the benefits of fluoridation waspresented to the court in support of continuing thefluoridation, as well as the lack of any credible linkbetween fluoridation and incidence of cancer. Theplaintiffs case appears to be based in large part on onestudy which purported to show such a connection, butwhich has been shown authoritatively to be invalid.Nevertheless, the judge ruled that the bulk of the evidence showed that fluoridated water can cause cancer. In a newspaper letter he stated, "I heard a greatdeal of scientific testimony and made my decisionbased upon the testimony."

As of this writing, West View has appealed toCommonwealth Court, and the issue is complicatedby the jurisdictional authority of the State Department of Environmental Resou'rces in granting permitsfor fluoridation. Even if West View now wins its appeal, which it should, at least on the basis of the bestscientific evidence, the initial ruling is another important example of an environmental decision goneawry, and, perhaps more significantly, one involvinga judicial determination.

There is no doubt that many environmental controversies involving conflicts among laws, interpretation of legislative intent, and competing interestsprotected by law appropriately and necessarily requirea judicial determination for resolution. And certainlythe courts often have to deal with scientific questions,such as in patent litigation. But are they in a positionto evaluate adequately the evidence on a complexscientific question? Should they hear the competingclaims and evidence and decide whether saccharin isa human carcinogen? Whether fluorocarbons aredepleting ozone in the stratosphere? Or, indeed,whether fluoridation is harmful to human health?

We seem to be developing and utilizing a variety of

sometimes clumsy mechanisms to deal with environmental matters, and the atmosphere is often supercharged and the voices strident. In July 1978, at thefinal EPA hearing concerning its proposed regulationsfor the control of trace organic chemicals in drinkingwater, there seemed to be an adversary and sometimesalmost carnival milieu, hardly conducive to a calm anddeliberate determination of a policy that could bestadvance the public interest. One useful mechanism foranalyzing competing scientific claims is the NationalAcademy of Sciences ad hoc panel report. However,even there the quality of the effort can be variable, andthe recommendations not fully and thoughtfully incorporated into regulatory decisions. One example isthe hasty governmental decision banning major usesof fluorocarbons, when such a report recommendedadditional data collection for a specified period withvery little risk.

To improve our environmental decisionmaking inthe public interest, what may then be needed is agreater reliance on mechanisms that can thoughtfullyarticulate and elucidate the status of the scientificunderstanding and uncertainties. It has been suggestedthat a "science court" could play such a role in evaluating scientific controversies impinging on publicpolicy. The use of this court's "judgments," which ineffect and hopefully would be the best available scientific concensus, would then be likely to improve thequality of such policy decisions, as well as thoseemerging from traditional courts that must deal withthese questions.

Dr. Julian B. Andelman is Professor ofWater Chemistry at the Graduate SchoolofPublic Health. University ofPiltsburgh.Pitlsburgh. Pennsylvania.

Volume 13. Number 2. February 1979 135

~INSTRUMENTSt~"eNEWSCOMBUSTION CO TROL' HEALTH & SAFETY' E TAL' PROCESS

•

MSA has some answers.Your workplace atmosphere must meet

OSHA regulations on over 500 gas, vaporand dust hazards whose TLVs (ThresholdLimit Values) have been determined.

MSA has the spot and continuous monitoring instruments to help you detectmost of the hazards on the official list.

One way to start on your hazardousatmosphere monitoring problems is todiscuss them with an MSA field representative.

CIRCtE 17 ON READER SERVICE CARD

Questions about OSHAlimits on hazards?

Call us (we're in the Yellow Pages). Orcircle the appropriate Reader ServiceNumber. MSA Instrument Division, 600Penn Center Boulevard, Pittsburgh, PA15235.

this solid-state unit is simple. A calibration check kit is available for reproducibletesting and certification_

Ask your MSA instrument specialist formore details or write for literature.


pany saved half of its annual fuel bill foroperating the dryers, and savings have already paid for the MSA instrument system. The plant is planning a similar installation in its finishing department.


and increases the amount of makeup airto reduce vapor concentration. Result:The plant is a safer place to work. Theinsurance firm has since increased theallowable top limit to 30% LEL. The com-

New carbon monoxideindicator joins the MSAportable instrument line.

MSA now offers a battery-operated COindicator that will work a full shift betweencharges. The Portable Carbon MonoxideI ndicator, Model 70, provides over eighthours of detection of airborne CO in the0-100 parts per million (ppm) rangeor 0-500 ppm range.

The Model 70 helps you keep track of"the silent killer" in garages, loadingdocks, coke plants, open-hearth furnaces.manufacturing plants, refineries and similar locations. When CO concentrationreach preset TLV levels, the instrumentprovides a visual alarm, plus an audible

alarm if you wish. The alarm point can beset at any desired level.

For compliance records, the Model 70CO Indicator is calibrated for use with aI-volt recorder, or it can be adapted easilyto other recorders.

Recharging is by liS-volt ac source orfrom a 12-volt battery. Maintenance on

The printing and dyeing operation in afabric finishing plant involved the removal of mineral spirits from the cloth ina gas-heated dryer. Insurance regulationscalled for control of solvent vapor below15% LEL. To achieve this level, the operator was forced to change air in the dryeras often as four times a minute- wastingfuel and heat.

An MSA instrument specialist studiedthe problem, came up with a two-pointcombustible gas analyzer system withsensors mounted in strategic monitoringpoints. The MSA instrument system monitors and measures the concentrations ofcombustible vapors so accurately that thedryer can be operated safely at muchhigher solvent concentrations. That translates directly to fuel savings.

The analyzer was set up to provide anaudible alarm at 20% LEL; if the vaporconcentration reaches 25% LEL, it automatically shuts off the gas, starts the fan.

Factory cuts fuel bill for dryer in halfby monitoring combustible solvents.

~ I

Make sure/cheek MSA

One operator of a l20-million Btuheater fired with fuel oil had a history ofplugging troubles with other analyzersuntil he tested a Model 803. Now he reports, "This was the first analyzer installedthat successfully worked when we merelyfollowed instructions."

Another company, operating severalmarine-style 20,OOO-ib steam boilers,likedthe demonstraiion of the 803 so well thatthey kept the demonstration model andordered another for full evaluations.

If you need a dependable, accurateoxygen analyzer that stays out of troubleand saves you fuel, get details on theModel 803.


On-stack oxygenanalyzer saves fuel whilemeasuring emissions.

MSA's new Model 803 Oxygen Analyzer was designed to solve many of thepractical operating problems that you facein accurate monitoring of hot,dirty flue gases.

The Model 803 sensor cellmoun ts directly on the stackfor shortest possiblesampling line. II operateshot to keep all gasesabove their dewpoints and minimizeplugging. Thestabilized fuel cellsensor measuresoxygen-not aneffect of oxygenso it produces ahigh-level signal.II analyzes 0.1 % to 21 % 02. The lower theoxygen concentration, the better the readability on its logarithmic scale.

Users of the Model 803 Oxygen Analyzer have commenied on iisfasi responseto changes in furnace operat·ing conditions. And its close matchup betweenoxygen readings and theoretical calculation of 02 content gave them fuel savingsthat paid for the analyzer quickly.


INTERNATIONAL

By the 1990's, solar could supply8-15% of all of Israel's energyneeds, Natan Arad, director-general of Israel's National Energy Authority, estimated. At present,300000 solar heaters provide onethird of that country's domestic hotwater needs, thereby saving 3% ofthe national electricity consumption, Arad noted.

WASHINGTON

EPA proposes its first "cradle togra~e" hazardous waste disposalregulations. Under the proposedrules, all producers of more than220 Ibs (100 kg) of hazardouswaste per month would have to establish a system to track the wasteuntil its final disposal. Full information about the wastes' composition would have to be provided tocompanies transporting or disposing of the wastes. Lined landfillswould have to be located at least500 ft from any water source, andwater-impervious clay soil wouldhave to be layered over closed landfill sites. Landfills would have to bemonitored continuously.

A decade-long air quality compliance dispute between the EPA andTVA has been settled. The Tennessee Valley Authority's Board approved an agreement with theEPA, Alabama, Kentucky and 10citizen health and environmentalgroups which will, by 1983, bring10 of its coal-fired power plantsinto compliance. This agreementends the lawsuits brought againstthe TVA for noncompliance.Among the measures taken by theTVA to meet air quality standardsare the burning of medium- andlow-sulfur coal and the use of fluegas scrubbers to remove sulfurdioxide at some plants, the use ofcoal-cleaning methods, and the useof electrostatic precipitators or fabric-filter baghouses to control flyash. The pollution control equipment is expected to cost about $450million/y in the early 1980's.

CURRENTS

NOAA administrator Frank

NOAA's administrator RichardFrank announced the U.S.' participation in a year-long global weatherexperiment. The U.S. is among the147 nations participating in thisWMO- and ICSU-sponsored program. The various projects, some ofwhich began on December I, willhelp meteorologists to developmore accurate methods for forecasting the weather. Instrumentionis perfuse; included will be specialairplanes to take wind tests, stationary weather satellites, orbitingpolar satellites, ocean buoys, research balloons and 50 wind-testingships. The collected data will be fedto computers, assessed and used byweathermen around the world toimprove their weather predictingskills.

Despite an o~erall austerity budgetfor fiscal 1980, EPA's operatingbudget will increase to $1.3 billion,up$O.1 billion from fiscal 1979.The EPA's construction grants program, however, will be slashed to$3.8 billion, down from fiscal1979's $4.2 billion.

EPA's fourth annual NationalWater Quality Report to Congressfinds some improvements, but reports that 89% of 246 river basinsin the U.S. are plagued by waterpollution problems from municipaldischarges. Information suppliedby the states on these 246 basins indicates that 72% of the river basinsare affected by industrial discharges to varying degrees.

EPA proposes the "bubble" conceptwhich allows industry to decide themost cost-effecti~e way of meeting

air quality standards at multiprocess plants. This move away fromthe traditional "command and control" approach to pollution controlwill permit plant management topropose the most cost-saving planhwide mixes of pollution control solong as the overall clean air requirements are met. This moreflexible regulation is seen as an incentive to industry to come up withinnovative solutions to pollutioncontrol.

The USGS has recei~ed $96 millionin appropriations for water-resources studies for fiscal year 1979;this represents about 15% of thetotal U.S. Geological Survey appropriation for earth science andresource investigations. The USGSmonitors the quantity and qualityof surface- and groundwater resources at more than 40 000 datagathering stations throughout theU.S.

To defray the costs of complyingwith the "toxics" law, small businesses may apply for special loansfrom the Small Business Administration. These businesses mayapply directly to SBA for longterm repayment loans available at6%% interest. They would have todocument the costs of new testing,plant conversions or new equipment needed to comply with theToxic Substances Control Act.

A caU for toxicologists. Four regulatory agencies asked the U.S. CivilService Commission to set up anew job classification for toxicologists. The heads of the ConsumerProduct Safety Commission, theEPA, FDA and OSHA asked thata separate "toxicology register" beestablished to help them in hiringthe toxicologists needed to carryout the mandates of the health andenvironmental laws.

STATES

To meet federal air-quality standards, the Washington, D.C., metropolitan area needs a vehicle in-

Volume 13, Number 2, February 1979 137

spection and maintenance (11M)program, according to the Metropolitan Washington Council ofGovernments (COG). COG alsosays that the area will need an extension of the compliance deadlinefor ozone and carbon monoxide to1987. The District, Maryland andVirginia are planning on meetingthe January I, 1979 deadline forsubmitting state implementationplans. However, Virginia will onlypropose its 11M program to its1979 legislative session, after January I; and Maryland is now drafting an 11M program for submissionto its 1979 legislative sessions. TheDistrict, which has an 11M program, will not enact it until the twostates enact similar programs.

TVA's Moore

A water quality suney of the Tennessee Valley drainage basin findsthe quality deteriorating. For example, fish in the Virginia portionof the Holston River and in an embayment of the Tennessee Rivernear Huntsville, Ala., are contaminated with mercury and DDT, andare hazardous to health if eaten.These are the two most seriouslypolluted sites, but the TennesseeValley Authority (TVA) surveyfound 17 other "critical" locationsand 28 other "major problem"areas in the Tennessee River drainage basin, "Many people tend tothink that the rivers and streams ofthe Tennessee Valley ... are free ofpollution problems. But unfortunately that just isn't so," saidHarry G. Moore, Jr., acting director of environmental planning forTVA. The survey is entitled"Where the Water Isn't CleanAnymore."

Ohio has adopted new air pollutionrules regarding alerts caused byozone. The new regulations requirethat an alert be called wheneverozone reaches 0.2 ppm or 200 onthe pollution standard index (PSI),which is twice the level of the oldregulation alert. An emergency episode for ozone would be called


when ozone reaches 0.5 ppm or 400on the PSI, which is lower than theold regulation. Ohio will continueto issue a health warning to affected areas when ozone levelsreach 0.08 ppm or 100 PSI. Ned E.Williams, director of the Ohio EPAsays that "Our number one culpritand contributor to the ozone problem in Ohio is the automobile."

The Minnesota Pollution ControlAgency (MPCA) rejected a plan todevelop a former chemical dumpsite in St. Louis Park. The site wasformerly owned by the Reilly Tarand Chemical Co., which used it todispose of creosote wastes. Thesouthern portion of the site is heavily contaminated, and agency staffbelieve that the contamination mayhave migrated into the soil and underground waters of the northernportion. The state Health Dept. ordered the closing of four wellsnorth of the site when laboratory

.analysis of the well water showedtrace levels of polynuclear aromatichydrocarbons. It is feared thataquifers providing drinking waterto several western Minneapolissuburban communities may bethreatened. MPCA is suing ReillyTar, now located in Indiana, forcontamination-related damages.

New Jersey and New York are involved in a pilot program, funded bythe U.S. EPA, designed to gain citizen participation in the control oftoxic substances. Thirty-six publicinterest groups and 500 people areto participate in the program.Twenty-five of these groups willdivvy up the $106 000 distributedby the EPA; II organizations willparticipate voluntarily.

Two local New Jersey governmentalentities are seeking federal funds tofinalize a preliminary resource recovery system design. The Hackensack Meadowlands DevelopmentCommission and the Bergen County Board of Chosen Freeholders areapplying to the U.S. EPA for $174275 under the President's UrbanPolicy for resource recovery projectdevelopment. The proposed systemwill handle 2500-3000 tons of solidwaste per day.

MONITORINGA portable electrostatic precipitatoris being developed by the Universityof Denver Research Institute undera 3-y, $2.6 million grant from the

U.s. EPA. The prototype devicewill be built for the collection ofhigh resistivity, fine-particle emissions at their SOUTce. The two-stageprecipitator will be built on asmany as four semitrailers, and willbe transported to industrial sites todemonstrate its operation at different geographical locations and withvarious types of particulates undervaried operating conditions.

TECHNOLOGYUp to 99% of hydrogen chloride(HCI) is removable with the "Mitsubishi-TESI Dry Process Poisonous Gas Treatment System," according to Mitsubishi Heavy Industries, Ltd. (Japan). The nameTESI is from a u.s. firm, TellerEnvironmental Systems, Inc., withwhich Mitsubishi has a "technicaltie-up." Essentially, HCI is removed by a lime slurry and filterbag system, and the product is apowder. Tests are taking place witha maximum throughput of 5000N m) Ih, at Mitsubishi's Isogo Factory at Yokohama, Japan.

Coal gasification can be improvedby use of a honeycomb catalystmade of ruthenium. The honeycomb design replaces conventionalpelleted catalysts, says MattheyBishop, Inc. (Malvern, Pa.). Thecompany believes that the new design is more efficient in convertingthe gas mixture that comes fromcoal, to methane. The open structure permits freer flow of reactantgases, and does not obstruct pipingwith "fines." Moreover, honeycomb catalysts are much easier tohandle than are pelleted catalysts,Matthey Bishop says.

This system recycles "black water"and comes up with an odorless,clear product. It is a "closed loop"toilet system which controls, retains, and treats human wastes atthe point of origin. Known as theCycle- Let, it can be used as a nodischarge, or limited discharge system. Since the Cycle-Let requiresno fresh water for operation, asmuch as 600 000 gpy of water canbe saved by its use. No sewer hookups are needed. An electrical control system warns of any malfunction, audibly and visually. Depending upon level of usage, sludge needbe removed only every 1-5 years.The Cycle-Let is made by theThetford Corp. (Ann Arbor,Mich.).



port Beach, Calif.). OTEC is oceanthermal energy conversion. TheOTEC-l test platform will be theUSNS CHEPACHET (T-AO-78),which will be reclassified as anoceanographic research vessel.Ocean thermal uses a heat transferfluid which, in vapor form, runs aturbine to generate electricity.After running the turbine, thevapor sinks to an installation incold, deep ocean water where itcondenses. The condensate is thenpumped up to warm ocean depthsnear the surface, where it reevaporates to form the gas to run the turbine. TRW, Inc. is the principalsub-contractor.

Solar cell array

A 3500-watt (peak) solar electricpower system has been dedicated atSchuchuli, Ariz., on Papago Indiantribal lands. It is being managed bythe Dept. of Energy's NationalPhotovoltaic Conversion Program.The system will service 96 residentswith enough power for 15 four-ft 3

refrigerators, a wringer-type washing machine, a sewing machine, a2-hp, 5000-gpd pump for the community well, and 40 fluorescentlights. The solar cell array has 192photovoltaic modules, each containing 42 solar cells. Excess energy is stored in a specially-designedbank of lead-acid storage batteries.Capital cost was $108 483, with theenergy cost estimated at $1.76/kWh.

What if adipic acid can effect efficient S02 removal? Then, smallerflue gas desulfurization (FGD)scrubbers may become possible,says Michael Maxwell of the U.S.EPA (Research Triangle Park,N.C.). What the acid does is to stabilize limestone scrubber pH drop,and make the FGD system "moreresponsive." Maxwell notes thatS02 concentration variations donot seem to affect efficiency, sovery possibly scrubbers may nothave to be designed so large as toaccommodate "worst case" situations. In tests at TVA's ShawneeSteam Plant (Paducah, Ky.), FGDsystems with adipic acid averaged97-98% efficient. Adipic acid is aprincipal component of nylon production.

How well do ozone 0 3 and chlorinedioxide (CI02) technologies work tomake drinking water safe? EPA/Cincinnati made a careful studyand evaluation of many technolo-


gies, and of water treatment philosophies in the U.S., Canada, andEurope. Also covered is preozonation of the water with subsequent"biological activated carbon" treatment (£5& T. October 1978, p1141). Fundamental uses, and engineering design of various systemsare discussed in detail. The reportnumber is EPA-600/8-78-018; itwas prepared by the Municipal Environmental Research Laboratory,EPA, Cincinnati, Ohio 45268.

DUSTRYA contract to develop liquid metalsas solar energy heat conductors wasawarded to Westinghouse's advanced reactors division (Madison,Pa.). The initial $25 000 contractwill determine how temperaturechanges will affect properties ofmaterials, such as liquid sodium,proposed as heat transfer agents.

Whether there will be severe energydisruptions in the future will be determined by the extent to whichoverregulation of the nation's oilcompanies inhibit necessary capitalinvestments, according to JerryMcAfee, chairman of Gulf OilCorp. McAfee said that there wereadvances in "soft" areas of technical development, public awareness,and energy use, but that the critical"hard" area-regulated pricinghas not been adequately addressed.He warned that such price controlswill discourage U.S. production,and serve to increase reliance on oilimports from potentially unreliablesources.

A contract for test performance ofOTEC-l was awarded to GlobalMarine Development Inc. (New-

MeA vice president FrOSl

Society may benefit from pollutioncontrol regulations, but investmentin compliance with them wouldrarely, if ever, increase productivityand innovation. This is the assessment of Edmund Frost, vice president and general counsel of theManufacturing Chemists Association (MCA, Washington, D.C.).Frost noted that the chemical industry will expend $3.4 billion onpollution control equipment thisyear. This expenditure will be forregulation compliance, most or allof which, Frost said, must be considered as non-productive.

Private contractors may handle municipal waste collection more andmore, partly because of "Proposition 13" fever, William T. Lorenz& Co. (Boston, Mass.), whichmakes economic forecasts, believes.The 145 million t handled in 1977will be 200 million t by 1985. Also,Lorenz predicted that industry,which spent $615 million to handleand dispose of wastes in 1977, willpayout $1.2 billion in 1985. Theprimary cause for this jump will benew hazardous waste standardsand requirements, Lorenz foresees;also, operating expense levels forindustry will go up from $1.2 billion in 1977 to almost $2.2 billionby 1985.

Volume 13, Number 2, February 1979

Hlltlfllk llf "11lk.l'l" IIlJI<Jlll, ·.tlll' 1

See it at the Pittsburgh Conference, Booths 822-929

CIRCLE 6 ON READER SERVICE CARD 141

The pollutioncontrol industry

Its market share could be $3.5 billion by 1983, representing a growthof 11-12% per year. Some sectors may move faster than others

Loud, indeed, has been the hue andcry from many quarters of industry,concerning environmental·regulations.That would hardly come as a surprise,when one considers capital and operating costs brought about by theseregulations-many of which may notgo to a directly productive purpose.But is there any sector of industry thatmight benefit from these regulationsin some way?

Yes, there is. That sector is the pollution control industry (PCI). It hasabout 600 companies in all phases ofair, water, and solid waste/resourcerecovery. In all fairness to the PCI, itshould be mentioned that many of itsindividual component companies try tohelp client firms meet regulations forthe lowest achievable cost, and, if at allpossible, find ways to offset compliance costs.

An updateIn 1972, Arthur D. Little, Inc.

(ADL, Cambridge, Mass), under acontract with the U.S. EPA, made a


study on the impact of environmentalregulations on the PCI. Results of theearlier study can be found in "Economic Impact Study of the PollutionAbatement Equipment Industry,"Report to EPA by Arthur D. Little,Inc., December 1972 (EPA Contract

o. 68-01-0553). One would think,therefore, that an update would beneeded. Thus, ADL prepared such anupdate for the EPA, completed lastyear. Objectives were, essentially

• to identify any constraints on theindustry's ability to meet needs andmarket demands stemming from theEPA's regulatory activities

• to evaluate performance of PCIcompanies and their attitudes towardfuture investments

• to estimate markets and resultingemployment associated with the industry, and its role in satisfying environmental regulatory requirements.

Terry Rothermel (ES& T. April1978, p 379) and five of his colleaguesrepresented ADL for the study's

preparation. EPA's project managerwas Edward Brandt, who was with theEconomics Division, and has movedover to the Permits Division since thereport appeared. They gave the bulk oftheir attention to air pollution (ape),water pollution control (wpe), and resource recovery (RR) sectors of thePC I.

Growth and profitsFrom 1972 to 1976, leading com

panies of the PCI experienced a 1622%/y growth rate, as compared to a9% rate for all U.S. manufacturing.Profitability was "about average" forU.S. industry-I 0-11 % after-tax return on stockholder's equity. However,the water treatment chemicals sectordid much better ($250 million in salesin 1977, with, maybe, a 19%/y growthto 1983); indeed, it was among themost profitable in U.S. industry.

For 1977, the PCI market share wasabout $1.8 billion. ADL foresees amarket share of $3.5 billion by 1983,representing a growth of 11-12%/y,

PMtlculate conIroI so.- Inatrunle!'t-

American Air Filter Babcock & Wilcox Beckman InstrumentsEnvlrotech/BueIl Combustion Monitor Labs

EngineeringJoy ManufactlM'ing Combustion Equipment KlA Scientific

AssociatesResearch-Cottrell Envirotech/Chemico Lear SiglerU.S. Filter Research-Cottrell Enylronmental Data

Corp.Wheeiabrator-Frye UOP Tyco

Meloy laboratories

NalcoBetzCalgon (~ck)Drew (U.S. Filter)Dearborn (W.R. Grace)Mogul (Dexter)

EPA's 8raDdt

"The report provides some usefulinsights into the economic characteristics of the industry, and howEPA policies affect decision-making and risk"

guidelines may sharply curtail thispractice, and should be promulgated inthe near future, according to what washeard at the Forum.

R&D motivationsMany in the PCI feel that needed

pollution control technologies-bothair and water-arc generally available,according to the report. Others mayargue forcefully against that positionon the grounds that since pollutioncontrol is largely a "non-productive"

--oupplIeeFischer & PorterGeneral'SignalBetzBeckman InstrumentsLeeds & NorthrupFoxboroGreat LakesJohnson ControlsTaylorHoneywellTechnlcon

• According to Alll report listings.

E~

EnvirotechEcodyneRexnordFMCPenwaltNeptune InternationalDorr-OliverPeabody International

....ADL's Rotbermel

"EPA's interest in understandingthe impacts of their policies uponthe PCI made that industry verywilling to provide the informationvital to the preparation and completion of this study"

purchased under a bid shoppingscheme. Money is saved for the generalcontractor's benefit-which is thewhole idea of bid shopping.

Extreme concern about the bidshopping practice was expressed byEPA, and by member companies ofthe Water and Wastewater Equipment Manufacturers Association(WWEMA, McLean, Va.). Thematter was brought up at WWEMA'sWashington Affairs Forum, held atWashington, D.C., in December. ew

"Throwaway your degree"Several months ago, an engineer

with a company serving the wpc fieldwryly told an ES& T editor: "Whenyou compete for a municipal contract,throwaway your degree ... and comeup with the lowest bid. Know-how,capabilities, experience, future reliability, alternative technical options,and cost-effectiveness don't really cutany ice."

Perhaps this assessment is some·what exaggerated, but, be that as itmay, ADL considers the municipalbidding process to have the greatestimpact of concern on the PCI. Thisprocess essentially involves expenditures of federal grant money for spe·cialized sewage treatment equipment/instrumentation systems. Ofspecial concern, for instance, is thatlow-bid purchasing may impede technological innovation, and result incostly operation/maintenance prob·lems in the future, according toADL.

Also of concern is "bid shopping"after wastewater treatment (wwt)awards are made. Here, the municipality may procure equipment andinstrumentation according to priceconsiderations only, with resultingimpairment of total system quality andperformance. Construction grantfunds are used to pay for equipment

based on 1978 dollars, and a 5-7% innation rate. RR systems and nue gasdesulfurization (FGD) systems couldenjoy faster growth. As for employment, job-equivalents associated withthe 1977 market share numbered35850. This number could well rise to43900 by 1983, ADL forecasts.

With respect to financial resourcesin this industry, ADL believes thateven the larger of the componentcompanies normally have sales of$200-700 million/y. They "are notamong the multi-billion dollar firmswhich command the greater financialresources within the U.S. manufacturing industry. Hence, the industryhas been limited by the resources of itsleading participants, as well as bydisappointing profitability," accordingto the report.

Perhaps account should be taken ofrecent mergers/acquisitions within theindustry, and by companies outside theindustry, which acquire PCI companies. Cases in point are Whcelabrator-Frye's merger with Neptune,and Allis-Chalmers' acquisition ofAmerican Air Filter Co., Inc. It mightbe interesting to sec what effect on financial resources these mergers/acquisitions might have in the near future.


investment, users would continue toseek lower-cost solutions; hence, amotivation for R&D, ADL says.

But R&D motivation may be"wishy-washy," at best. One reason isthat even the larger PCI firms enjoyonly $200-700 million in annual sales,with "average" profitability withinU.S. industry, so these firms-withnotable exceptions, perhaps-wouldnot be inclined to commit heavyfunding to pollution control R&D.Moreover, larger, billion-dollar corporations coming into the "PCI club"may lack the necessary businessknow-how for this field, and thus,would approach R&D most gingerly.

On the other hand, the federal establishment's plan seems to be to lookto the private sector for R&D efforts,mainly in the form of development ofnew, proprietary technologies. Accordingly, EPA's R&D budgets forthis item have been declining. Theproblem is that the private sector's,particularly potential control systemusers', motivations for innovation maybe subject to question for various reasons, ADL believes.

Some may move faster

Earlier, with respect to apc, it wasnoted that FGD systems might enjoy

a faster growth than that of the PCI ingeneral. The promulgation of stringentS02, and, perhaps, particulate andNOx standards, pursuant to the CleanAir Act of 1977, may have this effect.Moreover, ADL's Rothermel reminded ES& T that much "catch-up"work is still needed in the FGD field.But also, stricter standards for particulate control may well extend theperiod of uncertainty for companies, interms of technological performance,operating experience, and market position, according to ADL. A problemis that apc, especially with regard toparticulate control, "is in danger ofhaving technology created in the contract," instead of being developedthrough the medium of the pilot plant.That situation, in turn, could lead tounreliability, and a commensurateundermining of user confidence.

Also, with regard to particulateemissions control, that segment of theape business has been the most stableand profitable, ADL noted. Its stateof-the-art has been making steadyprogress which could, however, bedisrupted, if new, very stringent standards come into being, ADL believes.

Perhaps, then, the main questionconcerns the role of technology forcing, as in particulate control, for ex-

ample. Now, maybe environmentalconcerns may require higher ape performance. But ADL queries whethera tcchnology-forcing standard-wherea tcchnology presently exists and isprogressing-might not be as effectiveas it could be in an alternative situationin which no pollution control technology exists, at all.

Keeping ahead

In the past, PC I customers werelargely concerned with meeting minimum regulatory requirements. Thefuture, however, may bring about aneed to keep up with, or even ahead ofpollution control regulations. Thus,emphasis on capital investment andnecessary technology could give someway to operating performance andcosts, AD L predicts.

Later this month, there will be agood opportunity for PCI firm representatives and their customers, andregulatory people to discuss all of thesematters face to face. That will be at theThird Annual Meeting of the Environment Industry Council, to be heldon February 28-Mdrch I, at Washington, D.C. For more information,contact the Environment IndustryCouncil, 1825 K Street, N.W.,Washington, D.C. 20006.

ES& T hopes to see y'all there. JJ

In the future, the main emphasis ofenvironmentalmonitoring and control technology,

as well as court cases, will be on

Compliance with regulations

Court challenges involving the various environmental laws, including theClean Water Act of 1977 (P.L. 95217), will continue occurring for sometime. But cases governed by this lawwill probably concentrate more onactual compliance. "Courts will continue to accord wide latitude to EPA insetting general and individual standards, so long as the court is convincedthat EPA did its homework, and explained its reasoning. Rightness orwrongness from a general point ofview, economic or technological, doesnot enter heavily into the matter.

"Industries will seldom prevail incourt on future review questions,"George Coggins, professor of law atthe University of Kansas, said at the

144 Environmental SCience & Technology

71 st Annual Meeting of the AmericanInstitute of Chemical Engineers(AIChE), which included a 22-sessionprogram on compliance, and was heldat Miami Beach, Fla., in November.He noted that "basic interpretationalproblems have long been ironed out,and are no longer a reasonable groundfor challenge." Moreover, "the beatingEPA has taken in several cases [oneexample was American Meat Institutev. EPA, 1975, involving regulations forthat industry, developed from petroleum industry data) should lead it into

The compliance sessions werejointly sponsored by the AIChE.and the American Chemical Society.

using more careful and complete procedures, and bcttcr articulation of thereasons for its decisions."

Monitoring instruments

As for the technology of compliance,Coggins also observed that no significant amount was "forced." Rather,EPA. he said, has largely "confined itsattention to demonstrated methodsand processes, although occasionallyrequiring technology transfer." A casein point was California and HawaiianSugar Co. v. EPA. It dealt withBPT/BAT regulations based on activated sludge and sand filter technologytransfcr. Herc, EPA prevailed. Manyin the environmental field agree withthat evaluation concerning technology

The interrelationship problem

Source: Paper by James Commms, JACA Corp.

forcing; certainly, many others willlake issue.

Be all that as it may, monitoringinstrumentation is one important aspect of technology for compliance.This instrumentation must be so developed and constructed as to meetEPA guidelines for test procedureswith respect to the National PollutionDischarge Elimination System( PDES), as Robert Booth of EPA/Cincinnati reminded an AIChEmeeting session. Such instrumentation(for water) would include, for example, pH meters, ion-selective electrodemeters, and many other precise analytical instruments. Documents describing quality assurance techniquesneeded to provide valid data areavailable from the EPA. Contact theEnvironmental Monitoring and Support Laboratory in Cincinnati. Provisions for alternative test procedurescan be made in certain cases.

For the future, Booth said, instrumentation needs could encompass

• low opera tor dependence• capabilities of lower detection

limits with high degrees of reliability• capabilities of monitoring specific

organic compounds in comparativelycomplex sample matrices

• capabilities of automatically accommodating desired quality controltechniques to assure data validity.

Computer controlThe computer is a principal tool for

advancing compliance technology. C.Wells of Envirotech Operating Services (Belmont, Calif.) explained howa digital computer automaticallycontrolled activated sludge processworking at the 10.37-mgd FairfieldSuisun (Calif.) Regional Water Reclamation Plant. The computer wasused on one side of a parallel train tocontrol dissolved oxygen (DO), returnsludge density, and mixed density.

Control of the other side of the trainwas manual, with identical feed, forpurposes of comparison.

Computer control apparentlybrought about improved sludge settleability (sludge volume index, orSVI); improvement was about 40%(with manual control, the SVI was 199± 80 mL/g). DO was controlled to±0.3 mg/L by computer, and to ± 1.8mg/L in the manual system. Totalorganic carbon was 25.4 ± 16.5 mg/Lin the efnuent from computer control,and 25.5 ± 16.2 mg/ L in the efnuentfrom manual control. But the computer-controlled efnuent quality wasachieved with one-half of the manually-controlled settling volume.

The marked SVI improvement bytight computer control allowed theplant to operate with only one secondary clarifier. For the manual system,two were required. Also, computercontrol of the process allowed the useof about 18% less air for the activatedsludge process than the manual systemneeded.

The use of less air, brought aboutthrough automation of the air header,could save much electric power; electricity costs currently exceed$45 OOO/mo for the plant. Moreover,better control of filamentous organisms that impair the SV I was achievedthrough tight computer control.

Automating the bugsComing "down the pike" is a hand

book for automation of the liquid- andsolids-train biological activated sludgeprocess for achieving efnuent compliance. The handbook should appear inJune or July. To be aimed at consulting engineers and government agencies, it is being prepared for EPA byEMA, Inc. (St. Paul, Minn.), EMApresident Alan Manning told AIChEmeeting attendees.

One part of the book will cover

successful control strategies at 23wastewater treatment plants. The bookwill also show weakness in presentsystems. such as insufficient attentionoften paid to control of hydraulics. Asfor sludge drying, multiple-hearth incineration, rather than vacuum filtration will be emphasized. Manningsays that the latter process can havepoor economics, because of chemicalcosts, and control difficulties. But forincineration, automatic control mustbe very tight, and properly set up forevery aspect, such as temperaturecontrol, oxygen level, combustion zonelocation, and similar factors, or energycosts could really mount up.

To shore up certain weak points inautomated biological activated sludgesystems, Manning recommended

• an integrated control scheme tobe developed/demonstrated for theactivated sludge process

• demonstration of feasibility anddesirability of dynamic control of planthydraulics

• a management handbook forplant operation/maintenance

• development/demonstration of ameasurable filterability index, necessary for full automation of sludge dewatering processes

• better understanding, and demonstration of combustion process automation, particularly for multiplehearth incineration

• a preventive maintenance program for instrumentation.

InterrelationshipsAny technical and economic evalu

ation of a planned environmentalcontrol system, to be built to complywith regulations, must take the interrelationships of air, water, and solidwaste into account. If this is not done,at the outset of a system analysis, theresult can be makeshift solutions notconstituting a technical or economicoptimum, warns engineer JamesCommins, president of JACA Corp.(Fort Washington, Pa.).

For example, Commins cited thecase of an industrial dryer whose par-

Stone & Webster's Siegel"control only through technology"


As one ofits first major efforts,the four-agency Interagency LiaisonRegulatory Group issues its report

on 24 hazardous materials

Regulatinghazardous substances

ticulatc cmissions were controlled bya wet scrubber. Scrubber water discharged to a reeeiving stream had to betreated for pH and suspended solids.Apparently, during the original economic analysis, water regulations werenot considered. The result was a system choice whose cost-effectivenesswas not optimal.

Another example was that of theasphalt batching plant that used a wetscrubber to capture particulates in itsair stream. Because of new "zero discharge" water requirements, scrubbermakeup water was taken from thesame pond to which spent water fromthe demister was discharged. Improperdesign of that pond, and of input filters. led to the system's being out of"spec" on particulate loading. Corrective design of the water sourcebrought the system within specifications. but because of that necessity,extra costs were incurred.

These case histories served as awarning of what happens when thewater lair /solid waste interrelationships are not considered in their entirety, as they apply to an antipollutionproject. Commins recommended waysof considering the interplay of the environmental laws, and of technical/economic factors, so as to achieve themost cost-effective compliance.

How not to complyWith regard to air pollution control,

there are at least two new ways to failin compliance with EPA's regulationsevolving as a consequence of the CleanAir Act Amendments of 1977, according to Richard Siegel of SlOne &Webster Engineering Corp. (Boston,Mass.), who coordinated the programon environmental regulations andcompliance. He said that these "nonos" are use of "compliance fuel" andtall stacks.

Instead, EPA now mandates continuous emission reduction, such thatcontrol will have to be achievedthrough technology. This technologywill culminate in use of Best AvailableControl Technology (BACT), andLowest Achievable Emission Rates(LAER) for new facilities, dependingupon whether they are located in areasattaining ambient standards (BACT),or not attaining standards (LAER).LAER is a technology-forcing controllevel which does not consider economics as an object. Moreover, asgleaned from the compliance symposia, it is probably safe to say that tomeet most pollution control requirements-which may be expected togrow ever tighter-various combinations of hardware and software systems technologies will be the key. JJ


Jimmy Carter took office pledgingto eliminate waste and duplication insetting regulations, thereby increasingtheir effectiveness while decreasing theburden on the regulated industries andthe public. In the area of rcgulatorypolicies protecting the public from theuntoward consequences of hazardoussubstances, increased efficiency isparticularly important.

Carter threw out his gauntlet early.The regulatory agencies met his challenge with a vengeance.

Together whatever, ..One of the best ways to ensure

against overregulation is throughcoordinative efforts among agencieshaving similar regulatory responsibility. Letting the "government's lefthand ... [know] what the right hand isdoing," is the way OSHA's head andcurrent IRLG chairman Eula Bingham describes it.

Two of the earliest efforts in thisdirection were the Toxic SubstancesStrategy Committee (TSSC), whichhas representatives from J7 agenciesand is chaired by the Council on Environmental Quality, and the fouragency Interagency Regulatory Liaison Group (I RLG), which was formedin August 1977 by Susan King,Douglas Costle, Donald Kennedy andEula Bingham, respectively the headsof the Consumer Product Safety

Commission (CPSC), EPA, the Foodand Drug Administration (FDA) andOSHA.

Since the formation of TSSC andIRLG, the cooperative spirit has givenrise to the Interagency Toxic Substances Data Committee, the Interagency Toxic Substances TestingCommittee, the Regulatory AnalysisReview Group. the ational Toxicology Program, and the RegulatoryCouncil, to name just a few.

While cooperation may appear to berampant and, to some extent, excessive, the need is apparent. Early on, theIRLG took inventory of the projectsconccrned with toxic substances control, and found that its four membersalone had 300 ongoing projects at acost of $39 million. Three other nonregulatory HEW agencics-NC!,N IEHS. and N IOSH-had another600 projects whose total cost exceeded$95 million.

Agreement on toxicsWith this inventory of potential

duplication, and the Carter administralion's thrust to eliminate such duplicative efforts, the four agencies, onOctober II, 1977, published an interagency agreement in the FederalRegister relating to the regulation oftoxic and hazardous substances. As theIRLG, the agencies agreed to shareinformation and other resources to

CPSCs Kin/( EPA's eostle FDA's Kennedy OSHA's Bin/(ham

develop "common. consistent or compatible practices." This cooperation. itwas felt, would bring about effective.cost-effective health-protection programs.

Under this October agreemcnt.eight work groups were established.One of these groups, the RegulatoryDevelopment Work Group. chaired byHenry E. Beal of EPA. recently published "development plans" for 24hazardous materials (box) that two ormore of the agencies regulate or intendto regulate.

The document. "Hazardous Substances Summary al\d Full Development Plan:' inventories the regulatoryactivities currently in progress for 24wide-ranging toxic materials-fromacrylonitrile to substances present inwaste disposal to agricultural land. Foreach substance or group (some of thecategories are not single compounds).the report summarizes

• the agencies' statutory authorityto regulate

• the history of regulations in effeet

• the adverse biological effects• the opportunities for avoiding

connicts in standards sctting, and foreliminating duplicative efforts

• the economic ramifications ofproposed or pending rcgulations

• recommcndations for future aclion.

To call the document "developmentpia ns" is. however. an exaggera I ion.The recommendations-which TobyClark. special assistant to EPA administrator Cost Ie. acknowledges asnot being an outstanding feature of thedocument-arc in many cases vagucor nonexistent. With poor or no recommendations. can these be calleddevelopment plans"? Clark accepts thiscriticism. but emphasizes that thedocument represents the first evolutionary stage- which he terms coordination- in the regulation of ha7.ardous substances.

An evolutionary process it is. The

Reguhllory Development WorkGroup's efforts appear 10 be nuid andongoing. For example. plans have already been made to publish quarterlyupdates of the present 24 schemes.Expansion of these quarterly reportsmay also occur whenever an agencybegins regulatory action on a newhazardous material; should this occur,the other agencies would be madeaware of the new initiative through an"alert" system. which has already beenset in motion.

To ensure that the coordinative effort is self-sustaining, new regulations

AcrylonitrileArsenicAsbestosBenzeneBerylliumCadmiumCbloroform &- cblorinated

solventsTricbloroethylenePerchloroetbyleneMethylchloroform

ChlorofluorocarbonsCbromatesColte-oven emissionsDibromochloropropaneDiethylstilbestrolEthylene dibromideEthylene oxide" residuesLeadMercury & mercury compoundsNitrosaminesOzonePRBsPCBsRadiationSulfur dioxideVinyl chloride; polyvinyl chlorideWaste disposal to food-cbain lands-ee: IRlG's Hazardous SubItuceaReport

arc to describe in their prefaces howthe IRLG agencies "worked together.and the effect such joint effort has onthe regulation."

Hopcfully these joint efforts willhave the desired effect enunciated byEPA administrator Cost Ie: 'The plansaim at ... minimizing the risks associated with [the careless manufacture,usc or disposal of] these compoundswhile maximizing their benefits."

And now to the detailsCostle cites asbestos as an example.

Here he says "Our goal ... is not tohalt essential uses such as fire proofingmaterial but to ensure that these canbe done in ways that don't jeopardizepeople's health or environmentalquality."

Asbestos is a good example. A recent HEW report (1::5& T. January1979. p 15) estimates that 8-11 millionworkers have been exposed to thismineral. All four agencies have setstandards for the substance. Millionsof dollars have been spent on healtheffects research. Yet controversy stillrages over the health consequences ofingesting asbestos and asbestiform fibers: therefore. more studies are beingeond ucted. -

The asbestos "development plan"recommends closer cooperation withthe Dept. of Transportation. which hasrelevant jurisdiction under its Hazardous Materials Transportation Act,and HEW's Subcommittee to Coordinate Asbestos/ Asbestiform Research. and relevant programs withinthe Public Health Service. No otherrecommendations arc made. Conspicuously absent arc recommendationsconcerning coordinative healt h-effeelsresea rch projects.

One hazardous substance for whichall four agencies arc contemplatingregulatory action is cadmium. OSHAis planning workplace standards. andEPA is considering air-pollution controls. The CPSC, EPA and FDA recently issued a joint voluntary standard


E.panding lhe world of analytical chemistry.

Subcommittee on Environment andAtmosphere, FDA CommissionerKennedy outlined research areasneeding further scrutiny. Among theseare: the development of short-termtests for measuring neurotoxicity;methods to quantify risks; and morepredictive animal models and risk/benefit analyses.

These are areas that the IRLG orthe four agencies individually are likelyto pursue in the future. In fact, theEPA and the FDA have already established a joint laboratory in NorthCarolina to study the subtle neural andbehavioral effects of toxic materials.

Achievements to date

The four agency heads toutedIRLG's first-year achievements at thefirst interagency forum on December12, 1978. In addition to the "Hazardous Substances" document, they citedthe development of programs for -inspection referrals whereby an inspectorfrom one agency can refer possibleviolations of other laws to the pertinentagencies. Also, the four agencies haveagreed upon a joint computerized information system on toxic substancesthat will list all regulations and relevant legal decisions. The agencies arenow in the process of developing uniform health testing guidelines; the firstseven are expected to be publishedearly this year.

With the specter of deregulationhanging over their heads, the fouragencies are working very hard atmaking the IRLG effort successful. Ifsuccessful, the prospect of a legislativeveto-a concept that has reared itshead in Congress intermittently overthe last several years, and one that, inthese innationary times, is likely tofind a very favorable climate for takinghold in the 96th Congress-can bestaved off.

The fatal naw in this whole schemeof cooperation may be the zealousformation of interagency groups.What, for example, are the coordinative conduits among the IRLG, theTSSC and the Regulatory Council?Are these merely overlapping jurisdictions or compatible efforts? Hasanother layer of bureaucracy merelybeen superimposed on the once individual regulatory fiefdoms, or willthese cooperative efforts produce moregovernment efficiency?

It is still too early to answer thesequestions. For the moment, it is certainthat the regulated industries now havethe added burden of keeping a closewatch on the regulatory agencies andthe rapidly growing crop of interagency liaison groups and committees. LRE

to control the leaching of this metal(and lead) from cadmium-containingdecorations on glassware.

Here, the recommendations appearreasonable. The regulatory workgroup, it is suggested, should serve asthe informal coordinator of the variouscadmium-exposure analyses beingcarried out in the four agencies, and itshould also review waste-disposal criteria for the metal; and the implications of cadmium carcinogenicity,mutagenicity and teratogenicitydata.

The recommendations for the classof compounds labeled chloroform andchlorinated solvents are also moreforthcoming than those for asbestos.Although, even here, vagueness creepsin. To wit: "As the results of on-goingcontracts and studies come in, moremeetings should be held so that regulatory considerations can be a jointeffort."

Regulation of nitrosamines, the report uncovers, is just over the horizon.The EPA will address the nitrosamineissue in its development plan for aNational Ambient Air QualityShort-Term Standard for NitrogenDioxide; it is assessing the hazards ofpesticides containing nitrosamines, andhas already proposed a nitrosaminewater standard. The FDA and theDept. of Agriculture are consideringregulating nitrite and nitrate preservatives in cured meats; these substances, when ingested, are nitrosamine precursors in humans.

For nitrosamines, the IRLG development plan recommends that "policydecisions and statutory language [be)clarified to clearly delineate FDA andEPA responsibility in regard to nitrosamines in water." The plan urges thedevelopment and validation of analytical methods for determining nitrosamines. Most importantly, the planrecommends the pooling of information and other resources regarding thissubstance in air, water and food todetermine whether regulatory action"should be taken."

A first step

The 24 summaries should only beconsidered a first effort; in those caseswhere the recommendations are vagueor nonexistent, corrections ought to bemade in the quarterly updates. Nevertheless, despite the generally poorquality of the recommendations, thisinventory effort did make two significant contributions: it delineated theareas for cooperation and sharing ofresources, and it uncovered importantareas of research that have receivedlittle or no funding support.

In testimony before the House

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We will see you at this year's conference inCleveland, at its convention center on March 5-9.Plan to attend and hear the Pittsburgh Conference

on Analytical Chemistry and Applied Spectroscopy

Pittsburgh Conference:the environmental papers

I I.

SYMPOSIUMThe Application of High Pressure

Liquid Chromatography toEnvironmental ProblemsPractical Applications andRegulatory Considerations

arranged byP. C. Talarico,

Waters Associates, Inc.

Monday Morning, Room 235AP. C. Talarico. Presiding

8:30 (041) Keynote Address-Impact of HPLC on the Monitoring Requirements for Trace Organics- W May.U.S. Bureau of Standards9:00 (042) Uses of LC in Analyzing

Non-Volatile Organics in Waste-Efnuent-H. Wallon. University of Colorado9:30 (043) Use of HPLC in Moni

toring Trace Level Organics for ChronicToxicity-G. Wilson. E G & G BIOnomics10:00 Recess

10:20 (044) Cleanup and Concentration of Em'ironmental Samples forHPLC-C. Creed. LCS Laboratories. A.Wolkoff

10:40 (045) Determination of Polynuclear Aromatics in Industrial HygieneSamples by High Performance LiquidCbromatography-G. Gibson. U. S. Department of Labor

11 :20 (046) Determination of SelectedCarcinogens by HPLC-W Hendricks.U.S. Department of Labor-OSHA

Monday Afternoon, Room 235AC. Creed. Presiding

1:30 (131) Monitoring Waste Waterror Munitions by HPLC-D. Hellon.Midwest Research Institute2:00 (132) HPLC Determination of

Pesticides in Water- T. Steinheimer. U.S.Geological Survey

2:30 (133) Analysis of IndustrialWaste Waters by HPLC-R. Hites.Massachusetts Institute of Technology3:00 Recess

3:50 (134) Use of HPLC to Isolatea Mutagen from a Plant Waste Efnuent-K. Carlberg. NEICjUSEPA, R.H. Laidlaw

4:20 (135) Analysis of Pesticides inFish in HPLC-J. Moore. Gulf BreezeERL

Environmental AnalysisWater Pollution I

Monday Morning, Room 235BC. E. Gonter. PresidingNUS Corporation8:30 (047) Organic Compound

Characterization of Wastewater for anEnvironmental Assessment Study-M. F.Marcus, H. H. Miller. P. H. Cramer,Midwest Research Institute8:50 (048) Determination of Arsenic

in Natural Waters-W A. Richards, M.A. Thomas, S. R. Goode, University ofSouth Carolina

9: I 0 (049) Metal Transport: Role ofNaturally Occurring Organic Substancesin Aqueous Systems-Co A. Crumm, O. T.Zajicek. University of Massachusetts9:30 (050) The Analysis of Trace

Water-Soluble Polymers in Waste Waterby HPLC-A. C. Hayman. G. Dallas, DuPont Instruments9:50 (051) Some Improvements in

Analysis of Industrial Wastes for PriorityPollutants- W Averill. J. E. Purcell.Perkin-Elmer Corporation10: I0 Recess10:20 (052) Analysis of the ConsentDecree PAHs in Water-K. Ogan, E.Katz. W. Slavin, The Perkin-Elmer Corporation10:40 (053) D. C. Argon PlasmaEmission Spectrometry Applied to Environmental Water Samples-M. S. Hendrick. D. Eastwood. U.S. Coast GuardResearch and Development CenterII :00 (054) The ICP-ES Analysis ofNURE Surface Waters of the RockyMountain States and Alaska-C. T. Apel.B. A. Palmer, D. V. Duchane, L. B. Cox, J.V. Pena. A. D. Hues, D. L. Gallimore. LosAlamos Scientific LaboratoryII :20 (055) Determination of pH inSoils and Specific Conductance in Wastewater using an Automated ISE System-:-A.Bucca/uri. J. Potts. R. B. Roy, TechmconIndustrial SystemsII :40 (056) Oxidative Methods forMinimizing Reagent Blank in the Determination of Low-Range Oxygen De-

The rugged, portable MIRAN-101Specific Vapor Analyzer gives youplenty of advance warning whenhighly toxic ethylene oxide fromyour sterilizer system is buildingup in the ambient air.

You get direct readout 01 ethyleneoxide concentrations with a dualrange capacity of 0-100 ppm and0-1.000 ppm.

The MIRAN-1 01 is calibrated atthe factory to monitor ethylene oxideor anyone of hundreds of infraredabsorbing gases. You can use itas a portable instrument for leakchecking and area mapping, or itcan be permanently located forcontinuous monitoring.

Why risk over-exposure toethylene oxide? Get completefactsontheMIRAN-l0ltoday.MIRAN IS a Trademark 01 The Foxboro Company

Foxboro AnalyticalA Division of The Foxboro Company

Wilks Infrared CenterPOBox 449South Norwalk. CT 06856(203) 853·1616

fOXBORO

See it at the PittsburghConference. Booths 822-929



mand-L. Stookey, B. Klein, ManchesterLaboratories, Inc.

Monday Afternoon, Room 2358A. Pollock, PresidingHarshaw Chemical Company

1:30 (J 36) Reduction of Foaming inthe Analysis of Volatile Organics in Industrial Effluent Waters when using Purgeand Trap GCTechniques-B. N. Colby, M.E. Rose, Systems, Science and Software

1:50 (137) The Ultratrace Determination of Thallium In Natural Waters byDifferential Pulse Anodic Stripping Voltammetric Techniques-J. E. Bonelli, H.E. Taylor and R. K. Skogerboe, U. S.Geological Survey

2: I0 (138) Isolation of PolynuclearAromatic Hydrocarbons from Water byAdsorption on Membrane Filters-F.Amore, Illinois State Water Survey

2:30 (139) Analytical ProblemsEncountered During the Restoration of aMercury-Contaminated Public WaterSupply-J. C. Cooper, C. Hackbarth, C.M. Hellwig, D. L. Venezky, U.S. NavalResearch Laboratory

2:50 (140) An Automatic Samplerfor Trace Organics in Water-J. D. Pope,Jr., A. W. Garrison, U.S. EnvironmentalProtection Agency

3:10 Recess3:20 (141) A Statistical Evaluation

of the DR-ELj4 Portable WastewaterLaboratory vs. Standard Methods-B.Culver, S. Schuler, D. Miller, C. Gibbs,Hach Chemical Company3:40 (142) Spectrophotometric De

termination of Phenols by Their Oxidationwith Sodium Metaperiodate-L. R. Sher·man, University of Akron

4:00 (143) High-Pressure LiquidChromatography of Nitrophenols-A. F.Haeberer, U.S. Environmental ProtectionAgency

4:20 (144) Determination of Acrylonitrile in Water at the PP8 Level-J.Going, K. Thomas, Midwest ResearchInstitute4:40 (145) Sample Preparation for

Environmental Analysis-D. R. Lorenz, H.Rodriguez, Waters Associates

Tuesday. March 6

Tuesday Morning, Room 2358J. Frohliger, PresidingUniversity of Pittsburgh

8:30 (222) A Portable PlasmaEmission System for the Determination ofMercury and Mercury Species in Air-D.D. Gay, U.S. EPA, K. O. Wirtz, L. C.Fortmann, H. L. Kelley, C. W. Frank8:50 (223) Statistical Studies of

1975-1977 Air Pollution and WeatherData for the Phoenix, Arizona Metropolitan Area-M. L. Parsons, Arizona StateUniversity, L. Y. Hara, D. D. Prall


9: J0 (224) Analysis of Air, StackGas, and Solution Particulates by Secondary Target Energy-Dispersive X-RayFluorescence-D. J. Kalnicky, ExxonResearch Engineering Company9:30 (225) Determining Trace

Quantities of Acrylonitrile in Air-R. L.Campbell, D. R. Marrs, N. W. Standish,Vistron Chemical Company

9:50 (226) Preparation and Evaluation of Silica and Asbestos Reference Materials for Pollution Studies-J. A.Mackey. ational Bureau of Standards,O. Menis, P. D. Garn10: I0 Recess

10:20 (227) Polymer Combustion:Analysis of Volatile Smoke Products by GCand GCjMS-R. O. Gardner, R. F.Browner, Georgia Institute of Technology

10:40 (228) Experimental Improvements in Chromatographic Analysis ofAmbient Level Hydrocarbons-R. Denyszyn, Scott Specialty Gases, J. M.Harden, D. L. HardisonI 1:00 (229) Quantitative Determination of Sulfur Gases by Gas Chromatography-E. R. Kebbekus, MathesonII :20 (230) The Evaluation of PPMLevel Sulfur Gases in Nz and Air Containedin High Pressure Aluminum Cylinders-F.J. Kramer. Jr.. S. G. Wechter, Airco Industrial Gases

II :40 (231) New Digitally ControlledAPI Mass Spectrometer Based SystemN. M. Reid, J. A. Buckley, J. B. French, C.Poon, Sciex, "I nco

Tuesday Afternoon, Room 235BH. Ryba, PresidingAlcoa Laboratories

1:30 (308) Determination of Ammonia in the Atmosphere by MultipleWavelength Absorption Spectrometry-J.M. Shekiro. Jr., K. R. O'Keefe. ColoradoState University

1:50 (309) Application of a TrappingConcentratorJGC System to the TraceAnalysis of Volatile Organics in Polymerand Air-E. J. Levy, Chemical Data Systems, Inc.

2:10 (310) A Simple TenaxCollectorjlnjector for Atmospheric Sampling-F.H. Jarke. lIT, Research Institute, S. Cotton, A. Dravnieks

2:30 (311) The Laboratory Environment-Air Pollution Control-J. Librizzi, Heat Systems-Ultrasonics, Inc.

2:50 (312) Surface Analysis Techniques as Probes of Metal Speciation inEnvironmental Samples-R. W. Lin/On, M.Bednar, M. E. Farmer, University of NorthCarolina

3:10 Recess3:20 (313) A Microcomputer Con

trolled Infrared Spectrometer for AmbientAir Analysis-J. G. Kocak. D. K. Wilks,Foxboro Analytical3:40 (314) Standards for Quantita

tive Gas Analysis-£. R. Kebbekus. D. D.Murray, Matheson

....

4:00 (315) Computerized Display ofChromatographic Data for EnvironmentalAnalyses-R. E. Clemell/, F. W. KarasekUniversity of Waterloo '

4:20 (316) A Microprocessor Controlled Process Gas ChromatographicSystem for Area Monitoring-J. M.Clemons. E. Leaseburge, Bendix Environmental and Process Instrument Division

4:40 (317) PhotoacousticSpectra of Organic Compounds on CoalFly-Ash- T. Mauney, D. F. S. atusch,Colorado State University

Wednesday Morning, Room 235AD. H. Freeman, Presiding

8:30 Introduction to the Symposium-D. H. Freel/IOn

8:35 (383) Organics in the Environment: Statistical Sampling and Instrumental Analysis-H. S. Hertz, ationalBureau of Standards

9:20 (384) Implications of Transportand Transformation for EnvironmentalPollutant Analysis-G. L. Baughman.Environmental Research Laboratory10:05 Recess10:20 (385) Strategies for ItratraceAnalysis of Prevalent Environmental Organic Contaminants-c. S. Giam. TexasA & M University

10:45 (386) Methodless Methodology-Strategy for Alkyl Phthalate Measurement in Marine Sediments-D. H.Freeman. J. C. Peterson, University ofMarylandI I: I0 (387) Nonvolatile Organic Impurities in Wastewater by Liquid Chromatography-H. F. Wallon. University ofColorado

II :35 (388) Aromatic HydrocarbonBiogeochemistry in a Model EcoSystem-N. M. Frew. A. C. Davis. K. Tjessem, J. W. Farrington, Woods HoleOceanographic Institution

Wednesday Morning, Room 235BA. J. Kat'oulakis. PresidingALKA V Analytical Laboratories. Inc.

8:30 (389) Analysis for SelectedToxic and Carcinogenic Organic Vapors inAmbient Air-J. W. Bo::elli, J. Kemp. J.LaRegina. B. Kebbekus, ew Jersey Institute of Technology

8:50 (390) Evaluation of Sorbentsfor Trapping of Organic Vapors from theAmbient Atmosphere-B. Kebbekus. R.Vaccaro. J. W. Bozzelli. ew Jersey Institute of Technology

9:10 (391) Chemical Characterization of Trace Elements in Ashes from Refuse Fueled Processes-G. M. Trischan,Midwest Research Institute9:30 (392) Analysis of Coal Lique

faction Products by MIKES-D. Zakett,V. M. Shaddock, R. G. Cooks, PurdueUniversity9:50 (393) Sampling and Analyzing

Techniques of Air Bag InOator Effluents-B. M. Joshi, E. L. Stokes, FordMotor Company10: I0 Recess10:20 (394) Determination of VinylChloride Monomer in the Ambient Air NearPoint Source Emissions-J. L. Lindgren.G. Speller, Texas Air Control Board10:40 (395) Analysis of AmbientParticulate Matter using a Fourier Transform Infrared Spectroscopic TechniqueK. H. Shafer, Battelle Columbus Laboratories, W. M. Henry, R. J. Jakobsen, R.BurtonII :00 (396) Sample Preparation in theDetermination of Free Crystalline Silica inRespirable Oust from Steelmaking Environments-a. P. Bhargava. A. S. Alexiou,H. Meilach, W. G. Hines, Steel Companyof Canada11:20 (397) Development of a PurgingTechnique for the Determination of VolatileOrganic Pollutants in Biological Matrices-M. D. Erickson. L. C. Michael, S. P.Parks, J. L. Barclay, E. D. Pellizzari, Research Triangle InstituteII :40 (398) Application of ProtonInduced X-Ray Analysis for Aerosol in theAtmosphere-S. Tanaka, Keio University,R. Chiba, H. Kutsuna, Y. Osada, Y.Hashimoto

Wednesday Afternoon, Room 235AR. W. Freedman. Presiding

1:30 (470) ICAP Analysis of Environmental Samples-Successes and Failures-F. N. Abercombie. D. J. Koop, R. B.Cruz, Barringer Research Ltd.

2: 15 (471) Inductively CoupledPlasma Atomic Emission SpectroscopyQuestions Often Asked and Their Answers-V. A. Fassel. Iowa State University

3:00 Recess3:20 (472) Practical Application of

ICAP to Environmental Analysis-C. D.Carr. Applied Research Laboratories

4: I0 (473) Analytical Aspects ofICAP in Water Quality Control-A. F.Ward. Jarrell-Ash Division

Wednesday Afternoon, Room 235BJ. P. McKaveney, PresidingOccidental Research Corporation

1:30 (474) The Determination ofTracer Compounds by Liquid ScintillationCounting after Preparation of the Samplesby Oxidation of the Host Matrix-J. E.Caton, Oak Ridge National Laboratory,M. P. Maskarinec, G. M. Henderson, R.W. Harvey, M. R. Guerin, Z. K. Barnes

1:50 (475) Some Limitations in theDetermination of Labile Species by AnodicStripping Voltammetry-P. M. Figura. B.McDuffie, State University of New Yorkat Binghamton

2:10 (476) Time Resolved SolventLeaching for Surface Characterization ofParticles-M. D. M. Tucker, Universityof Illinois, D. F. S. Natusch

2:30 (477) GC-MS Analysis ofVolatile Organics from Atmospheres Impacted by the Amoco Cadiz Oil Spill-B. J.Dowty. J. W. Brown, F. N. Stone, J. Lake,J. L. Laseter, University of New Orleans

2:50 (478) Determination of SeveralPolyaromatic Hydrocarbons at SelectedSites in Texas-J. L. Lindgren. Texas AirControl Board, H. J. Krauss, M. A. Fox

3: I 0 Recess3:20 (479) Determination of Poly

aromatic Hydrocarbons not Collected byParticulate Filter Media-J. L. Lindgren.Texas Air Control Board, H. J. Krauss, M.A. Fox

3:40 (480) Partial Chemical Speciation Techniques for Aquatic HumicMetal Complexes-D. S. Chase. J. D.Ingle, Jr., Oregon State University4:00 (481) Determination of Fly Ash

in Biological Tissue from Animals Exposedto Coal Combustion Fly Ash-S. H.Weissman. L. C. Griffis, R. F. Henderson,Lovelace Biomedical and EnvironmentalResearch Institute4:20 (482) Determination of Total

N-nitrosamines in Cutting Oils-R. D.Cox. C. W. Frank, University of Iowa

4:40 (483) Determination of Nitrateand Nitrite at the Parts Per BillionLevel-R. D. Cox. University of Iowa

Thursday Morning, Room 239A. P. Bentz. Presiding

8:30 (527) Artificial Oil WeatheringTeehniques-C. P. Anderson, Universityof Connecticut, T. J. Killeen, J. B. Taft, A.P. Bentz8:50 (528) Interlaboratory

Comparison of Environmental AnalysesAssociated with Increased Energy Production-F. R. Gllellther. H. S. Hertz, L.R. Hilpert, W. E. May, S. A. Wise, J. M.Brown, S. N. Chesler, National Bureau ofStandards

9: I0 (529) Laser-Excited MatrixIsolation Molecular Fluorescence Spec-

VI W _Iii ••.,

The highly-accurate MIRAN-1APortable Gas Analyzer catcheseven the most subtle increasesin toxic gases and vapors. 'It givesyou direct readout of concentrationsas small of 0.2 part-per-million, withan upper range in percents.

You'll spot benzene build-upquickly, plus have the capabilityto detect hundreds of otherpotentially-hazardous gasesand vapors.

For area mapping, leak detectionand monitoring of more than onetoxic gas or vapor, the MIRAN-1A isideal. Get complete details today.

MIRAN is a Trademark of The Foxl:x>ro Company

Foxboro AnalyticalA Division of The Foxboro Company

Wilks Infrared CenterP.O. Box 449South Norwalk, CT 06856(203) 853-1616

fOXBORO

See it at the PittsburghConference, Booths 822-929



trometry of Polycyclic Organic Compounds-E. L. Wehry. R. B. Dickinson, Jr.,R. R. Gore, University of Tennessee

9:30 (530) Investigation of the Useof Molecular Fluorescence for Identification of Hazardous Materials-L. P. Giering. J. T. Brownrigg, Baird Corporation

9:50 Recess

10:00 (531) GPC Enrichment andCarbon Chromatographic Fractionation ofHydrocarbons and Other EnvironmentalContaminants-J. D. Pelly. D. L. Stalling,L. M. Smith, Columbia National FisheriesResearch Laboratory10:20 (532) Problems with theChemical Analysis of Marine Sediments-F. E. Franklin. J. Borges, V.Dunning, C. W. Brown. University ofRhode Island

10:40 (533) A Facile Method for theDetermination of Trace(sub-ppm) Hexamethylenediamine in Water-J. Hanrahan,Allied Chemical Corporation

11:00 (534) Detection and Determination of Acetohydroxamic Acid in Industrial Wastewater-D. Richton. AlliedChemical Corporation

11:20 (535) Infrared Spectrophotometric Determination of NeopentylesterLubricating Oils in Water-G. J. GOIIfried. Biospheries, Inc., T. S. Yu, D. G.Shaheen

Environmental papers in othersessions for the seriousenvironmental watcher*

Monda), March 5Room BR9:30 (064) Determination of Lead

in Environmental Water Samples usingFlameless Atomic Absorption Spectrophotometry-R. J. Fal/st, Calgon Corporation

Room BR10:20 (066) Determination of TotalPhosphorus in Industrial Process Watersby Flameless Atomic Absorption-E. L.Henn. Calgon Corporation

Room 239I 1:00 (018) A ew Fully IntegratedGC/MS/DS System-M. S. Story, D.M. Taylor, T. R. Stevens, FinniganCorporation

Room MHII :00 (078) A New Glass CapillaryGas Chromatograph for the AnalyticalNeeds of Tomorrow- T. A. Rooney. R.R. Freeman, Hewlett-Packard Company

Room MHII :20 (079) Designing a NewChromatograph for Tomorrow's Applications-L. Mikkelsen, M. Murphy,Hewlett-Packard CompanyMonday afternoon

Room MH2: I0 (164) Industrial Hygiene Air

Samples Analysis-Improved ResultsThrough Automation sing Glass Capillary Columns and a Multi-Channel Data

• LT is the Link Theatre, MU the Music Hall, eRR. theClub Room B. and DR. the:: Ballroom of the ConvcnllonCenter.


System-R. C. Domingo. J. W. Bailly, D.R. Brezinski, DeSoto, Inc.

Room 3A2:50 (115) A Coupled

HPLC/GC System: Instrumentation andAutomation-S. P. Cram. A. C. BrownIII, E. Freitas, R. E. Majors, E. L.Johnson, Varian Instrument Division

Room 3A3:20 (I 16) A Coupled

HPLC/GC System: Applications-R. E.Majors, E. L. Johnson, S. P. Cram, A. C.Brown III, E. Freitas, Varian InstrumentDivision

Room LT3:25 (149) Application of Ion

Chromatography to the Analysis of Atmospheric Pollutants-J. D. Ml/lik.United States Environmental ProtectionAgency

Room BR4:20 (160) Evaluation of Simulta

neous Multielement Atomic Absorption-Electrothermal AtomizationAnalysis Applied to Natural Water Matrices-R. G. Rowley. P. R. Beaulieu, J.L. Maglaty, K. R. O'Keefe, ColoradoState University

Tuesday, March 6

Room BR8:50 (239) The Thermal Environ

ment of Furnaces of the Massmann Design-So Myers, D. C. Manning. F. J.Fernandez, Perkin-Elmer Corporation

Room MH10: 15 (250) EnvironmentalAnalysis with Glass Capillary Columns- W. Bertsch, University of Alabama

Room BR10:20 (243) Comparison of Proton-Induced X-Ray Emission (PIXE) withAAS for the Determination of Acid Leachable Trace Metals in Marine Sediments-G. C. Gram. R. K. Jolly, D. C.Buckle, The College of William andMary

Room 235A11:00 (219) Direct Monitoring ofAirborne Heavy Metal by Air PlasmaSpectrometry-So Hanamllra, ationalMeasurcment Laboratory

Room 205II :20 (190) Laser OptoacousticDetection of NOz in a Flow System-A.Fried, National Center for AtmosphericResearch. D. H. Stedman

Tuesday afternoon

Room 235A1:30 (297) Ion Chromatography

Coupled with Ion Exclusion (IC/IE): Instrumentation and Applications- W.Rich, F. C. Smith. Jr., L. McNeill, Dionex Corpora t ion

Room 235A2: I0 (299) Application of Ion

Chromatography to Analysis of IndustrialProcess Waters-J. A. Rawa, CalgonCorpora tion

Room LT2:25 (319) Utilizing a Micropro

cessor in a Dedicated Analyticallnstrument-c. J. Sitek alld R. B. Edwards.LECO Corporation

Room 235A2:50 (30 I) Anion Analysis by

HPLC-K. Harrison, The SeparationsGroup, D. Burge

Room 2392:50 (271) Surface Analysis of

Particulates-C. J. Powell. T. Jaeh.

ational Bureau of Standards

Room LT3:30 (320) Applying a Micropro

cessor to Multicomponent InfraredAnalysis-P. Wilks, Wilks-FoxboroAnalytical

Room MH3: 15 (334) Screening for Priority

Pollutants in Industrial Waste Waters- T. Sabatino. Rutgers University

Room 2403:40 (258) Low Level Nitrogen

Analysis with a New Elemental AnaIyzer-R. F. ellimo. Perkin-ElmerCorporation

Room CRB3:40 (293) The Analysis of Some

Waste Lubricating and Residual Fuel Oilsby High Performance Liquid Chromatography-J. M. Brown, W. E. May,National Bureau of StandardsRoom MH

4:35 (337) Column Selection forPesticide and PCB Analyses in WaterAdvantages and Pitfalls-F. Onl/ska.Canadian National Water Research Institute

Wednesday, March 7Room 2409: I 0 (340) Magnetic Resonance

and Infrared Spectral Studies of Structural Changes during Coal Liquefaction-M. R. NOllgh. H. L. Relcofsky, T.A. Link. D. H. Finselh, .S. Departmentof Energy

Room 2059: 10 (350) Application of an In

ductively Coupled Plasma/Direct Reading Polychromator to the 1ultielementAnalysis of Stream Sediment Extracts-G. F. Larson, R. W. Morrow. L.E. White, Union Carbide Corporation- uclear Division

9:30 (351) Sequential Determination of 60 Elements in Geochemical andEnvironmental Matrices by InductivelyCoupled Plasma-Atomic Emission Spectrometry-M. A. Floyd. A. P. D'Silva, V.A. FasseI, M. Tschetter, Iowa StateUniversity

Room 3A9:30 (366) Identification and De

termination of Minerals in Whole Coal byDiffuse Renectance Infrared Spectrometry-M. P. Fuller, P. R. Griffiths, OhioUniversity

Room BRI 1:40 (418) The Fate of TraceMetals in a Batch Type Coal GasificationUnit-Po M. Grohse, S. K. GangwaI, D.E. Wagoner, Research Triangle Institute

Wl'dnesday afternoon

Room 2052:10 (436) Total Sulfur in Hydro

carbons h)' Oxidative Microcoulometry:

10 ppb to 10%-R. T. Moore, Envirotcch, P. Clinton, V. Bargcr

Room 2052:50 (438) Trace and Minor Ele

ment Analyses of Liquefaction ProductsFrom West Virginia Coal-R. G. Lell, R.R. DcSantis, J. W. Adkins, R. A. Hahn,U.S. Department or Energy

Room CRB2:50 (464) A Semi-Automatic

Standard Addition Method for the Analysis of Pesticide Formulations- R. J.Obremski, J. Bernard, J. W. Mohar,Bcckman Instruments, Inc.Room 240

3:20 (429) A Resonance RamanMethod for the Rapid Detection andIdentification of Bacteria in Water- WF. Howard, W. H. Nelson, J. Spcrry,University or Rhode Island

Room 2053:40 (440) Determination of Total

Organic Carbon (TOC) in Sea Water byUV Promoted Persulfate Oxidation- y.Takahashi, Envirotech

Room 2054:20 (442) Total Nitrogen in Hy

drocarbons by Automated Chemiluminescence Detection System: 20 ppb toI%-J. M. Castro, R. T. Moore, EnvirotcchRoom 2054:40 (443) PPB Sulphate Deter

mination by MECA-VAP-S. L. Bogdanski, A. Townshend, I. S. A. Shakir,University or BirminghamRoom 240

4:40 (433) Use of the MolecularMicroprobe for Analysis of Sulfur Compounds in Coal and for Monitoring of P-NJunctions-F. Adar, R. Grayzel, D.Landon, Instruments SA, Inc.

Thursday, March 8Room 240

8:50 (508) Analysis of SynfuelWaste Water by Second-DerivativeSynchronous Luminescence Spectroscopy- T. Vo-Dinh, R. B. Gammage, A.R. Hawthorne, Oak Ridge NationalLaboratoryRoom BR

8:50 (576) Data Reduction forGCjMS Analyses of Water and WaterExtracts for EPA's Priority Pollutants-J. M. Rombough, NUS CorporationRoom 205

9:30 (520) ElectrochemicalDetection of Mercury-D. D. Nygaard,Bates CollcgcRoom BR10:20 (580) Application of CapillaryColumn GCjMS to Water PollutantAnalysis-E. M. Chait, T. A. Blazer, E.I. du Pont dc Nemours & Co.

Room 20510:40 (523) Advances in Ion Selective Electrodes Technology-J. Driscoll,E. Atwood, J. Fowler, HNU Systems,Inc.Room 235A10:40 (562) Nebulizers for ICPOESand AAS: Aerosol Characterization-J.W Novak, R. F. Browncr, Georgia Institute or Technology

Room 235BII :30 (570) Development of an Instrument for Continuous, Automated andLow-Cost Monitoring of the OrganicLoading in Water-W J. Cooper, U.S.Army Medical Bioengineering R&DLab.

Room 3AII :40 (545) Applications of a NewInfrared Spectrophotometer with Microprocessor Control-I. A. Steer, R. C.J. Osland, Pyc Unicam Ltd.

Thursday afternoon

Room BR2:30 (665) Chemical Compound

Glass Separation in Shale Oil Analysis-Po C. Uden, F. P. DiSanzo, S.Siggia, Univcrsity or Massachusetts

Room 235B2:30 (653) An Evaluation of Con

tinuous Monitoring Procedures for Cyanide-B. Fleet. S. das Gupta, HSA Reactors Ltd.

Room BR2:50 (666) Applications of High

Resolution Glass Capillary Gas Chromatography in Analysis of SyntheticFuels From Coal-C. M. White, U.S.Dcpartment or Energy, D. L. Vassilaros,M. L. LecRoom 235B

3:40 (656) A New On-Line Colorimetric Analyzer for Water and Wastewater-R. Clemens, J. Chisholm, C.Hach, P. Larson, D. Schoonovcr, HachChemical Company

Friday, March 9Room 235A8:30 (722) The Du Pont "Prep

I"-A Rapid Automatic Sample Processor for LCjGC AnalysiS-A. P.Goldberg, G. Dallas, Du Pont Instruments

Room LT8:50 (713) The Evaluation of a

Low Cost Computerized ICAP DirectReading Spectrometer for the RoutineAnalysis of Ecological Samples-J. P.Malley, V. J. Luciano, L. F. Marciello, A.F. Ward, Jarrell-Ash DivisionRoom 205

9:30 (695) Analysis of Coal andCoal Ash by Energy Dispersive X-RayFluorescence-B. D. Wheeler, N. Jacobus, EG&G ORTEC. Inc.

Room 20510:40 (698) Standardless Determination of Some Heavy Metals in Airborne Particulate Matters by X-RayFluorescence Spectrometry-K. Ohno,National Research Institute ror MctalsRoom 24010:40 (688) ASTM Method ofTesting for Determining the ArrheniusKinetic Constants for the Screening ofPotentially Hazardous Materials- R. B.Cassel, W. P. Brennan, R. L. Fyans, A.P. Gray, Perkin-Elmer Corporation

Room 240I 1:00 (689) Measurement of Critical Thermal Stability Parameters forPotentially Hazardous Materials-R. L.Blaine. P. S. Gill, Du Pont Instruments

With the MIRAN-1A Gas Analyzer,you will be able to conduct, withconfidence, area mapping and leakdetection tests for formaldehyde,along with hundreds of other potentially-toxic materials. The instrumentcontinuously samples and measures vapor concentrations and candetect formaldehyde at the 0.1 ppmlevel.

Get laboratory accuracy - andindustrial ruggedness -in aportable gas analyzer. Contact us todayfor complete details.MIRAN Isa Trademark of The FoxooroCompany

Foxboro AnalyticalADivision of The Foxboro CompanyWilks tnfrared CenterPO. Box 449South Norwalk, CT 06856(203) 853-1616

RJXBORO

See it at the PittsburghConference, Booths 822-929



=~__I~W~I__-------==o:

Economic penalties in CAAA

Michael R. DelandERT. Concord, MA

The Clean Air Act Amendments of1977 (CAAA) substantially increasedthe enforcement powers of EPA andthe States by adding two new types ofeconomic penalties. The two arecourt-imposed "civil penalties," whichmay be assessed for violations goingback to Aug. 7, 1977, and "noncompliance penalties," which will commence to run for violations after Aug.7,1979., Both of these new sanctions reflectCongressional frustration with continuing delays in the attainment of thehealth-related standards. Two civilpenalty provisions are an extremelypowerful new tool in the regulatoryarsenal, particularly when complemented by the noncompliance penalties, which are triggered automatically,and over which 'EPA and the Stateshave very' little discretion.

Anew testThe civil penalty provision supple

ments the criminal penalty sanctionsfor "knowing and willful" violations.(The criminal provision was toughened,to make "any responsible corporateofficer" personally liable.) The newcivil penalties provide much moreleverage for enforcement officials because civil liability need only be provenby a "preponderance of the evidence,"a substantially lighter burden than thecriminal standard of "beyond a reasonable doubt." Additionally,"knowledge" or "willfulness" are not'elements of the civil provision, so onlythe occurrence of the violation must beproved.

The premise of the civil penaltyprovision is that it is unfair for a rela-

tively small number of sources to continue to violate when the majority havemade the effort and capital outlay tocomply. The amount of the penalty (upto $25 000 per day per violation) maybe determined by considering the sizeof the business, the economic impact ofthe penalty on the business and theseriousness of the violation. It is intended to be used as a punitive sanctionas well as an economic incentive forcompliance.

The calculation of the amount of thecivil penalty is highly stru<,tured. Notonly are specific formulas provided,but the amount of the penalty to besought in each case is reviewed by apanel of top officials from EPA, theDepartment of Justice, and some stateagencies. The amount approved by thispanel is a minimum, and the U.S. Attorneys and others negotiating settlements of these cases are instructed notto settle for less than the approvedamount.

For noncomplianceTbe other new economic sanction

requires a mandatory assessment of"noncompliance penalties" againstnearly every violating source of airpollution after Aug. 7, 1979. Similarto the civil penalty promise, this penalty is designed to eliminate any fi·nancial incentive to defer pollutioncontrol investments. There are only alimited number of exemptions fromthese automatic penalties (for example, for innovative technology or insignificant violations). EPA draftregulations describe in detail themethod for calculating the amount ofthe penalty and the procedures governing the federal and state systems ofpenalty assessment and collection,

The basic approach of the proposedpenalty calculation formula is to determine the present value of the pollution control investments that shouldhave been made and the present valueof the investments that are being orwill be made. and to take the difference between the two as the source'seconomic benefit of not timelycomplying with the pollution controlregulations. Obviously, if major con-

trol equipment such as scrubbers isrequired, the penalties will be substantial.

The details for administering thenoncompliance penalty system mayvary in those states where the stateagency has submitted and receivedapproval for a plan for assessing andcollecting these penalties. Such plansmust fulfill the requirements of EPA'sdraft regu lations.

Calculation of penaltyThe source owner or operator must

calculate the penalty owed and establish a payment schedule. If the sourcefails to calculate the penalty, the enforcement agency may bire an outsidecontractor to do the calculation andadd the contractor's fee to the amountof the penalty. The enforcementagency must, within 30 days, reviewthe calculation and either accept it,request more information or recalculate it. The source may request abearing to challenge any recalculation.

The regulations sharply restrict botbthe subjects that can be raised in apetition for a hearing and the discretion of the hearing officer. Only twodefenses against assessment of a penalty may be allowed in a petition for ahearing: the violation did not occur, orthe source is eligible for an exemption(or both).

The regulations envision a fastpaced and simple hearing procedure,with final disposition of the case within90 days of receipt of a petition. Giventhe severe economic consequences ofthese automatic penalty provisions, thecalculation formula, and other crucialaspects, should be carefully scrutinizedand comments submitted before theregulations are finalized.

Once the penalties start to run onAug. 7, 1979, very little flexibility willremain with the regulatory agencies.The Amendments provide that civilpenalties can be assessed in addition tothe mandatory noncompliance penalties. Whether individually or in tandem, these new economic sanctionssubstantially increase the incentives tocomply with the Act.

"'~i),HUJ~l IIJOJn,<Jldj.1,1~ inll Volume13,Number2.February1979 155

Focusoncll1l11neAn international gathering of experts, the first World Climate Conference,meets in Geneva, Switzerland, from February 12-23 to assess and integratecurrent knowledge ofclimate with knowledge from other disciplines which,in combination with climate, affect human activities and the environment

156 Environmental Science & Technology 0013-936XI79/0913-0156$01.00/0 © 1979 American Chemical Society

F. Kenneth HareInstitute/or Environmental Studies

University 0/ TorontoToronto. Ontario M5S IA4

The 1970s may well go down inhistory as a decade when climate became a major destabilizing factor inthe world economy. In no previousdecade, except the 1930s, was as muchattention given to climatic anomaliesand their impact on mankind. The1930s saw severe drought in manycrop-producing areas, and there wasconsiderable damage to soils. But theworld's demand for food was thenmuch smaller, in part because thepopulation was only half of what it isnow and, in part, because of poverty.Yet, in the midst of crop failures andbread-lines, we had surplus supplies.

In the 1970s it has been different.The world is now richer and morepopulous. Large populations lie at themargin of self-sufliciency even in goodclimatic years. And the world graintrade is readily upset by quite smallclimatic differences, even thoughproduction from year-to-year varies byless than I% on either side of the upward trend observed since 1950.

Politicians, scientists respondMany politicians have become re

ceptive to the idea that world actionmay be needed to combat the impactof hostile climate. In Africa this viewis almost unanimous. The same attitude prevails in the central and westernstates and provinces of North America, where the specter of drought hasonce again shown itself. Along withbumper crops, the Soviet Union hasalso had two disastrous growing seasons-1972 and 1975-in this decade.

Faced with predictions in the mediathat events like these periodic droughtsare the forerunners of a lasting shifttoward worse conditions, the politicalworld has had to take account of theclimatic problem.

The scientific and technical worldhas not been slow to respond. Thismonth, the World MeteorologicalOrganization (WMO, a UN agency),in conjunction with several other worldbodies, is to stage the first World Climate Conference (WCC). This conference will, it is hoped, draw up a planof action for a World Climate Program(WCP), to which WMO is alreadycommitted in principle. WMO has anexcellent record in organizing and executing world research and observational programs, so these meteorological ventures are likely to succeed.

But they will be new and strange

exercises for a profession-meteorology and climatology-structured, asit is, on the physical sciences, chienyphysics, mathematics and chemistry.Meteorologists are comfortable withtackling problems of climatic research.And there will be a large researchcomponent in WCP, which will bejointly carried out, as was the GlobalAtmospheric Research Program, withthe International Council of ScientificUnions (lCSU), which brings togetherthe various nongovernmental scientificunions.

However, when it comes to the impact of climate on humanity, meteorologists and climatologists are on lessfamiliar ground. And the social scientists to whom they might turn arenot as internationally organized as arethe members of ICSU.

The idea of a conference was deliberated at the 1975 U.N. Conferenceon Food, where hostile climate wasseen as a serious threat to future foodsupplies. Quite independently, theWMO Executive Committee's Panelof Experts on Climatic Change putforward similar views. In January1974, and again in June 1975, theRockefeller Foundation also held small

"This Conference is a response bythe WMO and other U. . agenciesto the growing worldwide concernsabout the impacts of natural variations in climate upon world foodproduction, energy supply and demand, water resources, land use, andother aspects of society. It is also aresponse to the ominous indicationsthat man, through his own activities,may cause significant changes inclimate. There are now sufficientindications that some of these potential changes, such as those thatmight result from increased amountsof atmospheric carbon dioxide, couldhave a pervasive impact upon thenations of the world and may requireunprecedented forms of internationalaetions to deal with them effectively."

Robert M. WhiteChairman.

World Climate Conference

but innuential conferences on climaticimpact.

The 1975 Rockefeller FoundationConference (which I chaired) was heldat the Villa Serbelloni in Italy. Its report somehow reached Henry Kissinger's table, and he used it as a basis fora message to the U.N. The SovietUnion. at that time. also supported theidea of a world parley, and has sincestrongly backed the preparations forthis month's meeting.

Conference's structure ...It was decided by WMO's Execu

tive Committee that the first-stageconference should be a consultation ofinvited experts, drawn mainly fromdi cipline or professions outside theatmospheric sciences. About 100 experts will attend, reinforced in the firstweek, which will be devoted to overview papers, by 300 others who wish tobe there.

The list of persons invited is broadlyrepresentative of expert knowledge ofareas impacted by climate. It includesforesters, agriculturists, marine scientists, fisheries experts, energy specialists and many others. All majorparts of the world are represented.There is also a small nucleus of senioratmospheric scientists, who willpresent what is known about climaticvariation and variability.

The difficult task of picking the experts was left by the organizing committee to its bureau, which has had thejob of detailed planning. Its chairman,and that of the conference, is RobertM. White, until recently the administrator of NOAA, and now chairman ofthe Climate Research Board, ationalAcademy of Sciences. The othermembers are Jim Dooge, the formerpresident of the Irish Senate, and adistinguished hydrologist; and Yu.Sedunov, first deputy chief of theHydrometcorological Service of theU.S.S.R.

I have served with the bureau asconsultant to the secretary-general ofWMO, and have convened the overview papers. William W. Kellogg, ofthe National Center for AtmosphericResearch, who plays a similar role withrespect to WCP, has also had much todo with the input to the conference.

The main input will be a series of25overview papers, written by a remarkable team of authors who met inApril 1978, at Laxenburg, Austria, (asguests of the International Institute ofApplied Systems Analysis) to concerttheir efforts. Two versions of thesereports will be available. A summaryversion (averaging about 3000 wordseach) will be translated into all theconference's official languages (En-

Volume 13. Number 2. Februarv 1979 157

Economic, political repercussionsof recent climatic eventsO

glish, French, Russian, and Spanish).The more complete version (averaging10000 words) will be published afterthe conference in book form, and willconstitute the most thorough analysisof climatic impact ever published.

... And its contentThe conference will be opcned by a

keynote address from the chairman,Dr. White, summarizing the reasonswhy the group has been convened, andstressing its role in relation to theforthcoming World Climate Program.The keynote address will be followedby the opening overview paper, on climate and society, given by academician Yevgeny K. Fedorov, a memberof the Praesidium of the Supreme Soviet, and one of the pioneers of the remarkable Soviet research program onthe north polar pack-ice.

• 1970: The Sahel, the southernborder areas of the Sahara Desert,experienced a 5-y drought; the result was widespread death andfamine. A costly, sometimes ineffectual international food-aid program fed nomadic populations atrefugee camps.

• 1972: First a severe winterfreeze, then an extreme summerheat wave and drought reducedRussian grain production by 12%.Massive grain purchases by theSoviet government in the worldfood-grain market sent prices skyrocketing.

• 1972: EI Nino, a warming ofcoastal waters associated withchanges in atmospheric circulation,and overfishing brought on the"Adapted from Robert M. White.

158 Environmental Science & TechnoloQV

Fedorov discusses philosophicallythe extent to which political systemscan usefully absorb better climatological information and services. Hegently pulls the western world's leg bypointing out our inability to plan, andto identify the decisionmakers. But noideological gap opens between hispaper and White's. Indeed the wholedocumentation displays a degree ofunanimity rare in international affairs.

The second group of papers has todo with climate itself They are writtenfor lay audiences by professionals, andcover most aspects of current. knowledge of climate. Larry Gates of Oregon State University has written on thefundamental causes of climate and itsvariation. Bert Bolin, of the Universityof Stockholm, writes (with UNESCOsponsorship) on climate and global

collapse of the anchovy harvest offthe coast of Peru. The impact wasfelt Dn international supplies ofanimal protein and world demandfor soybeans.

• 1974: Poor monsoon rains inIndia and Southeast Asia resultedin reduced food production in thatregion.

• 1975: Half the coffee trees in'Brazil were destroyed by a severefrost. World coffee prices increaseddramatically.

• 1977; Abnormally severe coldweather in the eastern and midwestern U.S. drained the finitesupplies of natural gas. The resultwas the closing of schools and industries, and widespread unemployment.

ecology, laying stress on the fundamental assumption of the conference-that climate is an interactivesystem involving soil, plants, animalsand oceans. The intrusion of man intothis system is reviewed in a paper by R.E. Munn of the University of Torontoand Lester Machta of NOAA. I contribute a paper on climatic variabilityand variation, and Ju. P. Izrael, chiefof the Board of the Hydrometeorological Services of the Soviet Union,deals with the monitoring of climateand climatic change. Academician I.P. Gera;imov of Moscow writes aboutvariation of climate during geologicalhistory, drawing extensively on geological and paleobotanical evidence.

A third series of papers deals withthe scientific modeling of climate, andof its sensitivity to human interference.Academician G. I. Marchuk of theSiberian Academy of Sciences CentralComputing Center at Novo-Sibirskdeals exhaustively with the fundamentals of atmospheric modeling itself: a giant problem made even largerby the need to include the two-wayrelation with human society. JohnMason, head of the U.K. Meteorological Office, then analyzes whatmodeling studies have actually taughtus about such questions as the potential impact on climate of stratosphericpollution and of carbon dioxidebuild-up. Hermann Flohn, of theUniversity of Bonn, sketches scenariosof future climates by another kind ofanalysis. He delves back into the pastto find analogs of what may happen inthe future.

The conference will then go on tothe chief areas of climatic impact. Theseries of papers on agriculture wascoordinated by Michel Frere of theFood and Agricultural Organization.M. S. Swaminathan of the IndianCouncil of Agricultural Researchpresents a comprehensive overview ofthe present world food situation, andits vulnerability to climatic and otherdisturbances.

A series of sectoral papers then follows. Francesco Mattei, of the UfficioCentrale di Ecologia Agraria, Rome,writes on the notoriously vulnerableagriculture of the semiarid tropics. Aspecific study of the problems of Africaduring the Sahelian drought, and atother times of stress, conducted byJulius Oguntoyinbo of the Universityof Ibadan and Richard S. Odingo ofthe University of Nairobi, is presentedby these scientists. Hayao Fukui of theCenter for Southeast Asian Studies,Kyoto, gives a very detailed analysis ofthe agricultural problems of the humidtropics, dealing not only with irrigatedrice, but with rain fed agriculture and

F. Kenneth Hare is university professor.and director of the Institute for Environmental Studies at the University of Toran/a. Dr. Hare is a Felfow of the RoyalSociety ofCanada and the American Associationfor the Advancement ofScience.

Coordinated by LRE

development of new and sophisticatedinterdisciplinary modes of researchand operation, with a larger input fromeconomics and ecology than has beenusual in the past.

• The vital need to determine thedegree of resilience or vulnerability ofthe various national economies to climatic impact, and to consider waysand means of assistance to thosecountries or peoples who may in thefuture find themselves in jeopardy assome major anomaly strikes.

There will be many other items inthe plan, especially as regards climaticservices, applications and data gathering. At the root of all this, however,will be the unspoken motto of theconference: understanding climate inthe service of mankind,

Kenneth Arrow of Harvard, a formermeteorologist and Nobel Laureate ineconomics, considers decisionmakingproblems.

A plan of actionOut of this welter of authoritative

information, plus its own expertise, theconference will fashion a plan of action. The second week will be devotedto working group sessions aimed atsuch a plan, aided by careful preparatory work done in a series of informalplanning meetings. It would be impertinent to try to foresee the contentsof such a plan in detail, but no doubt itwill have to cover, inter alia, at leastthese points:

• The virtual unanimity in theoverview papers that the build-up ofcarbon dioxide and contaminants inthe atmosphere will induce significantclimatic change within· the next century; and that it is vital to try to foreseethe character of this change, so that itsimpact may be mitigated, or conceivably exploited.

• The recognition of the need forextensive research and modeling exercises whose scope will be extended tothe whole climatic system, whose sensitivity to human interference canhence be tested.

• The obvious need for more formaltechniques for climatic impact assessment. This will have to include the

ill _ _'& ,

Drought. Total precipitation, which was several inches below normal for the Bath, S.D.,area, was responsible for the loss of this corn crop

Other interacting forcesThe major question of energy-cli

mate interaction, which also has amajor bearing on the carbon dioxideproblem, is dealt with in a study by agroup from the International Institutefor Applied Systems Analysis, JillWilliams (now at the National Centerfor Atmospheric Research, Boulder,Colo.), Wolf Haefele and WolfgangSassin.

Water resources interactions, yetanother area highly sensitive to climatic fluctuations, are treated in apaper by John C. Schaake, of NOAA'sHydrologic Services Division, and Z.Kaczmarek, Director of the Instituteof Meteorology and Water Management, Warsaw. Health impacts arecovered in a WHO-sponsored paper byW. H. Weihe of the University ofZurich's Biologisches Zentrallaboratorium.

Finally, the overall impact of climate on human economic concerns iscovered by two papers from wellknown U.S. economists. RalphD'Arge, of the University of Wyoming, deals with the impact ofclimate onthe world economy, using chiefly thework which he directed under the U.S.Climatic Impact Assessment Program

tree crops as well. James McQuigg ofColumbia, Missouri, deals with theimpact of climate on middle latitudeagriculture and its offshoot, the international grain trade. Juan Burgoswrites of climate-related problems inLatin America. Chinese authors,Chang Chia-cheng, Wang Shao-wuand Cheng Szu-chung, present a casehistory of climatic change in the People's Republic of China, and its impacton agriculture.

In the same genre, A. Baumgartnerof the University of Munich deals extensively with forest-climate interactions. Like many other authors, he laysstress on the role of vegetation inmodulating the carbon cycle. David H.Cushing, of the Fisheries Laboratory,Lowestoft, England, discusses worldmarine fisheries, especially those of theAtlantic, and shows how the recentspell of relative warmth (essentially1910-1960) had dramatic impacts onrecruitment of fish stocks, and looks atthe effect of the 1972 EI Niiio on thePeruvian anchovy catch. A paper by T.F. Gaskell, executive secretary of theInternational Oil Industry Group onExploration and Production, London,deals with the relation of climate andweather to the exploitation of theocean's bottom resources, chiefly oil,and the transportation of the product.His paper, too, was sponsored byUNESCO.


Textileplantwastewater toxici1y

A study collected baseline data on priority pollutantconcentrations and chemical toxicity, in support of

BATEA standard-setting

Gary D. RawlingsMonsall/o Research Corp.

Dayton. Ohio 45407

Max Samfieldu.s. EPA

Research Triangle Park. NC 277//

In mid-1974 and mid-1976, twoU.S. Environmental ProtectionAgency (EPA) regulatory events occurred which led to a large researcheffort designed to evaluate the toxicityof textile plant wastewaters, and todetermine the most effective treatmenttechnology.

The first one occurred in June 1974,when EPA's Effluent Guidelines Division set forth guidelines for the degree of effluent reduction attainablethrough the application of the "BestPracticable Control Technology Currently Available" (BPCTCA), and the"Best Available Technology Economically Achievable" (BATEA), tobe achieved by existing textile manufacturing (SIC 22) point sources byJuly I, 1977 and July I, 1983, respectively. However, on October I, 1974,the textile manufacturing industry,represented by the American TextileManufacturers Institute (ATM I),Northern Textiles Association, andCarpet and Rug Institute, filed apetition with the U.S. Fourth CircuitCourt of Appeals, asking for a reviewof·the proposed 1983 effluent guidelines.

Grounds for the suit were that theBATEA had not been demonstratedfor the textile manufacturing industry.Thus, ATM I and EPA filed a jointmotion for delay of the petition, statingthat additional information would bedeveloped through a cooperative grant

study by ATM I and EPA's IndustrialEnvironmental Research Laboratoryat Research Triangle Park, N.C.(IERL-RTP).

BATEA determinationThe objective of the ATMI/EPA

Grant Study was to gather enoughtechnical and economic data to determine the BATEA for reducing criteriapollutants from textile wastewaters.Criteria pollutants for the textile industry include 5-day biochemicaloxygen demand (BOD,), chemicaloxygen demand (COD), color. sulfide,pH, chromium, phenol, and total suspended solids (TSS). On January 3,1975, the Court instructed ATM I andEPA to proceed as promptly as possible to a completion and review of thestudy.

To evaluate the best availabletechnology, two mobile pilot plantswere constructed and operated byATM l's contractor, Engineering Sciences, Inc. This strategy allowed forreal-time f1owthrough treatabilitystudies. Each pilot plant contained fivetertiary wastewater treatment unitoperations. In addition, a tertiarytreatment technology was laboratorytested. One of the mobile plants wasscheduled to visit 12 textile plants, andthe other to visit II.

Treatment operations in each mobile unit included a reactor/clarifier(using combinations of alum, lime,ferric chloride, and anionic and cationic polyelectrolytes), two multimediafilters, three granular activated carboncolumns, ozonation, and dissolved airflotation. Powdered activated carbontreatability tests were performed in thelaboratory, instead of in the field, withthe pilot plant. From these six-unitoperations, ATM I and EPA selected

seven treatment modes for evaluation(Figure I).

Each of the seven treatment modeswas to be individually set up, with operational and pollutant data collectedover a 2- to 3-day period. Based onthose data, the "best" system for eachplant was to be set up for 2 weeks ofoperational evaluation. These datawere then to be forwarded for economic evaluation.

Prior to pilot plant field testing, thesecond EPA regulatory event occurred, and formed the basis for thetoxicity study. On June 7, 1976, theU.S. District Court of Washington,D.c.. issued a consent decree (resulting from Natural Resources Defense Council, et al. us Train) requiring EPA to accelerate development ofeffluent standards for 21 industrialpoint sources, including textile manufacturing. Among other requirements, the Court's mandate focusedfederal water pollution control effortson potentially toxic and hazardouschemical compounds.

The original consent decree requiredthat "65 classes" of chemical compounds be analyzed in wastewatersamples. Recognizing the difficulty ofanalyzing for all chemical speciespresent in each category of compounds, EPA developed a surrogate listof 129 specific compounds representative of the classes of compoundslisted in the consent decree.

These compounds are referred to as"priority pollutants," and are dividedinto the following fractions for sampling and analytical purposes: volatileorganics, nonvolatile organics, pesticides, polychlorinated biphenyls,metals, asbestos, cyanide, and phenol.EPA also developed a sampling andanalytical procedures manual to be


used as a laboratory guide for theanalysis of these priority pollutants.

The consent decree obliges EPA toidentify which priority pollutants arepresent in industrial wastewaters, andto determine the ability of variouswastewater treatment technologies toremove priority pollutants. Therefore,EPA, with ATM I's cooperation, decided to conduct a separate studyparallel with the EPA/ATM I GrantStudy designed to measure prioritypollutants. Also. since the consent decree focused on the issue of wastewatertoxicity, ATM I agreed to have samplescollected for bioassay testing, in orderto have a complete and comprehensivewastewater characterization data base.Thus, the bioassay testing programestablished by EPA for evaluating thereduction in toxicity of water samplesby control technologies and outlined inFigure 2 was integrated into the program. The overall EPA-IERL/RTPtextile program consists of two separate projects, each with different activities running parallel in time, butconverging toward the same goal: determination of BATEA for textilewastewaters.

Dayton Laboratory was divided intotwo phases, in order to gather the mostinformation in a cost-effective manner.Phase I was designed to collect baseline toxicity and priority pollutant dataon secondary ernuents from the 23plants before the pilot plant programbegan. In this manner, 23 sampleswere to be subjected to the battery ofbioassay tests. Only those plants withtoxic secondary ernuents would beselected to determine reduction intoxicity by tertiary treatment systems.Also, appropriate bioassays could beselected, instead of performing theentire battery of tests for Phase II.Phase II was designed to collect samples before and after each tertiarytreatment unit operation to determinereduction in toxicity and priority pol·lutant concentrations at the plants se·leetcd from Phase I.

In addition to collecting samples forpriority pollutant analysis and bioassaytesting, EPA included the new Level Ienvironmental assessment technologydeveloped by EPA's Process Measurements Branch, IERL/RTP. LevelI, the first part of a three-phased en-

vironmental assessment approach, wasdesigned to focus available resourceson emissions that have a high potentialfor causing measurable health or ecological effects. Based on the results ofthe pilot test, approaches for Levels 2and 3 could be developed.

Field sampling

The basic textile plant wastewatertreatment plant consisted of an aera·tion lagoon with several surface aerators, followed by conventional clarifiers and chlorination. Raw waste andsecondary ernuent samples were collected at the points indicated in Figure3. Secondary ernuent samples werecollected between the clarifier andchlorination, because that is the streamthat would now into a tertiary treatment system.

Raw waste samples were collectedover an eight-hour period during anormal working day, with automaticcomposite samples. Eight individualsecondary ernuent samples were collected by grab sampling techniques, byuse of a 3-gal Tenon®·lined stainlesssteel bucket. Aliquots were removed

Program objectives

Monsanto Research Corporation(MRC) collected and analyzed thesamples for priority pollutant analysisand bioassay testing under EPA Contract 68-02-1874. The fundamentalobjective of the textile plant wastewater toxicity study was to determinethe reduction in toxicity, and prioritypollutant concentrations achieved bythe tertiary treatment technologiesbeing tested at 23 plants in the EPA/ATM I Grant Study.

The study conducted at M RC's

FIGURE 2

Bioassay testing

FIGURE 1

Tertiary treatment nodes for "best availablete~hnology" evaluation

Mode A: Reactor/clarifier-Muttimedia fitter

Mode B: Muttimedia fitter -Granular activated carbOn columns

MOlle C: Muttimedia fitter-Ozonator

Mode D: Ozonator

Mode E: Reactor/clarifier -Muttimedia fitter -Granular activated (Optional)carbon -Ozonator

Mode F: Coagulation-Muttimedia fitter

Mode G: Dissolved air flotation

Water sample

r

I Microbial mu\8genicitySalmonella ~ imurium

TA 1535, TA 100,~ 1537, TA 98

I

Cytotoxicity

I

Marine or freshwaterecology,

as appropriate

I

I

Range findingacute toxicity

rats, 14 day

I

•Terrestrial

ecologysoil microcosm

Freshwaterfathead IT!lnnow toxicity

algae bottleDaphnia toxicity

Marine:sheepshead minnow

algaegrass shrimp


FIGURE 3

Water toxicity sampling locations for Phase I

sample blanks were collected to determine if the sampler was contributing to the presence of organic prioritypollutants. Laboratory-prepared organic-free water was passed throughthe sampler, and collected. Results arepresented in Tablc I.

Results of GC/MS analyses of 64textile plant raw waste and secondaryernuent samples for organic prioritypollutants are available. Of the 114organic compounds in the prioritypollutant list, a total of 44 differentcompounds were identified in textilewastewaters, 38 in raw waste samplesand 33 in secondary ernuent samples.On an individual plant basis, thegreatest number of organic compoundsdetected in a raw water and secondaryernuent sample were 14 and 8, respectively, with an average number perplant of 7 in the raw waste and 5 in thesecondary ernuent. The predominantcompounds were bis (2-ethyl hexyl)phthalate in 54 samples (0.5 I'g/L300 I'g/L), toluene in 44 samples (0.4Jlg/L-300 Jlg/L), and ethylbenzene in30 samples (0.7 Jlg/L-3000 I'g/L). Asummary of the 13 priority pollutantmetals and cyanide concentrations inra w waste and secondary ernuentsamples is given in Table 2.

On an individual plant basis, it wasfrequently observed, especially for themetals data, that the concentration ofa specific pollutant was greater in thesecondary ernuent sample than in theraw waste sample. This phenomenonis due, in part, to the hydraulic retention time of the wastewater treatmentfacility. Since raw waste and secondary ernuent samples were collectedsimultaneously, concentrations in thesecondary efnuent were caused by rawwaste loads that entered the treatmentsystem 1-30 days prior to sampling.The average retention time for the 23plants was about 5 days.

Level I chemical analyses

Level I chemical analyses wereperformed on secondary effluentEffluent

Chlorinecontactbasin

samples must be looked upon as reliable estimates of which priority pollutants were present, with concentrations accurate to within a factor ortwo.

The 114 organic priority pollutantsare divided into four categories foranalysis: volta tile organics, baselneutral organics, acid organics, andpesticides and PCB's. Volatile organicswere sparged from the sample withhelium and adsorbed onto a Tenaxcolumn. Adsorbed species were laterthermally desorbed for identificationand quantification with a HewlettPackard 5981 gas chromatograph/mass spectrometer (GC/MS) with a5934 Data System.

Base/neutral and acid organicswere determined by extracting thesample with methylene chloride firstat pH > II, and then the aqueousphase at pH <2. Extracts were thendried on a sodium sulfate column andconcentrated to I mL in a KudernaDanish evaporator with a Synder column, Concentrates were then analyzedwith the GC/MS system.

Pesticide and PCB species weresimilarly processed. However, theywere extracted instead, with a mixturecontaining a volume ratio of 15%methylene chloride and 85% hexane.

Since raw waste samples were collected with automatic samplers with aperistaltic pump and Tygon tubing,

0 0 0 ")\

Clarifier0 0 0

J.Aeration lagoon Secondaryeffluentsample

from the bucket, and poured into appropriate sample containers. Care wastaken to ensure that the sample remained homogcncous throughout eachof thc 10-min pouring sessions. Containers for volatile organics analysiswere filled first, and scaled to minimizepossible evaporation losses. All samples were preserved in the field according to EPA specifications. Samples were then packed in ice andshipped via commercial air freight tothe appropriate laboratory for analysis.

Priority pollutants detected

Analysis of raw waste and secondary ernuent samples (totaling 64samples) for the 129 priority pollutantswere performed by MRC in accordance with the analytical methodologyrccommended by EPA. It is importantto realize that the purpose of EPA'sanalytical scheme is to screen samplesto dcterminc which of the 129 chemical species are prcsent, and to estimatetheir general concentration range.With a narrowed list of species, laterverification studies will more accurately quantify specics concentrationsin a cost-effective manner.

Currently, the recommended analytical protocol is in thc developmentalstage and requires further verificationand validation. Thcreforc, thc analytical results of textile plant wastewater

... and for Phase II

Intakewater

Secondary Slip-wastewater streamtreatment

Rlant

Recombinedwith planteHiuent


TABLE 1

Summary of organic priority pollutants found in automaticsampler tubing blanks

TABLE 2

Summary of priority pollutant metalsConcentration range, rnglL

to the test organisms, or by injection orfeeding, most tests are conducted byexposing the test organisms to test solutions containing various concentrations of effluent samples. One or morecontrols are used to provide a measureof test acceptability by giving someindication of test organism health andthe suitability of dilution water, testconditions, handling procedures, etc.

A control test is an exposure of theorganisms to dilution water with noeffluent sample added. Bioassay testsare exposures of test organisms todilution of water with effluent samplesadded.

Generally, the most important dataobtained from a toxicity test are thepercentages of test organisms that areaffected in a specified way by eachconcentration of wastewater sampleadded. The result derived from thesedata is a measure of the toxicity of theeffluent sample to the test organismsunder the test conditions.

Acute toxicity tests are used to determine the level of a toxic agent thatproduces an adverse effect on a specified percentage of test organisms in ashort period of time. The most common acute toxicity test is the acute

Raw waste sample secondary effluent sample

216

0.5 to 10.21.5t0461.3 to 1.70.6 to 1.12.6 to 55

3.22.48.3

Concentrationrange, "gIL

0.0005 to 0.070.005 to 0.02<0.00010.0005 to 0.010.0002 to 2.00.0002 to 0.30.004 to 0.20.001 to 0.20.0005 to 0.00090.01 to 0.2<0.0050.005 to 0.1<0.0050.07 to 38

mortality test. Experimentally, 50%effect is the most reproducible measureof the toxicity of a toxic agent to agroup of test organisms, and 96 h isoften a convenient, reasonably usefulexposure duration. The 96-h medianlethal concentration (96-h LCso) ismost often used with fish and macroinvertebrates. Thus, the acutemortality test is a statistical estimateof the LCso, which is the concentrationof toxicant in dilution water that is lethal to 50% of the test organisms during continuous exposure for a specifiedperiod of time.

However, the 48-h median effectiveconcentration (48-h ECso), based onimmobilization, is most often used withdaphnids. The terms median lethalconcentration (LCso) and median effective concentration (ECso) are consistent with the widely used termsmedian lethal dose (LDso) and medianeffective dose (EDso), respectively. Asused in this study, "concentration" isthe percent of effluent wastewaste perunit volume of test solution to whichthe organisms were exposed; "dose"refers to the measured amount of effluent wastewater given to the rats(mg/kg).

0.0005 to 0.060.005 to 0.2<0.00010.0005 to 0.050~0002 to 0.90.0002 to 2.40.004 to 0.20.001 to 0.20.0005 to 0.0040.01 to 0.2<0.Q050.005 toO. 1.<0.0050.03 to 8.0

Compound found

NaphthaleneDimethylphthalateDiethylphthalateBis(2-ethyl hexyl)phthalateDi-n-butylphthalatePhenolTolueneTrans-l,2-dichloroethyleneTrichloroethyleneEthylbenzene

Element

AntimonyArsenicBerylliumCadmiumChromiumCopperCyanideLeadMercuryNickelSeleniumSilverThalliumZinc

AcidsVolatiles

Fraction

Base/neutrals

samples from 15 of the 23 basic textileplants. Level I protocol identifiesclasses of compounds present in environmental samples, and measures thegeneral concentration range. Resultsindicate that total concentration ofmethylene chloride extractable organics ranges 3 mg/L-64 mg/L.

In the Level I procedure, eachsample was fractionated by a liquidchromatography column into eightfractions based on polarity. Infraredanalysis of each fraction indicated thepresence of aliphatic hydrocarbons,esters and acids: aromatic compounds,phthalate esters, and fatty acid groups.Low resolution mass spectrophotometric analysis of the eight fractions ofeach sample detected the followingtypes of compounds: paraffinic/olefinic, bis (hydroxy-t-butyl phenol)propane, tri-t-butyl benzene, alkylphenols, dichloroaniline, toluene-sulfonyl groups, vinyl stearate, and azocompounds.

Bioassay resultsThe primary objective of the entire

wastewater toxicity study is to determine the level of toxicity removal fromsecondary wastewater achieved by thetertiary treatment technologies selected in the ATMI/EPA BATEAstudy. To this end, the purpose of thisscreening study was to provide chemical and toxicological baseline data onsecondary effluents from the 23 textileplants, and to select plants for thetoxicity reduction study.

Bioassays used were selected byEPA and included tests for assessmentof both health and ecological effects.Health effects tests estimated the potential mutagenicity, potential orpresumed carcinogenicity, and potential toxicity of the secondary effluent wastewater samples to mammalian organisms. Ecological effectstests focused on the potential toxicityof samples to vertebrates (fish), invertebrates (daphnids and shrimp),and plants (algae) in freshwater, marine, and terrestrial ecosystems.

Biological testing, as well as chemical and physical parameters, should beconsidered when assessments of thepotential impact of industrial or municipal/industrial wastewaters on theaquatic environment are made. Biological testing involves determinationof toxicity for samples of treated effluents. In a toxicity test, aquatic organisms will integrate the synergisticand antagonistic effects of all the effluent components over the duration ofexposure.

Although toxicity tests with aquaticorganisms can be conducted byapplying wastewater samples directly

Volume 13, Number 2. February 1979 163

A total of 8 biological systems wereused for wastewater toxicity evaluation. Twenty-one different tester organisms were utilized.

Under guidance of appropriate EPAtechnical advisors, four of the eightbioassays were performed at fivecommercial laboratories, indudingMRC, experienced with the bioassays.The remaining four bioassays wereperformed by the EPA technical advisors.

The measure of toxicityThe viability test was a measure of

the cells' ability to survive exposure tothe effluent. The adenosine triphosphate (ATP) test measured the quantity of the coenzyme ATP produced,indirectly measuring cellular metabolic activity.

ECso for the algal tests means theconcentration of secondary effluent,which caused a 50% reduction in algalgrowth as compared to a control sample. The freshwater algae test wasperformed over a 14-day period, andthe marine algae test over a 96-hperiod.

For the fathead minnow, sheepshead minnow, and grass shrimpbioassays, death was used to measuretoxicity, which was expressed as LethalConcentration 50 (LCso)· LCso indicated the calculated concentration ofsecondary effluent that was expectedto cause the death of 50% of the testspecies. Since rats were given a specificquantity of secondary effluent, toxicitywas expressed as Lethal Dose 50(LDso). LDso indicated the quantity ofmaterial fed to the rats that resulted inthe death of 50% of the test animals.

The measure of toxicity to a soilmicrocosm was the quantity of carbondioxide (C02) produced after effluentexposure, as compared to that evolvedfrom a control sample. The quantity ofCO2 produced over a 3-wk period,after subtraction of the quantity produced by the control, was plotted ongraph paper. The slope of the curvethen represented the rate of increase ordecrease in CO2 production broughtabout by exposure to the effluent.

Results of the freshwater ecologyseries showed enough variation in responses to permit relative ranking ofthe toxicity of effluent samples.However, no general rule can be formulated concerning the relative response between fathead minnows anddaphnia. For example, Plant E's effluent was found to be toxic to daphniabut not to fathead minnows; at PlantT, the reverse was true.

For the marine ecology series, thedata indicate the grass shrimp weremore sensitive than sheepshead min-


nows. Also, fathead minnows weremore sensitive, in the majority of thesamples, than sheepshead minnows.

In terms of mutagenicity, none ofthe 23 effluent samples produced apositive response to any of the bacterialtester stains. Also, no acute toxicitywas observed in any of the rat testswhen rats were given the maximumdosage of 10 mLjkg of rat bodyweight.

Data interpretationAn objective of the Phase I screen

ing study was to rank textile plantsaccording to the toxicity of their secondary wastewater, and to select plantsfor detailed toxicity evaluation inPhase II. To accomplish this objective,members of the EPA Bioassay Subcommittee met to evaluate the bioassay data.

From the results, the subcommitteerecommended that the following ninetextile plants ranked in relative orderof toxicity being tested to determinethe reduction in toxicity achieved bythe tertiary treatment technologiestested in the ATMljEPA GrantStudy: N, A, W, C, T, Y, L, S, and P.(Plant R was also recommended forstudy under Phase II, because its secondary effluent samples were inadvertently collected before the effluentreached the settling pond.) In addition,the subcommittee recommended thatthe freshwater ecology series andAmes test be used to measure reduction in wastewater toxicity by thetreatment technologies. The marineecology series was not selected becausenone of the textile plants dischargewastewater into a marine environment.

During Phase II of this project,samples will be collected at the 10plants selected before and after each ofthe tertiary treatment unit operationsbeing tested in the pilot plant. In addition, samples of the textile plant intake water and secondary effluent willbe collected. In Figure 3 is an exampleof sampling locations for a typicaltreatment train.

Toxicity rankingPhase I toxicity screening provided

several significant results. Of the 129priority pollutants, only 45 of the 114organic species were detected. On anindividual plant basis, the largestnumber of organic species detected ina single effluent sample was eight, withan average number of five. Thalliumwas not detected in any of the samples.

Data collected from the battery oftechnology-based bioassays indicatedit was possible to rank effluents based

on relative toxicity. In general, toxiceffects detected in one test system werealso detected in other systems. None ofthe effluent samples, however, produced positive mutagenicity responsesor resulted in acute toxicity effects inrats.

Results of these tests were used toselect plants with relatively more toxiceffluents with which to study the reduction in toxicity by selected tertiarytreatment wastewater control technologies. Results of the Phase II workwill be available in mid- I979.

Additional readingGallup, J. D., Development Document forEffluent Limitations Guidelines and NewSource Performance Standards for theTextile Mills Point Source Category.EPA-440/1-74-0na (PB 238 832), U.S.Environmental Protection Agency,Washington, D.C., June 1974,246 pp.Draft Final Report Sampling and AnalysisProcedures for Screening of IndustrialEffluents for Priority Pollutants. U.S.Environmental Protection Agency, Cincinnati, Ohio, April 1977, 145 pp.Duke, K. M., Davis, M. E., Dennis, A. J.,IERL-RTP Procedures Manual: Level IEnvironmental Assessment BiologicalTests for Pilot Studies. EPA-600/7-77·043(PB 268 484), U.S. Environmental Protection Agency, Research Triangle Park,N.C., April 1977, 114 pp.Hamersma, J. W., Reynolds, S. L.,Maddalone, R. F., IERL·RTP ProceduresManual: Level I Environmental Assessment. EPA-600/2-76-160a (PB 257 850),U.S. EPA, Research Triangle Park, N.C.,June 1976, 147 pp.Manual of Methods for Chemical Analysisof Water and Wastes. EPA-625/6-76003a (PB 259 973), U.S. EPA, Cincinnati,Ohio, 1976,317 pp.

Gary D. Rawlings (I) is a Contract Manager at Monsanto Research Corporationresponsible for numerous environmentalR&D projects. For the past two years hehas been involved with characterizing industrial wastewaters for priority pol/utants and toxicity.

Max Samfield (r) is a project officer withthe Chemical Processes Branch ofEPA'sIndustrial Environmental Research Laboratory (IERL) at Research TrianglePark, N.c., and has been in that positionsince 1975. Priorto joining EPA, Samfieldwas assistant director of research forLiggell and Myers, Inc. He has published60 articles, holds five patents, and receivedhis Ph.D. degree in chemical engineeringfrom the University of Texas.

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Carl G. SchwarzerDept. of Health ServicesBerkeley. Calif 94704

Recently, the California Department of Health, Hazardous MaterialsManagement Section (HMMS) undertook a program to locate and identify the waste streams of variouscompanies in the San Francisco BayArea whose components might be recycled. The purpose of the programwas to conserve energy and chemicalresources by reusing materials whichnormally would be disposed of, and toreduce the volume of materials goinginto disposal sites.

Philosophically, the Departmentbelieves that land burial of hazardouswaste should be used only as a last resort. Burial of highly toxic wastespresents hazards that project into thefuture over an indefinite period; forexample, there is little assurance thatthe Class I sites so carefully selected toconfine hazardous waste materialstoday will function in this capacityforevermore.

This is not to say that land burialdoes not have its place as a disposalmethod. It should be used judiciously,but whenever possible, alternatemethods should be considered. The

best procedure for solving wasteproblems is to reuse the waste materialin other production processes to reduceits generation. This, of course, is not anovel idea; but what is new is the use ofhazardous waste materials in new anddifferent applications.

Economic feasibilityAlmost all materials are recyclable,

but to be viable the reuses must offereconomic incentives. All materials arenot economically recyclable; in some,more energy will be expended in recovery than the recovered value warrants. Hence, many factors need to beweighed. Recycling programs requirecareful scrutiny and evaluation to assure that a viable solution to theproblem will be achieved. Mixturecomplexity, the processing equipmentrequired, available technology, technical capability and geographic location are all factors that need to be addressed. And, of course, most important of all is the question of whether ornot a net gain of value is obtained.

If suitable processing or reclamationequipment and technology are notavailable, the material mayor may notbe reusable. A case in point is a mixture of epichlorohydrin, methyl ethylketone, methyl isobutyl ketone, ethanol, propylene chlorohydrin and water.This mixture is the result of an epoxy

resin process and is rectified and recycled on a routine basis by a largeepoxy resin manufacturer. A smalloperator would find this material to bean unseparable mixture, essentiallynon recyclable.

Simple mixtures, as a rule, are easierto process than multicomponent mixtures. For this reason, the HMMSencourages industry to keep wastestreams separated and as simple aspossible. However, this cannot alwaysbe done and, as a result, some nonreusable waste streams are generatedunder the best conditions. Thesewaste-solvent mixtures may still beuseful as fuels, however.

Geography, as well, plays a key rolewith regard to the reusability of awaste. Many tir..es optimum utilization of a waste requires its combinationwith a waste that is at a different location. The feasibility of reuse in thissituation is completely dependent uponthe proximity of the two wastes.Transportation costs can quickly negate such opportunities.

Department's effortsThe hazardous waste recycling

program has involved the investigationof many waste streams from a varietyof industries. Because of the unrestricted opportunities for exploring thewaste streams of completely different


Prior 10 IrpOllllemlhis heacy clay soil supports ollly lighr crops of salt gross

Lillie-sulfur silldge frolll 0 lIeorby chemical plom is being applied to a field

.",~

Wallboard olld papu fiber sludge alllelldlllem is opplied to the heacy cloy soil

types of industries, the Department hasbeen able to "marry off' wastes orcompanies that normally would havelittle or no contact with one another.The Department has supported only alow key effort to date. One man in theSan Francisco Bay Area has initiateda pilot program which has proven sosuccessrul in promoting waste recycling that it will probably be greatly expanded over the next year.

The most productive means of obtaining the needed inrormation forwaste reuse is by personal interview,which identifies a potentially usefulproduct that is presently being wasted,and uncovers potential consumers.Furthermore, by personal interview arelationship is established that ishelpful in not only locating usefulwaste streams, but also in convincingcompanies to investigate the use of awaste stream in their productionline.

An alternate method is the clearinghouse concept. As the name implies,this involves the collection and widedissemination or inrormation regarding industrial waste resources. Inrormation describing the type of wastematerial, concentration, impurities orcontaminants, as well as the physicallocation of each waste is obtained. Theuse or a questionnaire is the usual waythe data are accumulated, althoughpersonal interviews may be used. Theinrormation can be computerizedand/or published and disseminated inthe form of a list of materials available,and a list of materials being sought.

The clearinghouse idea, however,does not automatically solve theproblem. It is merely a tool that can beused to expedite waste informationexchanges. The system does not automatically assure that waste exchangesor uses will develop. Recycling andrecovery need to be worked at: theyrequire many hours of technical discussions, the services of technicalpersonnel, consultation and handholding to fit waste streams intopresent technology. While there is aneed ror the establishment or a databank, the passive clearinghouse concept does not work well without activesupport.

The problems with a listIn regard to the computerized lists

generated under the clearinghouseconcept, several difficulties are associated with the periodic mailing or awaste list to potential users. The listmay not get into the hands or the rightperson, especially in large companies:consequently its value is lost.

The time required to assemble and


Right. This plant processes waste solvents

Below. Pickle acid from this steel plant is chlorinated to produceferric chloride. which is used 10 treat sewage at a sanitary disposalfacility

distribute a list is relatively long(usually one month), but an arrangement might be made for the information to be published in a newspaper ona daily basis. This is not inconceivable.However, most companies are not receptive to the idea of holding wastematerials on-site for extended periodsof time.

In reality, however, a waste producer may not have a steady production of waste; he may produce, for example, 30 drums of "spent" acid overa period of time. Usually, he is not receptive to the idea of keeping the material any longer than necessary. Hewants a more positive response than tostore the material on-site hoping thatsomeday someone will take it away.

Most industries interviewed haveindicated that a list sent by mailprobably would not even be read unlessthey were actually looking for a specific material. Several reasons arecited.

Companies have a great fear ofchanging an established process thathas been proven successful over a longperiod of time. To interchange a purefeedstock for somebody's waste streamtakes a great deal of investigation andthought; a mistake could prove to beextremely costly. In addition, companies require assurance of a continued level of purity and quantity.Hence, in a great many cases, com-


panies will not seek out a source ofmaterials that may jeopardize eithertheir production rate or quality.

In the personal technical interview,some of these fears can be allayed.Problems of this kind can be discussedin detail and possible solutions addressed. A complete description of thewaste can be given and arrangementsfor samples made.

Hindrances

Many industries are sensitive aboutprotecting information regarding theirproduction rate and manufacturingprocedures. The types and amounts ofwaste components generated aresources of information that a competitor can use to his advantage to obtainvaluable production data. Hence, in arecycling program it is necessary toaddress and solve this problem.

Another problem that occurs withmailed questionnaires involves reported accuracy of the composition ofthe waste streams. Incomplete or deficient information can lead to poorexperiences. A case in point involvedthe transfer of 48 drums of 92% aceticacid which was shipped to the recipientand subsequently returned. The generator had failed to note that the acidalso contained 2% chromic acid!

Another factor that frustrates theefficient use of the clearinghouse pro-

cedure involves interaction of governmental agencies. It is sometimes difficult to obtain clearance to recyclewithout the services of an intermediaryagency.

For example, a galvanizing wastepond located in the San Francisco BayArea contained sufficient zinc and ironcontent to be of use for soil applicationin the Brentwood area (40 miles away)where these elements are deficient. Afarmer was located who needed thematerial and was willing to test it onhis soil.

The Department of Health Servicesanalyzed the material to assure that nohcavy metals deleterious to the landwere present in any significant concentrations. Agriculturists at theUniversity of California at Davisagreed that the material might indeedhave beneficial effects on the soil towhich it would be applied. The problem now revolved around the locationof the pond and the area in which thematerial was to be used.

The pond was located in an areaunder the jurisdiction of the SanFrancisco-Oakland Water QualityControl Board. This agency was concerned about removing this potentiallyhazardous material as soon as possible(probably to a Class I disposal site)since they wanted the assurance thatthe pond would be properly phased out.The exigency of time revolved around

the fact that the company had ceasedoperations in the area and was indeedpreparing to abandon the area as aproduction site.

The agency, which had control overthe area where the ma teria I was to bedisposed, wanted to be assured, as didthe farmer, that the pond contentswould be beneficial before applying 3.5million gallons of the material broadlyand indiscriminately over the land. Theagency also wanted to make a test plotwhich involved raising a crop andevaluating the results. This, of course,would postpone the removal of thepond contents for six months to ayear.

The problem was solved by the Department's Hazardous ManagementSection in bringing Water QualityControl Board representatives, thefarmer, the prospective hauler and theproducer of the waste all together at ameeting where all questions could beaddressed and answered to the satisfaction of all those involved. Thisproblem could not have been rectifiedby just using the clearinghouse concept.

Perhaps one of the most difficultproblems regarding the clearinghouseconcept is the fact that there is a tendency to collect all the "dogs." Theuseful components we assume willeventually be used or put to work. Ifthings work, the easily recyclablewaste will be quickly removed from thelist. But some materials may have avery low potential for recycling andthese will tend to accumulate. Theclearinghouse concept makes assessment difficult, but the dynamic technical interview concept allows for anappraisal to be made at the time of theinterview-before the material is entered into a recycling list.

Interview approach works

Making a list of materials availableand distributing the list is a minor partof a reeycling program, but it has itsplace. A more dynamic approach involves interviews in which technicaldiscussions are held regarding thewaste streams. Quantity, contaminants, and other discretionary information of importance can then be secured. Many such interviews are required before a recycling programreally begins to "tick" and gain momentum. Then the industry will respond to this "fee-free brokerage"service.

When this occurs, another facet ofthe program can be invoked. Assistance can be rendered by suggestingalternative procedures for waste usagethat can be of great economic value to

a company. These alternate procedures, which may not be apparent tothe waste producer, are the direct results of the interviewer's vast knowledge of industrial information accumulated by his contacts in the industry.

Although the task of interviewing amyriad of companies to define theirwaste streams might seem formidableif not impossible, the process can begreatly shortened. A practical means ofachieving this goal, and accumulatinga large amount of information, is tobecome familiar with the efnuentsfrom the various types of industry. Forexample, most steel processing plantshave a waste stream known as "pickle"acid. It usually contains about 10-15%ferrous chloride or sulfate and a fewpercent of acid. If a need for this typeof material arises, a large portion of thesteel industry is available as asource.

Industrial participation in the program has been gratifying. In mostcases, complete cooperation has beenreceived. Industry has not only sanctioned the program, but is gratified tolearn that the state has instituted aprogram to help it solve its disposalproblems. To some, the service offersincome from an unexpected source; toothers, it reduces the amount of moneyspent on disposal fees; and to still others, both incentives are provided.

At the present time, most plantmanagers are willing to discuss theirprocesses and waste streams with stateinterviewers. Recycling advice is givenwhenever appropriate. At other times,technical advice, which allows thegenerator of a waste stream to convertit into a useful and valuable by-product, is supplied. These services aregiven without cost.

The Department learns of potentially useful waste products in otherways, notably through our disposalsite-surveillance activities. Inspectionsof waste disposal sites, both Class I andII, by field personnel frequently revealthat large quantities of high-qualitycommercial materials are being disposed of. Large loads of chemicals inunopened bags and drums are frequently discarded. The operators of thedisposal sites are asked to contact ouroffice if materials suspected of havingrecoverable value are brought to thesite. Cooperation between the site operators and our inspectors results in theretrieval of much valuable materialthat has been delivered for disposal.

Managers usually welcome recycling advice and, in most cases, quicklyfollow up the contacts that are suggested. After all, the alternative torecycle is disposal, usually at consid-

erable expense. When two parties arebrought together, the work of the Department has ended. Our sole functionis to bring the right parties together toavoid disposal. The details of thetransactions such as whether the material is sold, given away outright, orwho pays for transportation are left tothe two principals involved. There havebeen times when the transactions havebeen unsuccessful, but this is the exception rather than the rule.

Reclaiming nonhazardous wastes

Much useful nonhazardous materialis being thrown away also. This usuallyoccurs because disposal is easy andconvenient and relatively inexpensive.A case in point involved a breakfastfood manufacturer who discarded 18semitrailer loads of breakfast food intoa Class II (domestic refuse) site. Thismaterial was boxed and "cartoned"and ready for distribution at the timeof disposal. Why was it discarded? Toomuch vegetable oil had inadvertentlybeen used during manufacturing, thuspossibly affecting the shelf life of theproduct. It was cheaper for the manufacturer to dispose of the materialthan to reopen the boxes and recoverthe breakfast food for animal consumption.

Our program was explained to thebreakfast-food manufacturer, whereupon he offered to cooperate with usfor alternate disposal in the event offuture problems. Six weeks later, themanufacturer contacted us about another batch of breakfast food damagedby an overhead sprinkler failure. Wecontacted a pheasant farmer who wasdelighted to receive the material; hesaved $4000 on his feed bill for thatyear!

Many other examples of nonhazardous waste disposal of usable materialshave been observed. Whenever possible, we assist in recovering nonhazardous industrial waste materials forreuse as well as the hazardous materials.

Categories of hazardous wastes

Our interviews with company personnel indieate that about five broadcategories of hazardous waste arebeing generated. These include:

• materials or "articles" of commerce

• process wastes that are reusablewithout treatment

• materials that are reusable withtreatment

• waste materials that have little orno value

• materials that no one wants torecover.

In the first category, materials of


Ferrous sulfate is used at this geothermal well to remove hydrogen sulfide from steamprior to reinjecting the steam into a return well

commerce, we have found many kindsof materials being discarded. For example, many gallons of concentratedcaustics and sulfuric, nitric, and hydrochloric acids are being disposed ofdaily. These are in addition to thenonusable dilute solutions that arebeing thrown away. Needless to say,unused materials of commerce are theeasiest materials to recycle. In additionto known users of these materials, orthose who have expressed an interestin such products during our originalinterview, there are a number of competent, dependable chemical brokersin the San Francisco Bay Area who aredelighted to take these so-called wastematerials off the hands of the generator. Usually they are able to purchasethese products at discount rates.

Many drums of useful chemicals arediscarded on a regular basis. Why arethey being discarded? Many times theproducts are "outdated" or have beendiscovered during a clean-up or havebeen stored for a long period of timeand are being disposed of because theyare no longer of value to the owner.

A frequently encountered reason fordisposal is the very tight quality-control restrictions that are imposed bysome industries. This is especially trueof the food and semiconductor industries where chemicals of generally acceptable quality are discarded becausethey cannot meet the very tightly-


controlled standards of these industries. These materials are discardedrather than returned for credit becausethe producer does not want to riskcontamination of future batches of thesame product.

In the second category are processing wastes that are reusable withouttreatment. These are waste materialsthat can be reused as industrial feedstocks per se. In this category belongthe cafdboard for pulping, copper, andother metal solutions for metal recovery, certain solvent streams, and a diversity of other materials. They alsoinclude filter charcoals, oils that can beused for fuel, used diatomaceous earthfilter cakes which provide siliceousmaterials for cement manufacturers,a variety of valuable metal materials,and sludges which sometimes may require simple separation from watersuspensions.

Caution is required to assure thatthese materials, when reused, will notcause untoward effects. For example,cardboard is repulpable and is commonly repulped to make more cardboard. However, if the cardboard iscontaminated with polychlorinatedbiphenyls (PCB's), pesticides orchemicals, the new cardboard shouldnot be used for food packaging, but itcan be used for other purposes such asthe manufacture of concrete foundation forms.

Another example of "reuseablewithout treatment" waste involves apaper recycling company which has acertain percentage of paper that is notrepulpable. This they biodegrade tomake a loam used in lawn preparation.During our interview, it was broughtout that they would really like to makea complete fertilizer by the addition ofnitrogenous and phosphorous materials. Tanneries produce a highly proteinaceous material from their dehairing process. This is difficult todispose of since it contains caustic sodium sulfides and undissolved hair aswell as various other proteinaceousorganic materials. The tannery oxidizes the waste to convert the sulfides,neutralizes with sulfuric acid, andsends the products to a disposal site.

This material is ideal as a nitrogenous soil amendment when used withthe biodegradable paper loam. Wesuggested that the tannery contact thepaper company for disposal. The tannery volunteered to use phosphoricacid in place of sulfuric acid to neutralize the alkalinity and upgrade thenutritional value of the soil amendment.

There was only one catch. The distance between the two sources was toofar and the sales price of the productcould not justify the transportationcosts. This brings us to another point.Resource recovery and recycling wouldbe greatly aided and abetted if morestringent restrictions were put on disposal and the cost of disposal increased.

Opportunities are plentifulA good example of the successful

recycle of a waste product is "galvanizers pickle acid." This material contains about 8-10% zinc sulfate as wellas some iron salts. It can be used as anagricultural additive in areas deficientin zinc; it is commonly used in citrusorchards.

The pickle acid can be fortified withbaghouse dust produced by some scrapsteel processors. Baghouse dust fromthis source contains as much as 25%zinc oxide. So this material in conjunction with more waste sulfuric acidis used to increase the zinc sulfateconcentration in "galvanizers pickleacid." Higher concentrations are moreamenable to the recovery of solidzinc-iron sulfate by a dehydrationprocess. This process is presently inoperation in California.

Another "steel pickle acid" contains10-15% ferrous sulfate. This productis being used to treat the steam beingused to develop electrical power in thegeothermal area around Calistoga.The Air Pollution District in that area

does not allow venting of the hydrogensulfide in the steam, so it is treatedwith ferrous ulfate solution. A sludgeconsisting of iron sulfide and elementalsulfur is recovcred, which in itself isuseful as a soil amendment in manyareas.

These and other developed uses havecreated a shortage of "pickle acid" inthe Bay Area. Now that is pretty unusual' A shortage has developed for amaterial which at one time was aprime pollutant of the rivers and thebay of this area.

Opportunities for recycling wasteare manifold and pop up in manystrange places. For example, a relatively small company is involved in thebusiness of recovering metals such asnickel. copper, and some gold and silver from waste streams arising from anammonia copper solution waste produced by printed circuit board manufacturers.

A caustic waste stream containingsodium sulfide is produced by a nearbyrefinery. Both the metal-containingwaste and the sulfide-containing wasteare considered hazardous waste inCalifornia and require rather costlydisposal in our Class I disposal sites.

The treatment of thc metal-containing solution with the sulfide causticprecipitates the heavy metals whichare recovered. The amount of heavymetal remaining in residual waste is ata concentration which allows disposalto the sanitary sewer system.

The third category of wastes havepotential use, but require some ingenuity or inventiveness to convert themto useful materials. These are usuallydisposed of by using the alternatemethods approach. One example involves the semiconductor industry,which produces a large amount of acidstripper-a mixture containing 96%sulfuric acid, and 2% chromic acid. It'sthe bane of the industry and is usuallyburied. This material can be used forrefining used crankcase oil. Usedcrankcase oil contains heavy metalssuch as lead, calcium and barium, soadding a little bit of chromium isn'tgoing to do any harm. The oil andwaste acid are mixed and allowed toseparate into sludge and treated oil.The sludge is very acidic and normallycontains about 10000-20000 ppmlead and varying amou nts of otherheavy metals. But now we have enriched it with 2% chromium.

The problem now is to separate themetals from the acid sludge. If weneutralize the acid sludge with ammonium hydroxide, we make ammonium sulfate, a marketable agricultural fertilizer. The fertilizer can besold directly or returned to the am-

monia producer for credit, and thefilter cake, which contains a rich coneentration of heavy metals, primarilylead and chromium, can be profitablyprocessed for metal recovery. Recycling possibilities such as these are athand. The problem is getting somebody to do it.

Another tough example of a wasteneeding innovative thinking is a wastemixture called mixed acid etch. Theetch is used in the semiconductor industry to process so-called siliconwafers. It should be called "theseven-year-etch" because it justdoesn't go away. This material contains 60% nitric acid, 20% hydronuoric, and 20% acetic acid. This waste isextremely dangerous, but when handled correctly, "it just lays down androlls over."

The secret is to mix it with lime oracetylene lime plus calcium hydroxide-a waste stream coming from themanufacture of acetylene from calcium carbide. Lime neutralizes the acidsand, after treatment, we have a solution containing calcium nitrate, calcium nuoride, and calcium acetate.Calcium nitrate is a first-class fertilizer. It commands a premium priceand is used on golf courses and by lettuce growers.

The second useful product generated by this process is calcium acetate.The calcium acetate in the neutralizedacid etch behaves in a manner similarto lime or gypsum in the soil, but is fastacting because, as a liquid, it penetrates the soil better than gypsum,which requires tilling to be effective.

The third useful product generatedby this treatment is caleium nuoride.This material is useful in cementmanufacture and as a raw material forhydronuoric acid manufacture. In thelatter use, high-grade calcium nuoridebrings $200-300 per ton.

The last category involves thosematerials that no one wants to recover.This category includes ehemical car-einogens, polychlorobiphenyls(PCB's), dibromochloropropane(DBCP), DDT, and other materials,which, when buried, wait in their subterranean lair for the opportunity torear their ugly heads and plague ourenvironment sometime in the future.These materials should be destroyed inan incinerator capable of eradicatingthem forever. But even these materials,if properly handled, can be of somevalue as fuels.

PCB's and DDT solutions can beincinerated in cement kilns, which areideal for this purpose. The name temperature of the kilns are in excess of2000 0 F and the residence time is long.The hydrochloric acid that results

from the burning of these chlorinatedmaterials reacts with some of thelimestone that is used to make cement.This reaction has the desirable effectof reducing the free alkalinity in thecement, and the caleium chloride thatis formed is useful in controlling the settime and temperature of the cement.

A one-man effortAs previously stated, the Depart

ment of Health Services' WasteRecycle Program has been a one-manpilot effort in San Francisco Bay Area.The primary approach has been detailed technical personal interviewswith industries. This is a time-consuming job, but it is more productivethan questionnaires because it allowsthe interviewer to follow unexpectedleads as they are generated. A low-key,fee-free state-controlled waste brokerage office can be greatly instrumental in forestalling the tremendousamount of waste that is now going intodisposal sites.

The State of California has enacteda law, AB 1593, which among otherprovisions, requires the disposer tojustify not having recycled recoverable,useful waste products. It also mandatesthe recovery and recycle of usablematerials whenever it is economicallypossible. Chapter 6.5, Article 7, 25170of the California Health & SafetyCode calls for the investigation of themarket potential, and the feasibility ofusing hazardous wastes and the recovery of resources from hazardouswastes. The law further addresses itselfto the promotion of recycling and recovery of resources from hazardouswaste, and to the establishment of aclearinghouse to assist in the recoveryof useful wastes.

It is clear that California is intent onapplying a program that has beendemonstrated to offer great incentivesfor conservation and environmentalprotection, as well as economic profitability for those who participate. Theinitial success of our low-key effortsassures us that the goals of the LockyerBill, AB 1593, will be attained.

Carl G. Schwarzer is a waste managementspecialist with the state ofCalifomia. Hehas been iI/valved iI/the developmel/t ofaprogram for reusil/g iI/dustrial discards.

Coordinaled by LRE


ISPS:Critiqueofproposed I'Illemaking

The control technology issues are highlighted for therevision ofnew source performance standards

for electric utility steam-generating units,which EPA is expected to finalize next month

172 Environmental Science & Technology 0013-936X/79/0913-0172$01.0010 © 1979 American Chemical Society

NO,

Pollutant

SOlPM

Robert W. DunlapBarbara J. Goldsmith

t:nuironmental Research &Technology, Inc. (/::RT)Concord, Mass. 01742

On September 19, 1978, the Environmental Protection Agency (EPA)published proposed New Source Performance Standards (NSPS) forelectric utility steam-generating units(43 FR42154).lnthepreamblctotheproposed rulemaking, EPA discussedseveral alternate standards for sulfurdioxide (SOl)' particulate matter(PM), and nitrogen oxides (NO,). Theagency stated that they would continueto examine the various options possiblefor the final standard during the 60day public comment period on theproposal, since all the data necessaryfor final rulemaking were not yetavailable. EPA held public hearings onthe proposed standards on December12-13, 1978 and will promulgate finalregulations in March 1979. This article presents the proposed standardsand discusses the technological optionsavailable to meet these standards.

BackgroundUnder Sec. III of the Clean Air

Act, NSPS are required to be appliednationwide to specific source categories. The first new source standard forsteam generators was established onDecember 23, 1971 for three criteriapollutants: SOl, NO" and PM. Anemissions limitation was required foreach pollutant, as follows:

Emissions limitations(Ib/million Btu)

Solid fucl I.iquid fucl1.2 0.80

0.10 0.10(20% opacity) (20% opacity)

0.70 0.30

The 1.2 Ib/million Btu emission levelfor SOl allowed sources to comply byeither burning low-sulfur fucl or usinga technological system of control inconjunction with burning higher-sulfurfuels.

On August 6, 1976, the Sierra Clubpetitioned EPA to revise the standardfor SOl to renect changes in controltechnology that had occurred since theoriginal standard had been promulgated. On August 7, 1977, the 1977Amendments to the Clean Air Act,containing major changes in federalregulation of air pollution, were signedinto law. In particular, with respect toelectric utility steam generators, theAmendments require that EPA issue

revised NSPS within one year. TheAct mandates that the NSPS revisionfor electric utility steam generators:

• renect application of the besttechnological system of contilll/ousemission reduction that EPA determines has been adequately demonstrated,

• establish a limitation 011 maximum allowable emissions that EPAdetermines is "achievable,"

• require "a percelltage reductionill emissiolls, " and

• take into consideration cost,non-air-quality health and environmental impacts, and energy requirements. The September 19, 1975 EPAproposal was published in response tothe 1976 Sierra Club petition as wellas the requirements of the Clean AirAct.

The standards shown in Table Iwould apply to new, modified, or reconstructed units on which construction is begun after September 18,1978, and that arc capable of firingmore than 73 mcgawatts (MW) ofheat input (250 million Btu per hour).The standards include both a limitation on the maximum rate of emissionsand a percent reduction in total emissions. Separate standards for coal-,gas-, and oil-fired units were established.

Technological issuesSeveral of the most important issues

that have arisen in the standard-settingprocess for the revised NSPS forelectric utility steam generators arcassociated with specific emission limitation/percentage reduction requirements for SOl, PM, and NO"and the control technologies availableto meet the standards. The majortechnology-related issues associatedwith the proposed standards include:

• sulfur dioxide standard: technological feasibility of meeting theemission reduction/averaging timerequirements proposed in the standardfor boilers burning various types ofcoal

• particulate standard: adequatedemonstration of available controltechnology (electrostatic precipitators,baghouses) to meet the proposedstandard; and potential adverse impacts of FG D systems on particulatecontrol levels (acid mist formation)

• nitrogen oxides standard: statusof combustion modifications for NO,control.

The S02 standard

Debate on the appropriateness ofthe SO, standard has centered on thethree k~y elements of the standard andtheir alternatives: the 85% uniform

percentage reduction requirement, the0.2 Ib/million Btu "emissions noor,"and the 1.2Ib/million Btu "emissionsceiling." The preamble to the proposedrulemaking specified alternativesbeing considered by EPA; these aredisplayed by a graph in Figure I.

EPA has proposed an 85% reductionrequirement for sulfur dioxide emissions (24-h average) with 75% reduction allowed no more than three daysper month. This requirement isequivalent to long-term removal efficiencies at or above 90%.

The Department of Energy (DOE)and the electric utility industry haveboth argued strongly for percentagereduction requirements less stringentthan this for low- and medium-sulfurcoals. The Natural Resources DefenseCouncil (NRDC) and other environmentalist groups, on the other hand,have argued strongly for more stringent percentage reduction requirements, such as a 90% (24-h average)requirement and an emissions limitation ceiling less than 1.2 Ib per millionBtu.

EPA has proposed that the standardinclude a maximum control level(known as an "emissions noor") of 0.2Ib/million Btu below which no percentage reduction requirement wouldapply. A control level of 0.2 Ib wouldrequire almost all coal-fired plants(regardless of the type of coal burned)to meet the 85% reduction (24-h average) requirement-including plantsburning low-sulfur coal. Hence, EPA'sproposed S02 standard is commonlyreferred to as the "full control" option.

On the other hand, specification ofa higher maximum control level suchas 0.8 Ib would permit certain plantsfiring low-sulfur coal to reduce theiremissions by less than 85% without theneed for full scrubbing; this has beentermed a "partial control" option.Figure I shows two partial controlregulatory options that have beensuggested. Both require some percentage reduction at all emission levels,but these would be non-uniform reductions.

One option, suggested by DOE, establishes a minimum 33% reductionrequirement below the 0.8 Ib noor;coals with potential emissions between1.2 Ib and 5.3 Ib per million Btu wouldbe governed by percent reduction requirements equivalent to the 0.8 Ibnoor (33 to 85% reduction). Anotherpartial control option, advocated bythe electric utility industry, wouldsubstitute staged percent reductionrequirements for the noor, utilizing aminimum 20% reduction for verylow-sulfur coals, and progressively


TABlE 1

• A SOII"ce-spec1l1c opacity standard may be established If opacity Is >20 % 8\1811 when complyingwith the particulate emission limitation.• UmItations (fuel.speclflc) for liquid and geseous IueIs are ooc:hanged from the 1971 standard exceptas above. Required percent reductions: 70% for liquid fuels. 75% for gaseous fuels.C EPA (In consultation with DOE) would Issue commercial demonstration permits for the rlrSt threelull-scale demonstration facilities of each of the following: solvent-<elined coel, atmospheric andp1'8SSlI'lzed fluidlzecl-bed combustion, coal liquefaction. For soIvent-<efined coal and fluidized bedcombustion, 80% reduction of S02 (2441 average) is allowed with emission limitations lor PM andNO; as above. For coelliquetaclion, an NO, emission I:mltatlon of 0.7 Ib/MM Btu Is requlred. Additional permits up to a maximum ot 15 000 MW equivalent of collective gen«ating capacity maybe Issued If required. Subsequent facilities would be required to IMe1 the NSPS as above.

Although a number of interrelatedtechnical issues are involved, theprincipal issue associated with theproposed standard concerns the specification of a maximum level of percentage S02 removal capability andthe averaging time for enforcement.

The two parameters (percent removal/averaging time) are closelylinked, as an examination of Figure 2shows. Here, the probability of meeting 24-h S02 removal efficiencies areplotted for a number of full-scale U.S.scrubber installations (EPA data,drawn from the supplemental background information document for theS02 standard). For example, for oneperiod involving 25 days of data, theMitchell station scrubber (WellmanLord system) had about a 10% probability of being less than 87% efficientand a 50% probability of being lessthan 90% efficient. This scrubber alsoshowed greater than 92% efficiencyabout 10% of the time.

For the time period studied, then,the Mitchell scrubber satisfied EPA'ssuggested daily percent removal standard (85% removal except for 3 daysper month); this scrubber also satisfieda longer term (here, 25 days) 90% removal standard. Other scrubber performance data shown on this plot indicate better performance by theEddystone station scrubber (magnesium oxide system; 8 days of data), andpoorer performance by the BruceMansfield scrubber (thiosorbic limesystem; II days of data for Test II, 20days of data for Test I) and the CaneRun scrubber (carbide lime system; 89days of data). EPA's projection of future FGD performance capabilities isshown on Figure 2 as the "Line ofImproved Performance."

This projected performance capability is based on data assembled at the10-MW Shawnee prototype facility,and on observations at full-scalescrubber facilities in the U.S. andJapan, including facilities for whichdata are displayed in Figure 2. Notethal none of the scrubber systems referenced in Figure 2 represent conventional lime/limestone systems, thebase technology invoked by the standards.

Although FGD performance efficiency for a given averaging time canprobably best be stated in these probabilistic terms, system performance istypically cited only with terms such as"90% efficiency," without reference tothe averaging time over which thiscapability has been demonstrated. Inaddition, past vendor performanceguarantees have generally been basedon short-term acceptance tests (6-8 hduration), not on system performance

dard, the Agency has stated it willcontinue to examine the need for exemptions from the ceiling and the appropriateness of specifying morestringent maximum allowable emission levels (such as 1.0 or 0.8 Ib permillion Btu). EPA selection of the 1.2Ib/3-day exemption ceiling is basedupon present estimates of the potentialimpact of such a ceiling on nationaland regional coal production.

Based on a modeling assessment,EPA believes the proposed limitationwith exemptions will allow the use ofsubstantial Midwestern coal reserves.Without exemptions, use of these reserves might be precluded, even if coalcleaning were used as a precombustiontreatment. Additional modeling workto consider such impacts more precisely was scheduled for late 1978under joint DOE/EPA sponsorship.

Flue gas desulfurization capabilitiesAssessment of the technological

capabilities of FGD systems (for example, scrubbers) to remove S02 fromnue gases has been the subject of numerous studies over the past decade.

_1ImIl<I_Solid fuels 1.2Ib/MM Btu (24-h 85% averaged dally (24-h

compliance averaging compliance averagingperi~xemption perlod-75% exemptionallowed 3 days/month) allowed 3 days/month)

Gaseous/liquid 0.8 Ib/MM Btu 85% averaged daily (75%fuels allowed 3 days/month)

Solid fuels Opacity of emissions 99%limited to 20% (6 minaverage)-27%allowed 6 min/h a

Gaseous/liquid 0.03 Ib/MM Btu 70% (oil only)fuels

Bituminous 0.6 Ib/MM Btu 65%coal

Subbituminous 0.5 Ib/MM Btu 65%coal, shaleoil, coal-derived fuel

higher percent reduction requirementsup to 85% removal for a coal with potential S02 emissions of 8 Ib per million Btu.

EPA has proposed an emissions"ceiling" for coal-fired units of 1.2Ib/million Btu heat input (24-h average), except for up to three days permonth coincident with the three daysof 75% control in the percent S02 reduction standard. The emissions ceiling retains the 1.2 Ib per million Btustandard in the current NSPS, but thecurrent standard does not requirecontinuous 24-h compliance. (40 CFR60 Subpart D requires reporting ofexcess emissions when average emissions over any three-hour period exceed the 1.2 Ib standard. Compliance,however, is based on a short-termperformance test conducted after system start-up and at such other times asmay be required by the Administrator.) Hence, the proposed emissionsceiling represents a more stringentemission limitation than the currentstandard because of the 24-h averagingtime.

In the notice to the proposed stan-


1.6r----.::----;:------:--------------,

Lb,. SO,lmillion Btu(allowable)

FIGURE 1

Graphical comparison of S02 control alternatives

1412108

FG D technology. Perhaps the mostcritical challenge to be faced prior tofinal NSPS promulgation is the resolution of these divergent interpretations of FGD capability. CurrentDOE/EPA agreement on the linkage(in a probabilistic sense) betweenpercent S02 removal and averagingtime effects is an important step forward, inasmuch as scrubber performance data can now be compared overdifferent averaging times.

The PM standard

The particulate matter standard hasbeen proposed in three parts:

• an emission limitation of 0.03Ib/million Btu

• an opacity standard unchangedfrom the standard now in force

• a percentage reduction requirement defined so that compliance withthe emission limitation will result incompliance with the percentage reduction requirement. Hence, the oneissue associated with the rulemakingis the proposed emission limitation.Two principal factors associated withthe 0.03 Ib limit have received attention; each is briefly discussed here .

PM control technology capabilities

EPA has based its proposed standards on the performance of a "welldesigned and operated baghouse orelectrostatic precipitator (ESP)." TheAgency's determination that thesecontrol systems are the best adequatelydemonstrated systems for particulatecontrol at these emission levels wasbased on a number of factors, including:

• analysis of emission test results

90% (averaged monthly,equivalent to 85% daily)

6

Lb,. SO,lmillion Btu (potential)

at the levels required by EPA's proposed standard. DOE makes the engineering judgment that the proposalfor 85% removal averaged daily"pushes FG D technology too fast."

The electric utility industry, asrepresented by the Utility Air Regulatory Group (UARG), also questionsEPA's conclusions regarding projectedFG D performance capability, butagrees that the revised NSPS shouldrequire the use of FGD or equivalentcontrol technologies for new coal-firedplants. The UARG percentage reduction proposal (Figure J) is partiallybased on UARG's belief that a slidingscale requirement affords teehnological flexibility for new plants that burnhigh-sulfur coal. UARG argues thatthis requirement would allow plantsthat burn high-sulfur coal and "findthe scrubber does not meet design expectations" to shift to a slightly lowersulfur coal with a lower percent S02removal standard, thereby ensuringcompliance.

Environmental groups, on the otherhand, argue that FGD technologycapabilities are greater than the capability demanded by EPA's proposal.The Natural Resources DefenseCouncil, Inc. (N RDC), for example,states that the technological evidencenow available "indicates that scrubbers can achieve, and have routinelyand reliably achieved, in a cost-effective manner, removal efficiences inexcess of 90%, averaged over moredemanding averaging times than aday."

The technological capability issuepivots on differing interpretations ofthe existing data base for operational

over continuously sequential 24-hourtests. As a result, confusion exists regarding the performance capabilitiesof FG D systems currently in service,and there is a general difficulty incomparing the performance of variousFGD systems.

Much debate centers about the interpretation of FGD performance datagathered at various prototype, pilotscale, and full-scale facilities. Valuabledesign and performance capabilityinformation can be gained in each sizerange. Controversy, however, centersabout the use of information gatheredat prototype and pilot scales to inferperformance capabilities at full-scalefacilities. The fundamental questionshere are what constitutes a reliabledesign basis for full-scale FG D systemapplications, and whether such a design basis has been developed, at theperformance levels demanded by thestandard.

EPA's proposed 85% S02 removalstandard (24-h averaging time, withthree exemptions allowed per monthdown to 75%) is based on specificAgency assertions that:

• An FGD system that couldachieve a long-term mean S02 removal of 92% would comply with theproposed 24-h requirement (the "lineof improved performance" on Figure2).

• Lime/limestone FG D systemscan achieve such long-term S02 removal capabilities, if certain changes(for example, improved pH controls)are made in design, operation, andmaintenance practices. With morereactive absorbents, even greaterlong-term removal capabilities can beaehieved.The first of these EPA conclusions isbased on EPA's observations and statistical analysis of continuous monitoring data at full-scale FG D facilities(Figure 2). The second EPA conclusion is based on EPA's projection ofFGD performance capability, from thedata base assembled at the 10-MWShawnee prototype facility and fromobservations at full-scale facilities,both U.S. and Japanese.

DOE has recognized that long-termaverage performance in excess of 90%is necessary to guarantee daily attainment of an 85% SO? removalstandard (the first of EPA;s assumptions). However, DOE does not agreethat FGD technology will performreliably at such levels as early as 1983,when new plants will begin to operateunder the revised standard.

The Department has concluded thatdata on currently operating FGD systems do not provide a suitable designbasis to predict scrubber performance


Probability, percent

FIGURE 2

FGD 24-h average efficiency distribution

FGD system parameters

Mean Inlet SOt No. 01VIUny/Stlilion FGO Type - Iblmlillon Btu T..tingOll~

Philadelphia Electri<:!MgO 325/3 5.1Eddystone

Northern Indiana PublicServlceJMitchell Wellman - Lord 115 6.3 25

Louisville Gas & EleetriclCane Run Carbide Urne 181 5.75 89

Pennsytvama Power CompanylThiosorbic Ume 825 6.3 20Bruce Mansfield (Test I)

Pennsylvania Power Company/ThiosorbicUme 825 5.4 11Bruce Mansfield (Test II)

DOE has expressed concern that theproposed standard would preclude theuse of ESPs on low-sulfur coal, andbaghouse technology has not beenadequately demonstrated for utilityscale application. The Departmentsuggests that the standard be set at ahigher level (0.05-0.08 Ib) whichwould not preclude the use of ESPs.

The electric utility industry believesthat baghouses are not a demonstratedtechnology for large coal-fired units,particularly those firing higher sulfurcoals; that no long-term data exist onbag life at large bituminous coal-firedelectric generating facilities, and thatthere are "no grounds for confidence"that the limited operating experiencegained to date on small boilers can be"realistically extrapolated to predictthe performance of much larger installations on utility boilers firing coalswith widely varying characteristics."The industry also suggests that whencosts are taken into account, ESPs arenot adequately demonstrated forachieving a 0.03 standard. UARG hastherefore recommended an emissionlimitation standard in the range0.05-0.08 lb.

The central issue here, similar to theargument concerning S02 scrubbercapabilities, is the issue of what constitutes a reliable commercial designbase for future large-scale applicationsof particulate control units for commercial utility boilers. For the case offabric filter controls, two large systemshave recently been activated in theWest (the 750-MW Monticello Station of Texas Power and Light Company and the 350-MW HarringtonStation of Southwestern Public ServiceCompany). EPA had plans to testemissions at the Harrington Station ofSouthwestern Public Service Companyin late 1978 and these tests are expected to inOuence the rulemaking.

FG D systems & PM emissions

In setting the particulate matterstandard, EPA considered a higheremission limitation (0.05 Ib) that theAgency believed could be met by wetparticulate matter scrubbers. Thisoption was rejected in favor of the 0.03Ib limit; the proposed standard willeffectively require aflue gas train inwhich particulate collection (by baghouse or ESP) precedes S02 removal(/ypically by a wet scrubber).

Since there were no existing plantsavailable for testing where a high-efficiency ESP or baghouse was followedby an FGD system, the proposedstandards are based on emissionmeasurements taken at particulatecOlltrol devices prior to any FGD/rea/melll. Compliance with the stan-

ing pulverized coal. The ESP testswere performed on larger units (461300 MW) with seven tests on unitsrepresenting "difficult particulateemission control cases." Typically, thelatter tests were on units firing lowsulfur coal, where high efficiency collection of particulates by ESP units ismore difficult (one of these units metthe proposed standard).

Based on these emission tests andprojections of performance, EPA hasconcluded that ESPs can be used forhigh-sulfur coal applications to meetthe proposed standards at reasonablecosts. The Agency also concludes thata baghouse control system could beapplied on utility-size facilities firinglow-sulfur coal at a lower cost than anESP.

97

C 962l 95~

98

from steam generators employing either fabric filters (baghouses) or ESPsfor particulate control

• consideration of the technologicalbarriers to operation of baghouses orESPs at the performance level chosen

• consideration of current construction or commitments for construction of fabric filter systems forcoal-fired steam generators.

EPA's emission tests of existingbaghouses or ESPs have indicated thatsome existing units (6 of 8 baghouseunits on coal-fired plants; 9 of 22 ESPunits on coal-fired plants) would meetthe proposed emission limitation. Thebaghouse tests were performed onrelatively small units (6-44 MW), including one 44-MW utility boiler fir-


dard, however, will be based on measurements taken at the outlet of thenue gas treatment train (after theFGD unit).

There is a potential for FG D units toincrease particulate cmissions, eitherby entrainment of scrubber liquids atthe mist eliminator, or by particulatematter generation through condensation of sulfuric acid mist. On the otherhand, FGD units may also removeadditional particulates from the nuegas stream after primary removal byan ESP or baghouse.

Tests conducted by the Agency onFe; D units at plants firing low-sulfurcoal, lead EPA to conclude that theproposed particulate matter standardcan be met at such plants. In the casewhere an FG D system is used withhigher sulfur coal, EPA suggests sufficient data arc not yet available tofully assess the potential of the FG Dunit to increase particulate emissions.EPA has scheduled tests at the Louisville Gas and Electric Cane Run Station to investigate this subject, andThese TesTs /l1ll)' in/luence The I'ulemaking.

The NO, standardEPA's proposed NO, standards in

corporate separate emission limitationsfor:

• the combustion of subbituminouscoal, shale oil, and any solid, liquid, orgaseous fuel derived from coal (0.5Ib/million Btu)

• the combustion of bituminouscoal (0.6 Ib/million Btu).

Standards for units that burn gaseous and liquid fuels not derived fromcoal arc unchanged from those originally promulgated in 1971 (40 CFR60, Subpart D); standards for ligniteare unchanged from those promulgated in early 1978 (43 FR 9276); theexemption of coal refuse from theSubpart D standards is continued.Percent reduction requirements forNO, arc proposed for the various fuelcategories, but these requirements arcnot controlling. Hence issues associated with this part of the rulemakingarc concerned with the new 0.5 and 0.6Ib/million Btu emission limitations

Status of NO, controlThe new sta nda rds are based on

cmission limitations achievablethrough com bustion modi fica tiontcchniques. Thesc techniques limitNO, formation in the boiler by nametcmperatures and by minimizing theavailability of oxygen during combustion. However. there arc potentialside effects as a result of the modifications including boiler tube wastage(corrosion). slagging. increased emis-

sions of other pollutants, boiler efficiency losses, and possible operatinghazards (explosions). EPA believesonly boiler tube wastage could be apotential problem at the NO, emissionlevels necessary to meet the proposedstandards.

Viable techniques for reducing NO,emissions via combustion modificationinelude staged combustion, use of lowexcess air, and use of reduced heatrelease designs. Staged combustion isaccomplished by redistributing the airnow to the boiler such that a coolersecondary combustion zone is encountered by the combustion gasesafter they leave the name front. Lowexcess air reduces the oxygen availablefor NO, formation and is accomplished via operational adjustments.

Reduced heat release lowers combustion gas temperature and is accomplished by increasing the combustion chamber size for a given firingrate. Combinations of these techniquesarc used by the four major boilermanufacturers (Combustion Engineering Inc., Babcock and WilcoxCompany, Foster Wheeler Corporation, and Riley Stoker) to achieve lowNO, emission operation.

Based on emission test results andan assessment of the technology, EPAhas concluded that if the potential sideeffects associated with low NO, operation were not considered, it wouldbe reasonable to establish an NO,emission limit for pulverized coal-firedunits at 0.5 Ib/million Btu heatinput.

However, for high-sulfur Easterncoals where tube wastage is a potentialproblem, EPA does not believe anemission limit below the proposed 0.6Ib level would be reasonable, eventhough emission data alone would tendto support a lower limit. For low-rankWestern coals, where there is a muchsmaller tube wastage potential at lowNO, levels, EPA proposes the 0.5Ib/million Btu emission limit.

UARG suggests that available datademonstrate that only one manufacturer (Combustion Engineering) couldmeet the proposed standards on acontinuous basis. The industry hasexpressed concern that the proposedstandards could therefore have anantieompetitive effect.

Manufacturer capabilitiesBased on a study by a consultant

(K VB), the industry has assessed eachboiler manufacturer's capabilities asfollows:

• Combustion Engineering (CE):Although some units subject to currentNSPS have emissions at or above therecommended limitations, CE's unique

tangential fired boilers have thegreatest potential for low NO, emissions;

• Babcock and Wilcox (B& W):This manufacturer should be able toachieve the 0.6 and 0.5 Ib emissionlimitations for bituminous and subbituminous coal with its wall-firedboilers, new dual register burners, andredesigned windbox. However, moredevelopment and demonstration workwill need to be accomplished to confirm this;

• Foster Wheeler (FW): No dataexist on FW units on subbituminouscoal. The one unit firing bituminouscoal will marginally meet a 0.6 Ib permillion Btu limitation. FW is in theprocess of developing a new low NO,burner, but has not yet demonstratedits effectiveness;

• Riley Stoker (RS): One emissionstest indicated that the emission limitation on subbituminous coal may beachievable, while two other tests indicate the emission limitation on bituminous coal cannot presently be met.With Riley's present burner and boilerdesign, the emission limitation on either coal may be difficult to achieve.

EPA has examined the impact ofcombustion modifications for NO,control on boiler tube corrosion; theAgency's assessment differs from theUARG position. Through an engineering contractor, EPA has experimentally measured corrosion rates byexposing corrosion coupons installedat the end of probes and inserted into"vulnerable" areas of the furnace bothunder baseline and low NO, firingconditions. The total exposure of thecoupons for each test was 300 hours.

An assortment of boilers was examined, including B& W, CE, and FWdesigns. Based on the results of thesestudies and other design information,EPA believes that new units thatwould be designed to comply with theproposed NO, emission limits wouldnot expcriehce serious tube wastage forthe following reasons:

• Coupon corrosion tests indicatethat tube wastage is not significantlyaccelerated during low NO, operationof modern Combustion Engineeringboilers. CE has stated that its modernunits would be capable of achieving theproposed standards for both easternbituminous and low rank western coalsand lignite;

• Babcock and Wileox has designeda new burner that will permit a furnaceto be maintained in an oxidizing environment, thus minimizing the potentialfor furnace wall corrosion when highsulfur bituminous coal is burned;

• Foster Wheeler and Riley Stokerare developing new burners that may


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AcknowledgmentThis article is a condensation of a

briefing paper prepared for the Department of Energy Assistant Secretary forEnvironment by Dr. Robert W. Dunlap,Dr. David v. Nakles, Barbara J. Goldsmith (ERT), and Roger Strelow (Leva.Hawes, Symington, Martin, and Oppenheimer) with the assistance of Karen M.Higgs (ERT) and Andrew D. Weissman(Leva, Hawes, Symington, Martin, andOpenheimer).

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Sources and Fates of Aromatic Compounds in Urban Stormwater Runoff

Moira J. MacKenzie'

Surveillance and Analysis Division, Environmental Protection Agency Region II, Edison, N.J. 08817

Joseph V. Hunter

Environmental Science Department, Rutgers University, New Brunswick, N,J. 08814

• Petroleum-derived aromatic hydrocarbons and associatedsulfur compounds in urban stormwater runoff and DelawareRiver sediment samples were characterized using a gas chromatograph equipped with a flame ionization/sulfur specificflame photometric detector system. Total petroleum hydrocarbon concentrations were determined gravimetrically instormwater emanating from a northern Philadelphian stormsewer. Comparison of hydrocarbon and sulfur fingerprints ofthe aromatic fractions of environmental samples to referenceoils indicated that crankcase oil was the most likely source ofaromatics in stormwater runoff. A weathering study on usedcrankcase oil showed a loss of diaromatics accounting for theirabsence in the environmental samples. A method of transportby which land-based oil enters the aquatic environment andreceiving water sediments was proposed. Dibenzothiophenewas identified in the environmental samples by retention timeand mass spectrometry. Concentrations of dibenzothiophenein stormwater runoff ranged from 44.2 to 62.3 ng/L.

The ever increasing dependence of today's society upon atechnology based on petroleum fuels and products has led towidespread oil pollution of the environment. Until recently,the study of oil pollution focused on oil spills and recordedsources of pollution such as refinery and industrial effluents.Unrecorded sources of land-based oil have now been shownto contribute a significant amount of petroleum-derived hydrocarbons to the aquatic environment via stormwater runoff(1, 2). According to Brummage (3), disposal of used lubricating oils may be the most significant source of inland oilpollution. This is supported by an estimation that 1.1 billiongallons of automobile and industrial lubricants are releasedto the environment annually (4). Unrecorded sources of pollution such as stormwater would be expected to reflect a significant amount of these lubricants.

The nature and source of the petroleum components instormwater may be examined by gas chromatography to givea characteristic hydrocarbon fingerprint. The use of a sulfurspecific flame photometric detector in conjunction with aflame ionization detector gives additional information on thesulfur components which are usually "lost" on the hydrocarbon envelope. Although sulfur compounds represent, at themost, only 4% of a petroleum oil, Adlard et al. (5), Garza andMuth (6), and Warner (7) have shown that sulfur fingerprintscan be a valuable aid in oil characterization and source correlation.

While petroleum studies have been primarily concernedwith the aliphatic hydrocarbon fraction (2), the majority of

0013-936X179/0913-0179$01.00/0 © 1979 American Chemical Society

the sulfur compounds occur in the less frequently studiedaromatic fraction. According to Martin and Grant (8), thesulfur aromatics in petroleum oil are predominantly thiophenes. Warner (7) identified benzothiophene, dibenzothiophene, naphthobenzothiophene, and their alkyl derivativesin oils and marine samples,

The present study was directed toward the characterization,source, and probable fa te of aromatic sulfur compounds inpetroleum oils from stormwater runoff. Gas chromatographicfingerprints of the aromatic fractions from several environmental samples and standard oils were obtained using a dualflame ionization/flame photometric detector system. Emphasis was placed on the identification and quantitation ofaromatic compounds in urban runoff emanating from a stormsewer in northern Philadelphia, discharging to the DelawareRiver.

Sampling and Experimental Methods

The drainage basin sampled encompassed an urban areaof 1520 acres. Land use data and a thorough description ofsampling technique may be found elsewhere (1). Briefly, thestorm events were sampled every 5 min for the duration of thestorm. Samples were composited on a flow-proportionate basisand analyzed according to the scheme outlined in Figure 1.

The particulate and aqueous phases were separated by aSharples Type T -1 continuous centrifuge at 15 000 rpm. Theparticulates, greater than l/Lm, were dried at 40°C for 24 h.The soluble fraction was gravity fed to an activated carboncolumn (40 g, 32.0 X 2.5 cm bed) at a flow rate of 10 mL/min,through an all-glass system. Following adsorption, the carbonwas dried at 40°C for 24 h.

The soluble organics were extracted from the activatedcarbon by soxhlet extraction. The dried particulate fractionwas also soxhlet extracted to remove adsorbed organics. Eachfraction was successively extracted for 6 h with 250 mL ofhexane, then benzene, and finally chloroform. This resultedin three extracts for the soluble and three for the particulate.All solvents were pesticide grade and all glassware was solventrinsed and baked at 250°C.

To examine the petroleum-derived aromatic hydrocarbonsand aromatic sulfur com pounds a silica gel separation schemewas employed (9). The particulate and soluble fractions wereevaporated to dryness on 45 mL of silica gel (activated at 225°C for 48 h) on a rotary evaporator at 45°C. The silica gel wascharged to a 67.5 X 20 cm i.d. Pyrex column with a fritted glassdisk. The silica gel was first eluted with 80 mL of hexane toobtain the aliphatic hydrocarbons and then eluted with 80 mLof benzene to obtain the aromatic hydrocarbon and sulfur


WaterISample

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ICarbon Adsorption

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Siliel Gel

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Eluate Eluaje

Aliphatic AromaticWeight Weight

IIR

IFree Sulfur Removal

IGLC Analysis of

Particulate Aromatics

Figure 1. Analytical scheme

compounds. The eluates were evaporated to dryness underreduced pressure and their weight recorded. Concentrationsof total petroleum-derived hydrocarbons in stormwater weredetermined based on the sum of the aliphatic and aromaticfractions in the soluble and particulate fractions.

Sediment samples from the Delaware River were randomlycollected around the Marcus Hook area, south of Philadelphia,and composited. The samples were oven dried and groundwith a mortar and pestle. Five hundred grams was soxhletextracted with 1000 mL of chloroform for 72 h. Five hundredmilliliters of the extract was evaporated to dryness on activated silica gel. The above elution was performed to obtainthe aromatics.

Standard oil samples were furnished by the U.S. CoastGuard Research and Development Center, Groton, Conn. Theused crankcase oil was obtained from a local garage. All oilswere subjected to the above·mentioned separation scheme.

To study the effects of weathering on used crankcase oil,a Pyrex pan was coated with 100 mL of the oil and placed onthe roof of the lab for 14 days in June. The pan was situatedsuch that it received at least 10 h of sunlight a day. On the 14thday the oil residue was rinsed from the pan with methylenechloride and adsorbed to silica gel by rotary evaporation. Thearomatic bydrocarbons and sulfur compounds were subsequently separated by elution.

Gas chromatographic analyses were performed on a Tracor


222 gas chromatograph equipped with a Tracor FID/FPD(sulfur mode) dual detector system. A dual pen recorder allowed for simultaneous response. A 6-ft, 4-mm i.d. glass column packed with 3% OV-17 on 80/100 mesh Supelcoport wasprogrammed from 125 to 275°C for fingerprint analyses.

The identification of benzothiophene, dibenzothiophene,and the triaromatics was based on GC retention time data andmass spectrometry, using a Finnigan 3200 GC/MS equippedwith a Systems Industries 150 data system. Electron impactas well as chemical ionization spectra were obtained for confirmation. To quantitate dibenzothiophene in the stormwatersamples, a standard curve of dibenzothiophene was run using50 I'g of dodecyl sulfide as an internal standard (Figure 2). Allsamples were quantitated with the same amount of internalstandard. Prior to all injections, the aromatic fractions wereresolubilized in methylene chloride and passed through acopper column to eliminate the possibility of free sulfur contamination (10).

Results and Discussion

Concentrations of aromatic hydrocarbons in stormwaterwere determined for three different rain events and may befound in Table I. Gas chromatographic analyses of the solublearomatics indicated that there was an absence of sulfur compounds in this phase. It may be noted that about 95% of tbetotal aromatics was associated with the particulates, and

Table I. Petroleum Hydrocarbons in Stormwater Samples

storm event discharge volume of hydrocarbondate storm, 106 L type

4/3/75 1.726 aromatics

total petroleumhydrocarbons

8/16/75 11.234 aromaticstotal petroleum

hydrocarbons11/21/75 15.182 aromatics

total petroleumhydrocarbons

associated hydrocarbonsparticulates soluble

mg/L kg/storm mglL kg/storm

1.10 1.89 0.06 0.113.70 6.38 0.34 0.59

1.65 18.54 0.Q7 0.785.06 56.85 0.24 2.69

0.99 15.03 0.04 0.614.08 61.94 0.16 2.43

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DIBENZOTHI OPHE NEFigure 2. Standard curve for the quantitation of dibenzothiophenebyFPD

Figure 3. Gas chromatograms of aromatic hydrocarbons using a flameionization detector

similarity hetween l.he used crankcase oil and the stormwatersample may be noted.

Therefore, while the high boiling, high molecular weightcomponents of several petroleum products may have contributed to the oil pollution in urban runoff, used crankcaseoil appeared to be the most likely contributor based on fingerprint correlation.

The comparison of chromatographic fingerprints is basedon the similarity of origin and weathering effects. A closer lookat the lower boiling diaromatic region revealed that a major

therefore fingerprint analyses for source correlations werebased on the particulate phases of the stormwaters.

To establish the source of oil in urban runoff, the aromaticfractions of various oils were also characterized. Since thesource of oil in urban runoff was land-based, it may be assumed to be characterized by a refined oil. The heavier lubricating and residual fuel oils consist of high boiling compounds and are inherently resistant to extensive weathering,thus making them a prime suspect as a source of oil in urbanrunoff. Residual oils are primarily used for industrial heatingpurposes and are usually a blend of a gas-oil petroleum distillate and the heavy residual oil of a crude. The aromaticfractions of anumber 6 fuel oil and a residual fuel oil werechromatol(raphed and may be seen in Figures 3 and 4. Incontrast,lubricating oils, such as bydraulic and crankcase oils,are distinct distillate cuts of a crude and are generally classified accordinl( to their different viscosities (I J). Fingerprintchromatograms were obtained of the aromatic fractions of aused lube and crankcase oil and a hydraulic oil. The similarities and differences between tbe aromatics of the lube oils andthe environmental samples may be noted in Figures 3 and4.

The value of the sulfur profile is evident in these fingerprintcomparisons. The FlO fingerprints all show a large hydrocarbon envelope and the correlation is obscure. In contrast,the FPD sulfur profiles of the oils are quite different and a

HYDRAULIC OIL

"MINUTES

PARTICULATE FRACTION

1lI2117S STORM

15

MINUTES


Table II. Quantitation of Dibenzothiophene inPhiladelphia Stormwater Runoff

discharge vol. dibenzothiophene, a loading,dale 1 X 106 L ng/l mg/slorm

413/75 1.726 44.2 76.3

8/16/75 11.234 46.1 517.9

11/21/75 15.182 62.3 9458

iJ Concentrations adjusted for percent recovery of compound, 69.7%.

tively unchanged in the environment and prohably undergoconcentration in the sediments.

As previously noted, the lower boiling benzothiophenes(BT) and naphthalelles (N) were present in the used crankcaseuil but absent in stormwater panitlilates and Delaware Kiversediment samples due to weathering. On the other hand, dibenzothiophene (DBT) and phenanthrene and/or anthracenewere present in all samples (see Figure !;). Phenanthrene (P)and anthracene (A) could not be differentiated on the columnlIsed. These chromatograms were obtained by programmingthe colullln frolll 125 to 200 DC. The presence of DBT andnaphlhobenzothiophene in sediment samples has also heenreported by eiger and Blumer (/2) who tentatively identifiedthem in samples t.aken fro III Buzzards Bay, Mass. The identification of the alkyJbenzothiuphenes (('-1 and C-2 BT) anddibenzot.hiophenes «(;-1 DH'I' and C:-2 ))HT) was hased in part.un previuus work by Warner (7), and also on mass spectraldata.

The large unresolved sulfur envelopes noted in Figure 4 arethought to be composed primarily uf four- and five-ringthiophenes as well as aromatic sulfides, thiols, and thiaindansaccurding to Martin and (;rant (1/).

The concentrat.ions of dibenzothiophene in stormwatersamples Illay he fuund in Tahle II. An average of 6V.9% of thedibenzuthiupllene was recuvered hy the analytical method andseparation scheme. The concentrations were adjusted forpercent recovery of the COlllpound. While the concentrationsranged frolll 44.2 t.o (;2.:lng/L, the total luaJing of dibenzothiophene appeared to be exponentially Jependentupon thelutal volume discharged.

Due to t.he polycyclic nat.ure of dibenzothiuphene, its possible carcinogenic and/or mutagenic effects are subject toquestion (/:1). The persistence of this compound as well as thehigher molecular weight condensed thiophenes and otherpolynuclear aromatics suggests their concentrat.ion in theenvironment. While beyond the scope of this study, the

eventual accumulation of polycyclic thiophenes and aromaticsin the sediments may prove toxic to benthic communities.

Cunclusions

According to Giger and Blumer (12), the presence of polynuclear aromatics in sediments may he attributed to manysources. Runoff from the land appears to be a significantsource of these aromatics. Adsorption of polynuclear aromatics to particulate matter and eventual settling of theseparticulates offer a method of transport of land-based oil toreceiving water sediments.

Inland oils, as Brummage (:1) suggests, would be characterized by used automobile and industrial lubricants whichresist extensive weathering in the environment. Specifically,the source of aromatics in stormwater runoff may be attributed primarily to crankcase oil.

Acknowledgments

Thanks are extended to the Surveillance and Analysis Division of the Environmental Protection Agency in Kegion IIfor the use of their mass spectrometers.

Literature Cited

(I) Hunter, J. V., Yu, S. 1.., Whipple, W" ,Jr., Am. Water Hesour.A.,soc. Pwe., No. 20, I62-11 (1975).

(2) Wakeham, S. G., J. Watt'/' Pol/ut. Control Fed., 49, 1680 7( 1977).

(:1) Brummage, K. G., "The Sources or Oil Entering the Sea", in"Ha<.:krounu Papers for a Workshop on Inputs, Fates and Effectsof Petroleum in the Marine Environment", Pi> I -("i. NationalA<:ademy of Science, \Vashingtol1. U.('., 1975.

(4) KP.A. Heport, j,,·nviwn. Sci. 'fe("/II",I" 6,2:, (l9n).(fll Adlard, W. H., Creaser, L. r .. Mathews. P. H. D" Anal. Chem.,

44.64-7:\ (1972),(Ii) (;arza. M. Eo, .Jr.. Muth..J.. Jinvi/'tlll. Sri. 'fedllwl" 8. 249-5:,

( t974).('n \Varner.·J. S .• in "Pro('eedinKs of the l~ri;) Conferelll:e 011 Pn>·

ventilm of Contfl'! of Oil Polillt.ioll ", PP 9/-10 I, American Petroleum Institute, Washington. D,C .. 197:i

(8\ Marlin. H. 1.., Grant, ,J. A., Anal. Chem" :17, fi64··9 (I~lfjf»).

(9) Hosen. A. A., Middleton, F. M., ibid" 27,7904 (19f,;,).(10) Blumer. M., ibid., 2!1, !O:19 4:1 (1~)57).

(11) Kali('hevskv, V. A.. Peters. K H.. in "Petroleum ProductsHandhtH,k", V'. H. (;uthrie, Ed,. pp 21-:l, Mt.:Graw-Hill, New York.N.Y.. 191m.

(11) Gi~er. W., ~luJ11er, M., I-.,'m..'inm. St'i. T{'(·Jwul., 8. 249· ;-):)(I 974 l.

(1:1) HIllmer. M.. Sci. Allier.. 234, :\5 4f, (I m61.

Hf'Ceived {tJt' I'('r'i"II' Ff!!JnUlry 17, IY7X. A('('epled AUMU.'it 7, 197X. The(wllin,..'i ad,'nlJwledt-!,J the support ;!irwn by the NANN J-'ru;':I'ClfH (IfOw Natiot/tli Science I"/lundatio", "The I'drult'um Illdw;try in theII<-I,,//'''/''' I,'sl""ry" (:mnt N". NSF-liNV·/·/·I4XIU/J.


Design and Evaluation of a New Low-Pressure Impactor. 2

Susanne V. Hering and Sheldon K. Friedlander"

California Institute of Technology, Pasadena, Calif. 91125

John J. Collins and L. Willard Richards

Air Monitoring Center, Atomics International Division, Rockwell International, Newbury Park, Calif. 91320

• The last two stages of tbe low-pressure impactor describedin Part 1 of this paper have been calibrated using a laboratory-generated uranine aerosol. An electrostatic classifier wasused to obtain a near-monodisperse aerosol and the depositedmaterial was analyzed by fluorescence. For the final threestages, the particle diameters collected with a 50% efficiencywere found to be 0.12, 0.075, and 0.05 I'm. These cutoff diameters are the aerodynamic particle diameters at the reducedstage pressures; the relation to the particle Stokes diameteris discussed.

A low-pressure impactor has heen developed which is capable of the size segregation of aerosols from O.O.~ to 4.0 I'maerodynamic diameter. The design and previous laboratoryand field evaluation of the impactor have been reportedelsewhere (I). Presented here is the calibration of the 0.05and 0.075-1'01 stages of the impactor using a laboratory-generated uranine aerosol.

The impactor consists of eight single jet stages, samplingat a mass now of 1 L (NTP) per minute (Llmin). Particleslarger than 0.5 I'm in aerodynamic diameter are collected atnear atmospheric pressure using the first four stages of theBattelle (2) impactor (Del ron No. DCI5, Powell, Ohio). Tothis device four low-pressure stages have been added to sizesegregate the smaller aerosol. A critical orifice separating thelow-pressure and atmospheric pressure stage determines thesample rate. The jet diameters and the stagnation pressuresbelow the jet of each stage are listed in Table I.

In designing this impactor, it was desired to have an instrument which has both small cutoffs and which is sufficiently portable for field measurements. As the size of thepump limits tbe flow rate which may be obtained at these lowpressures, the impactor was designed to be compatible withmore sensitive analytical techniques. By using one jet perstage, the aerosol is confined to a small area which, for example, may be directly analyzed for aerosol nitrate or sulfurat the nanogram level (3, 1). For the low-pressure stages tocollect small particles with the mass now of I L/min (NTP)per jet, and also to attain sufficiently high jet Reynoldsnumbers to minimize cross-sensitivity between stages (5), itis necessary to use high jet velocities. The flow in the finalthree stages is compressible; the particle segregation resultsfrom the decrease in pressure rather than a decrease in jetdiameter.

Of interest in the calibration of the impactor is the collectionefficiency of each stage as a function of particle diameter. Fora particular stage, the diameter of a particle which is collectedwith a 50% efficiency is referred to as the cutoff diameter, d,.....In Part 1 (1), the fourth, fifth, and sixth stages of the impactorwere calibrated using monodisperse aerosols of polystyrenelatex spheres. The latex particles on each stage were countedusing an electron microscope. The collection efficiencies werecalculated assuming that all of the aerosol was collected in theimpactor.

It was not possible to calibrate the seventh and eighth impactor stages in this same manner. The number of particlespassing through the impactor to the after-filter could not bedetermined. In addition, the smallest available latex sphere

(0.0881'01 diameter) is larger than the cutoff of the seventhstage. Proper calibration of these final two stages is especiallyimportant because the jet velocities are sonic. If the flow wereincompressible, the cutoff diameters could be calculated fromthe value of the Stokes num ber corresponding to the cutoffsfor the upper stages. For these sonic stages, the flow regimeis sufficiently different that one cannot apply this theory.Experimental evaluation of the cutoffs is necessary.

Experimental

The impactor was calibrated with a sodium fluorescein(uranine) aerosol. A near monodisperse aerosol was obtainedusing a Thermo Systems, Inc., Model 3071 ElectrostaticClassifier (6). The samples were analyzed by fluorescence.

Aerosol Generation. A diagram of the aerosol generationand flow system is shown in Figure 1. The Thermo-Systems,Inc., Model 3075 constant output atomizer (7) contains acritical orifice to control the air now at :l Llmin. Syringepumps were used to feed a solution of 0.05% uranine in halfethanol, half-water at a now rate of 0.59 cm:1/min. The atomizer output was mixed with 11 Llmin of dry air and allowedto equilibrate in a 25-L volume; then 3 Llmin of the dilutedaerosol was dried by three successive diffusion dryers with acombined length of 1:17 cm.

The dried polydisperse aerosol was introduced into the sizeclassifier in which it acquired a bipolar Boltzmann chargedistribution by exposure to an s"Kr source. The aerosol flowof 3 Llmin was then introduced in an annular ring around a20-L/min flow of particle-free sheath air. Positively chargedaerosol is drawn by a cylindrically symmetric electric fieldacross the sheath air flow toward the central collector rod. Byvarying the collector rod voltage, aerosol of a chosen electricalmobility is made to pass through a slit at the base of the rod.Singly charged particles should be of the desired size, but somelarger doubly or triply charged particles will also be found.

In this study, two runs were made with larger aerosols of0.22 and 0.391'01 Stokes diameter. To obtain these aerosols,the aerosol and sheath air flows in the Electrostatic Classifierwere reduced to I and 8 Llmin, respectively. Also, the concentration of the atomizer solution was increased to 0.5%uranine.

A photograph of the particles from a 0.064-1'01 aerosol isshown in Figure 2. Each of the calibration aerosols was photographed and sized by electron microscopy. The particleswere collected on 500 mesh, carbon coated grids using apoint-to-plane electrostatic precipitator (AIRES, Albuquerque, N.M.). The magnification of the micrographs is obtainedby photographing a 54864 lines/in. diffraction grating.

Sample Collection. The calibration aerosol was sampledboth by the impactor and a total filter operated in parallel. Formost of the runs, an after filter was used with the impactor.Thus, the total filter acted as a check on the mass balance forthe system. The excess aerosol flow was vented through theelectrometer portion of an Electrical Aerosol Analyzer(Thermosystems No. 30:10), and the aerosol current wasmeasured to monitor the output of the aerosol generationsystem. Details of the now system can be seen in Figure 1.Note that the aerosol to be sampled by the impactor and totalfilter is first passed through an Sf'Kr charge neutralizer.

184 Environmental Science & Technology 0013-936X/79/0913-0184$OI.00/0 © 1979 American Chemical Society

DRYSHEATHAIR

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EXCESS

AIR

KEY:

,

@ FLOW CONTROL VALVE

o MASS FLOWMETER

Figure 1. Aerosol generation and sampling system

stage no. Oil em p,a mmHg cutoff. 101m, •

1 0.249 744 4.0· I •2 0.140 743 2.0·3 0.099 740 1.0·4 0.064 720 0.50·· c

orifice 0.036 150 •5 O. t 10 140 0.26 c

6 0.099 106 O. t2 c.• ••7 0.099 50 0.075 • • ••8 0.140 8 0.050· •

Table I. Low-Pressure Impactor Design andOperational Parameters

oil Atmospheric pressure:: 745 mmHg. b Calibration data from Delron Research Products (Powell, Ohio). C Polystyrene latex calibration of ref 1. d Thiswork.

Although these small particles are expected to follow theair now, the effect of splitting the aerosol stream between theimpactor and the total filter was test.ed. For the O.()()4- and0.39-l'm (micros('opic diameter) aerosol (.S), a filter was operated upstream of the impactor in parallel with the totalfilter. The air flow in hoth streams was I Llmin. The ratio ofthe loadings for this impactor "prefilter" to the tut.allilter was0.99 ± 0.02.

The pussihility of evaporation of the uranine at the reducedimpactor pre ures was also checked. Two IiIters were loadedwith equal amounts of the uranine aerosol. One of these filterswas then placed as an after-filter on the vacuum side of theimpactor, and filtered roum air drawn thruugh the impactur.

•'\ ........0.2 pm

Figure 2. Uranine aerosol, 0.064 I'm diameter

Two runs each with the filters subjected to the low pressuresfor 0.5 and 9.3 h both gave 3 ± 1% losses. The 9-h run is representative of the longest sampling times used in these experimenLs.

Earlier studies (1) demonstrated that it is essential to coatthe collection surfaces to prevent particle bounce and reentrainment. Vaseline was found to prevent particle buunce andto be compatible with chemical analyses. Therefore, for thiscalihration study, Va eline-coated collection surfaces were


(1)

Table II. Uranine Aerosol Particle Diameters

mlc:roscop5c aerodynamic diameter C

diam. 8 nominal b stage 8 stage 7 stage 6 stage 5 stages 1-4

0.39 + 0.10 0.40 0.56 0.55 0.53 0.52 0.49-0.07

0.22 + 0.04 0.28 0.32 0.31 0.31 0.30 0.28-0.03

0.085 ± 0.005 0.14 0.12 0.123 0.122 0.121 0.110.064 ± 0.004 0.10 0.093 0.093 0.092 0.091 0.0860.057 ± 0.007 0.075 0.083 0.083 0.082 0.082 0.0770.034 ± 0.003 0.050 0.050 0.049 0.049 0.049 0.047

0.0078 ± 0.0007 0.030 0.011 0.011 0.011 0.011 0.011

a Based on electron microgaphs. b As given by classifier. C Based on uraninedensity and microscopically determined diameter (see text).

used throughout. In most of the calibration runs, the samplewas collected on a stainless steel strip, 1 X 0.25 X 0.002 in.,mounted in the center of a I-in. diameter glass disk. Thesestrips are the same as those used for aerosol sulfur analysis bythe flash volatilization method (3). A Vaseline coating is applied to the center of the strip with a cotton swab. The impactor was also calibrated using 1-in. glass disks, for which theentire surface was coated with Vaseline.

Chemical Analysis. The uraninI' collected on each stagewas measured by fluorescence. For the Vaseline·coated impactor samples, a double extraction was employed to dissolveboth the grease and the uraninI' (8). The stainless steel stripsand glass disks used in the impactor were ultrasonically extracted for 20 min with 3 mL of benzene. To the benzene solution, 4 mL of 0.1 N NH.OH was added, the test tube shakento mix the two solvents, and then the ultrasonic extractionrepeated for an additional 20 min. The benzene served to extract the Vaseline, while the uraninI' is soluble in the ammonium hydroxide solution. To maintain consistency in theprocedure, the double extraction was also empluyed for thefilter samples using 5 IllL of benzene and 6 IllL of 0.1 NNH.OH per filter. Before analysis, the extracts were centrifuged, impactor samples for 30 min and filter samples for 45min. This served to separate the two immiscible suivents, andto remove suspended filter fragments. The aqueous layer wasthen analyzed with an Aminco Buwman spectrophutufluorollleter, using excitatiun and emission wavelengths uf :325 and510 nm, respectively.

Several tests were made tu check the analysis procedure.As uraninI' fluorescence is subject to quenching, it is impurtantto determine that the difference in the collectiun substratebetween the impactur and the tilter nut yield different responses tu the same uraninI' luading. In the first of these tests,uranine standards of 142.2 ng/mL in 0.1 N NH.OH weremixed with benzene, sonicated, centrifuged, and analyzed, asdescribed in the above extraction procedures. Tu mimic thefilter analysis, 5 mL of benzene was mixed with 6 mL of theuraninI' standard in the same beakers used fur the filteranalyses. The stainless steel strip analysis was also mimickedin this same manner. Solution vulumes were measured befureanalysis. The uraninI' recoveries, as compared with the uriginalstandard, are 93 ± 2% and 92 ± 1% for the filter and stainlesssteel strip type extractions, respectively. The tests were alsorun for clean filters and clean Vaseline-coated stainless steelstrips. The specified extractiun procedure was followed exceptthat the uraninI' standard (142.2 ng/mL in 0.1 N NH.OH) wassubstituted for the 0.1 N ammunium hydroxide in the aqueuusextraction. Compared to the uraninI' stalldard, the recoveriesfor filter and strip systems are 90 ± 1 arid 92 ± 1%, -espectively. Errors represent the standard deviation of three measurements. The recoveries are currected for the tilter and strip

186 Environmental Science &Technology

blank values, measured to be 0.7 ± 0.5 ng/mL for both substrates. Although the benzene is observed to affect the uraninI'measurement sumewhat, no significant quenching can be attributed to the filters or coated strips.

In another test, the extraction efficiency from Vaselinecoated strips spiked with uraninI' was checked. The uraninI'was applied to the strip using a microliter syringe, and thedroplet allowed to dry before extraction. For five samples, therecovery is 90 ± 3%, which is within the error of the value obtained fur the uraninI' standard-benzene system. Thus, theextraction is essentially complete.


Sizing of the Calibration Aerosol. The diameters of thecalibration aerosols are listed in the first column of Table II.For each aerosol, the average particle diameter is determinedby microscopic sizing of 50 to 200 particles. The widths of theaerosol size distributions are taken from the mobility widthsgiven by the size classifier manual. As a statistically smallnumber of particles was actually sized, the width of the sizedistribution was not experimentally determined. However,for those particles which were sized, 70-90% of the mass iswithin the stated size range.

Considerable discrepancy is found between the measureddiameters and the Stokes diameters calculated on the basisof the classifier settings. For example, particles, which according to the classifier should be 0.05"m, were measured tobe 0.034 "m in diameter. Yet 0.109-"m polystyrene latexparticles were classified to be within 5% of their nominal size.This discrepancy may result in part because of the roughnessof the surface of the uraninI' particles in comparison with thelatex. The expression for the slip factor used to calculateelectrical mobilities is based on data for smooth glass spheresand oil droplets. A second possibility is that some additionalevaporation of the particles may occur as they are drawn intothe dry sheath air of the classifier. However, particles collectedimmediately at the exit of the classifier, upstream of the impactor, are dry when examined microscopically. Experiencewith wet particles has shown that they are clearly visible aswet under the electron microscope. Should the particle drywhile on the grid, a mark is seen around the central particle.No evidence of evaporation or wet particles was observed forthese calibration aerosols. Thus, in this wurk, the aerosol diameters are taken from the microscopic measurements. Thedifierence from the Stokes diameter given by t.he classifier isshown in Table II.

Aerodynamic Diameter. For the low-pressure impactorstages, the particle diameters are of the same order, or smallerthan the mean free path. The aerodynamic diameter of theparticles, d", is:

(' ) 112d" = (I' c: d,

where I' =particle density, d, =Stokes diameter, and C, andC" are the slip corrections to the Stokes drag for particles ofdiameter d, and d,,, respectively. The slip factor is given by:

2AC = 1 + - [1.257 + 0040 exp( -0.55d/A)I

d

where d = particle diameter and A = mean free path. Forparticles much larger than the mean free path, C = I, and d"= v;d,. In the limit uf particles much smaller than A, thisexpression reduces to the free molecular relation d. = I'd,. Inthe transition regime, the aerodynamic diameter must befound by iteration of Equation I. This iteration may be madeto converge rapidly by noting that the exponential term variesslowly with particle diameter. Writing:

Table III. Aerosol Size and Mass Balances100

~>- 80uzw(3

60"-"-W

Z 40QI-Uw 20--'--'0u

uranine particle dlam.

0.39 + 0,10-0.Q7

0.22 + 0,04-0.03

0.085 ± 0,0050.064 ± 0.004

0.057 ± 0.0070.034 ± 0.0030.0078 ± 0.0007

(Impactor + after-fliter loadlng)1total fllter loadinG, %

102 ± 3

97 ± 3

99 ± 397 ± 5

98 ± 582 ± 875 ± 7

0.01 0.10 1.0

AERODYNAMIC DIAMETER (f-'m)

Figure 3. Impaclor calibration curvesUranine aerosol (this work): (+) slages 4,6, and 8: (*) stages 5 and 7. Polystyrene latex (rei 1): (0) stages 4, 8, and 8: (<Ill) slages 5 and 7

Table IV. Collection Efficiencies with and without anAlter-Filter

K = 2[1.257 + 0.40 exp(-0.55d/X) I (3)

where

C = 1 +KXd

(2)

slage no. microscopic particle dlam. with after-filter without aller-tiller

8 0.034 50 ± 2 51 ± 1

8 0.0078 16± 1 17 ± 1

7 0.034 16 ± 3 20 ± 3

7 0,0078 5± 1 4±2

the aerodynamic diameter is:

da = l/2[(Ka2XZ + 4pd,(d, + K,X))1/2 - KaX] (4)

Ka and K, refer to Equation 3 evaluated for d a and d" respectively, Setting K a = K s for the first iteration will give avalue of da accurate within at least 1% for p = 1.5, and within4% for p = 4.

As the aerodynamic diameter is a function of both the meanfree path and particle density, the value of da for the uranineaerosols varies with impactor stage, The values of da for eachof the uranine calibration aerosols are given in Table II. Thedensity of uranine is taken to be 1.46 g/cm:l, which is the average of values reported in the literature for both bulk uranine(9, 11, 13) and uranine aerosol (10-12). With the exceptionof Stein (9), the density of uranine aerosol (10-12) was notfound to be significantly different from the density of the bulkmaterial. As the particles are spherical, the Stokes diameteris assumed to be equal to the microscopically measured diameter.

Stage Collection Efficiencies. The measured collectionefficiencies for the uranine aerosols are plotted in Figure 3,together with the polystyrene latex calibration points previously obtained (1). Except for the two largest sizes, severalexperimental runs were made for each uranine aerosol. Errorsindicated in Figure 3 are the standard deviations of thesemeasurements.

The collection efficiencies are based on the total aerosolloading, which is measured by both the impactor with afterfilter, and by the total filter operated in parallel. A comparisonof these two measurements is given in Table III. Good massbalances of 97-100% were obtained for uranine aerosol 0.057~m and larger. However, for the 0.034- and 0.0078-~maerosols,the amounts deposited on the collection stages and after-filterare, respectively, 82 ± 8 and 75 ± 7% of the total filter loadings.Diffusional losses are greater for the low pressures in the finalimpactor stages. The calculated wall losses for laminar diffusion in the free molecular regime are 7% for the 0.034-/Lmaerosol, and 35% for the 0.0078-/Lm aerosol. Most of thesecalculated losses occur between the eighth stage and theafter-filter. Therefore, for these 0.034- and 0,0078-/Lm aerosols,the collection efficiences are based on the mass loading givenby the total filter, For the larger aerosols for which the massbalance is quite good, the efficiencies are based on the impactor and after-filter measurements.

Collection efficiencies were measured for two differentimpactor collection surfaces: I-in. Vaseline-coated disks andVaseline-coated 0,25 in. X 1 in. X 0,002 in, stainless steel strips.The strips were tested because they are used for the aerosolsulfur and nitrate analyses often employed with this impactor.For sample collection, the stainless steel strips are mountedon a I-in. glass disk, in which a shallow groove had beensandblasted to hold the strip. In this manner, the jet-to-platedistance is unchanged. Only the strip is analyzed. Both ofthese collection surfaces were used for the 0,0078-, 0.034-,0.057-, and 0,064-/Lm uranine particles. No significant difference is observed for any of the stages or particle sizes tested.The average ratio of the collection efficiencies measured withthe strips, as compared with the disks for all of these runs, is0,96 ± 0.08. It is concluded that little aerosol is deposited atthe edge of the I-in, diameter collection plate. The Vaselinecoating and sample analysis can be confined to the center ofthe disk with no loss of accuracy.

For the final stage, the stagnation pressure below the jetdepends on whether or not an after-filter is used. Using a47-mm glass fiber (Gelman AE) filter raises this stagnationpressure from 8 to 18 mmHg absolute. The velocity of the jetis unchanged, for it will remain sonic unless the stagnationpressure below the jet exceeds approximately 22 mmHg. Theother stages should not be affected so long as stage 8 remainssonic. For the 0.0078- and 0.034-/Lm aerosols, experiments weremade with and without the after-filter to determine the effectupon the stage collection efficiencies. The results listed inTable IV show the average of two or three runs in each configuration, As can be seen from these data, no shift in thecollection efficiencies occurs as a result of the pressure changebelow stage 8.

Since the results were about the same for the strips anddisks, or runs with or without the after-filter, all of these datawere averaged to prepare the efficiency curves of Figure 3.Reasonable agreement is found between this uranine calibration and the polystyrene latex calibration. The 50% efficiency cutoff for stage 6 is adjusted to 0,12/Lm from the previously reported latex calibration ofO.l1/Lm. The cutoffs forstages 7 and 8 are 0.075 and 0.05/Lm, respectively. The curvesare reasonably steep as desired to minimize the cross-sensitivity between stages. For the final stage, the experimentallydetermined collection efficiency of particles smaller than thecutoff diameter does not approach zero as rapidly as for the


100

~>- 80uzwu

60'"-'"-W

Z 400f-Uw 20...J...J0U

0.01 0.1 1.0

AERODYNAMIC DIAMETER (fLm)

Figure 4. Collection efficiency curves: stages 7 and 8

other stages. This is in part attributed to the presence of a fewlarger particles in the text aerosol (14).

Particle Rebound and Wall Losses. Figure 4 shows thecollection efficiency curves for the seventh and eighth impactor stages, including the collection efficiencies of the largerparticles. As can be seen, the efficiency does not reach 100%,but actually decreases for the larger particles. These curvesare similar to those of Rao and Whitby (15), who found thatrebound of the larger particles limits their collection. For thesehigh-velocity stages, it is not surprising that the larger particles bounce. Fortunately, the diameter for which the collectionefficiency begins to decrease with increasing particle size iswell above the cut point of the preceding stage. Thus, few largeparticles reach these stages. For example, even though the0.39-l'm (microscopic diameter) collection efficiency is only32% for stage 8, the mass loading measured by the impactoralone (excluding the after-filter) is 96% of the total filtermeasurement. Similarly, for the 0.22-J.lm (microscopic diameter) aerosol, 99% of the aerosol is retained within the impactor. Thus, rebound of the larger particles from the lower(smaller cutoff) stages is not a problem in practice.

The wall losses for the particles 0.10 I'm and smaller weremeasured by washing the inside impactor walls. The 0.1 NNH40H wash solution was directly analyzed for uranine byfluorescence. A second wash checked that most of the aerosolhad been removed. For these aerosols (0.10 J.lm and smaller),the losses were measured to be 5% of the total uranine sampled. The low-pressure stages accounted for 3%. Losses onstages 1-4 were 1%, and in the orifice itself, 0.05%. Wall losseswere also measured for each of the 0.22- and 0.39-J.lm aerosolexperiments. Here, attention was directed at the fifthstage, which immediately follows the flow-restricting orifice.As there is no plate below the orifice to dissipate the flow,particles in the jet could impact on the walls of the conical inletto the stage 5 jet. For these two runs, the total losses were 4%,with 3% attributed to stage 5. These losses could perhaps bereduced by increasing the distance below the orifice to allowthe jet to spread and the velocity to drop before reaching thewalls.

Physical Meaning of Low-Pressure Stage Cutoffs. Thelow-pressure stages of the impactor size segregate the aerosolnot according to the atmospheric pressure aerodynamic diameter, but according to the aerodynamic diameter at thereduced pressure. The cutoffs listed in Table I are the aerodynamic diameters at the pressure at which the impactor stageoperates, as this is the quantity which characterizes the collection efficiencies.

For atmospheric behavior this low-pressure aerodynamicdiameter is of little interest. To translate these sizes to a moremeaningful value such as the Stokes diameter or the atmospheric pressure aerodynamic diameter, a value must be assumed for the density of the aerosol. For these small particles


Table V. Stokes Cutoff Diameters

stage 8 i'age 7 stage 8 stage 5

0.5 0.10 0.15 0.23 0.47

0.8 0.062 0.093 0.15 0.32

1.0 0.050 0.075 0.12 0.26

1.2 0.042 0.063 0.10 0.22

1.4 0.036 0.054 0.087 0.19

1.6 0.031 0.047 0.077 0.17

2.0 0.025 0.038 0.062 0.14

3.0 0.017 0.025 0.042 0.094

4.0 0.013 0.019 0.032 0.072

6.0 0.0084 0.013 0.021 0.048

the actual (geometric) diameter is of interest since it determines the particle diffusion coefficient. For spherical particles,this particle diameter should equal the Stokes diameter, whichis related to the aerodynamic diameter by Equation 4. InTable V the Stokes diameters corresponding to the stagecutoffs are listed as a function of particle density.

Summary

The low-pressure impactor was calibrated using monodisperse uranine aerosols. Aerodynamic cutoff diameters at thereduced stage pressures were found to be 0.12, 0.075, and 0.050I'm for the sixth, seventh, and eighth stages, respectively.These are equal to the Stokes diameters for spherical particlesof unit density at atmospheric pressure. For nonunit densities,the actual (geometric) diameters must be calculated fromtheory. Collection efficiencies did not change when a glassfiber after-filter was used. They were also not affected by thecollection surfaces tested here, V4-in. stainless steel strips, or1 in. diameter glass disks. Wall losses were about 5%, probablyresulting from the impaction of 0.26- to 0.5-l'm particles onthe inlet of the stage 5 jet, and diffusional losses of particlessmaller than 0.04 I'm.

Acknowledgments

The authors thank Professor Jean-Paul ReveloI' the California Institute of Technology Biology Department for providing access to the electron microscope and Mr. Pat Koen forhis instruction and supervision in its operation.

Literature Cited

(1) Hering, S. V., Flagan, R. C., Friedlander, S. K., Environ. Sci.Technol., 12,667-73 (978).

(2) Mitchell, R. I., Pilcher, J. B.,lnd. Eng. Chem., 51,1039 (959).(3) Roberts, P. T., Friedlander, S. K., Atmos. Environ., 10, 403

(976).(4) Moskowitz, A. H., M.S. Thesis, California Institute of Technology,

1976.(5) Marple, V., Liu, B. Y. H., J. Colloid Interface Sci., 53, 31

(1975).(6) Liu, B. Y. H., Pui, D. Y. H., ibid., 47,155 (1974).(7) Liu, B. Y. H., Lee, K. W., Am. Ind. HYN. Assoc. J., 36, 861

(975).(8) Smith, W. B., Cushing, K. M., McCain, J. D., "Particle Sizing for

Control Device Evaluation", Southern Research Institute ReportNo. EPA-650/2-74-102, Oct 1974.

(9) Stein, F., Esmen, N., Koru, M., Am. Ind. Hyg. Assoc., 27,428(1966).

(0) Tillery, M. I., McKnight, M., ibid., 28,498 (1967).(1) Sehmel, G. A., ibid., 28,491 (967).(12) Moss, O. R., ibid., 32,221 (971).O:lj Stoeber, W., Flachsbart, H., Almos. Envirun., 7,737 (1973).(4) ,Jaenicke, R., Blifford, I. H., J. Aerosol Sci., 5,457 (974).(15) Rao, A. K., Whitby, K. T., Am. Ind. HYN. Assoc. J., 34, 174

(977).

Received for review March /3, 1978. Accepted August 23,1978. Thiswurk was supported in part by NIEHS Grant No. PHS ES00080-01and by NSF/RANN Grant No. ENV76-04/79. The Pasadena LungAssociation provided funds fDr instrumentation.

Evaluation of Boron Removal by Adsorption on Solids

Won-Wook Choi and Kenneth Y. Chen"

Environmental Engineering Program, University of Southern California, Los Angeles, Calif. 90007

• The adsorption method is moderately effective for theremoval of low levels of boron from solution. At the initialboron concentration of 5 mg/L or less, Filtrasorb (activatedcarbon) is the adsorbent capable of achieving more than 90%removal. The pH of the suspension and initial concentrationof boron are two critical factors in determining the removalefficiency. Boron can be removed by adsorption either asH3B03 or as B(OH)4-. The adsorption of boron is not only dueto the distribution of boron species but also to the type and/ornumber of active sites that may vary with changing pH,composition of solution matrix, and surface properties of thesolid.

Boron is of special concern in irrigation water because of itsbeneficial and toxic effects in plants. On the other hand, it isan essential micronutrient for higher plants (I). A number ofboron criteria in irrigation waters have been proposed. Forinstance, Wilcox (2, 3) has proposed the permissible limits ofboron in irrigation water as 0.3-1.0 ppm for sensitive crops,1.0-2.0 ppm for semitolerant crops, and 2.0-4.0 ppm for tolerant crops. With regard to citrus, Chapman (4) suggestedboron concentrations of 0.5, 1.0, and 2.0 ppm for possible-,definite-, and serious-hazard classes for irrigation waters.

The concentration of boron has been reported to be in theranges of 7 ppb to 0.2 ppm in tap water (5, 6), with a worldwideaverage of 13 ppb in fresh river waters (7), and about 5 mg/Lin seawater (8, 9). A recent extensive survey of geothermalfluids found that the boron concentration varies widely(10).

Boron in aqueous solution is normally present as boric acidand borate ions. The dominant form of inorganic boron innatural aqueous systems is the undissociated boric acid. Boricacid is a very weak and exclusively monobasic acid which behaves in solution not as a proton donor but as an electron acceptor (Lewis acid), taking OH- (I1, 12):

HaBOa + H20 <=' B(OH)4- + H+, K = 5.8 X 10-10 at 25·C

The ionization constant (K) of boric acid increases with increasing concentrations of strong electrolyte (11, 13,14). Itis mostly monobasic in dilute solution, but polymeric speciesmay be present at concentrations above 0.1 M H:1B03 (I1).Ingri (IS) reported that when the concentration is less than0.025 M total boron (0.1% B20 3 or 270 mg ofB/L), most of thespecies present are essentially only H:IBO:1 and/or B(OH)4-.Polyanionic species such as B:10:I(OH)4-, BS0 6(OH)4-,B30 a(OHls2- and B40 S(OH)42- are formed in solutions between 0.025 and 0.6 M at a neutral to alkaline pH (approximately pH 6 to 11) (IS, 16).

Despite its widespread use (5), little is known about theremoval of boron from waters and wastewaters. So far, the useof ion exchange resins such as Amberlite XE-243 is the onlymethod which is considered effective for the removal of boron(5, 17, 18). The lack of information on alternative borontreatment processes reflects the fact that boron has not beentreated as a potential toxicant until recently. However, theadsorption of boron by clays, soils, and other minerals hasbeen extensively studied by many investigators working in thefield of geochemistry and soil science (I 9-32).

In the present study, specific efforts were made in studyingadsorption of boron using various types of adsorbents suchas activated carbon, activated bauxite, and activated alumina.

Parameters examined include the boron concentration in thesolution, pH, duration of treatment (contact time), salinity,and competition with or interference by other chemicalspecies.

Experimental

(A) General Procedures for Adsorption Study. BatchAdsorption Experiment. A continuously mixed batch technique was selected for the batch adsorption experiments. Aprefixed amount of adsorbent (adsorbent dosage = 5 g/200 mLor 25 gIL) was weighed into a 250-mL linear polyethylenecentrifuge bottle. Immediately after the addition of 200 mLof test solution, the bottle was shaken on a wrist-action shaker(Burrell Model-75) for a predetermined period of contact timeat room temperature, 25 ± 2°C. The solutions were firstcentrifuged at 18000 rpm on a high-speed centrifuge (IECModel B-20A) and then passed through a 0.45-l'm Milliporefilter (Type HA) if necessary. For the rate study, a vacuumsyringe filtration technique was employed.

The pH of the solution and the concentrations of AI(III),Fe(III), Ca(Il), and Mg(II) ions were measured prior to determination of boron. A control (without adsorbent) was usedto evaluate error from adsorption on the container walls.

Background Solutions. Three different background solutions were used for the boron adsorption study: (1) deionized-distilled water (DOW); (2) clean seawater (SW) filteredthrough a 0.05-l'm Millipore filter; and (3) simulated geothermal water (SGW) synthesized for the present study.

The deionized-distilled water was made by passing tapwater through a mixed-bed ion exchange resin followed bydistillation using a Corning water distillation apparatus(Mega-Pure, Model MP-3). The pH and conductivity of thedeionized-distilled water were from pH 5.7 to 6.1 and 0.651.01l'mho, respectively, at 23 'C. The conductivity of solutionwas determined using a conductivity bridge (Barnstead,Model PM-70CB) and conductivity cell (Barnstead, ModelB-lO, cell constant = 1.0).

The chemical compositions of the simulated geothermalwater and seawater are described in Table I. The conductivityof filtered seawater was 34.5 mmho at 23 'C. The salinity ofthe seawater, determined by a Goldberg T/C refractometer(American Optical Corp., Model 10419), was 33.0%•. Theconductivity of the simulated geothermal water was 39.75mmho at 23 'C. The salinity determined was 36.50/...

Selection and Characteristics of Adsorbents. Selection ofAdsorbents: Sigworth and Smith (33) reviewed activatedcarbon as a potential adsorbent for the removal of inorganicspecies from waters. Recent studies (34-36) showed that someinorganic species, such as mercury, cadmium, and chromium,could be successfully removed from water by activated carbon.

Boron is known to be adsorbed by soil material and mineralsof aluminum, iron, and magnesium oxides and hydroxides(I9--22). Therefore, three types of adsorbents were evaluatedfor the present boron adsorption study: activated carbon;activated bauxite; and activated alumina.

In the preliminary stage of the study, nine adsorbents listedbelow were examined by an adsorption rate test in deionized-distilled water background.

Activated carbons: Hydro Darco 3000 (ICI America; surfacearea = 600-650 m2/g BET; mean particle diameter = 1.6 mm;raw material, lignite); Filtrasorb 300 (Calgon Corp.; surface

0013-936XI79/0913-0189$Ol.00/0 © 1979 American Chemical Society Volume 13, Number 2, February 1979 189

Table I. Chemical Composition of SimulatedGeothermal Water (SGW) and Seawater (SW) Usedin This Study

concn a

species SGW SW

Na 14000 12000K 1050 390Ca 0.6 434

M9 002 1262B nd 4.74Li 135 0.2Si 64 1.0CI 19700 19400F nd 1.32HC03- 1820 120C032- 18 12SO.2- 2250 2700TDS 39100 36500

pH 8.2 7.7-8.0

a All are in milligrams per liter except for pH. nd, not detected.

area = 950-1050 m2/g BET; mean particle diameter = 1.5-1.7mm; raw material, coal); Nuchar WV-1 (Westvaco, surfacearea = 1000 m2/g BET; mean particle diameter = 1.5-1.7 mm;raw material, pulp mill residue); and Norit (American NoritCo.; powder decolorizing; raw material, wood).

Activated aluminas: Aluminum oxide (E. Merck; neutral;activity grade I, for chromatography), ALCOA F-1 (AluminumCompany of America; surface area = 210 m2/g; 28/48 mesh;granular), KA-201 (Kaiser Chemicals, surface area = 350 m2/g;8/14 mesh; granular).

Activated bauxites: PorOcel (Inglehard Minerals andChemicals Corp.; 30/38 mesh) and Milwhite (The MilwhiteCo., Inc.; 30/60 mesh; volatile matter 4.5-6.5%; domestic).

None of the adsorbents was subjected to additional pretreatment. After the investigation of adsorption rates, onlyfour adsorbents (Hydro Darco 3000, Filtrasorb 300, ALCOAF-1, and Milwhite's activated bauxite) were selected for further investigations. It must be noted here that Hydro Darco,which was the least effective adsorbent for boron removal (seeFigure 2), was selected only for the comparison with Filtrasorb.

General Characteristics of Adsorbents: All the adsorbentstested caused a rise in pH in solution. A considerable rise inpH occurs in the presence of the commercial grade activatedaluminas; however, it is most probably an effect of caustic sodaused in the manufacturing process. For instance, Kaiser'saluminas are produced by a modified Bayer process in whichthe bauxite mineral is digested with caustic soda at elevatedtemperature and pressure to dissolve the alumina from thebauxite.

Although the major component of activated bauxite isAlzO:lo other oxides suchas Fe20:1, Ti02, and Si02 complexes(red mud) are present in appreciable amounts. Based on themanufacturer's information, for example, Milwhite's domesticbauxite contains 76.5% AlzO~, 4.0% Fe20:1o 3.5% Ti02, 10.0%Si02, and volatile matter. Therefore, the physicochemicalcharacteristics affecting adsorption of boron will differ fromthose of activated alumina.

Effect of pH on the Leaching of Boron from Adsorbents:The effect of pH,s (pH of filtrate after 48 h of contact betweenthe adsorbent and solution) on the leaching of boron fromadsorbents has been investigated in deionized-distilled water


40 -1.00

.Hydro Darco {Act. Corbon}

• Filtr050rb (Act. Corbon)

Q Milwhife (Act Bay_itt)

, 30 " ALCOA {Act. Alumino 1 -0.75

<D

E

I,

~<D

20 -0.50 E-' u

~

Q

0<D 10 -025

~~0

6 '0 120.0

0p H48

Figure 1. Amounts of boron leached from adsorbents as a function ofpHBackground solution was deionized-distilled water (DOW); solid concentration= 25 giL

background. Solution pH was controlled with HCl orNaOH.

(B) Experimental Parameters and Methods. Boric acid(reagent grade) was used as the source of boron throughoutthe study. Boron concentrations were determined by the improved curcumim method described in detail by Choi (37).

Rate of Adsorption. This set of experiments was used as ascreening test for the selection of adsorbents. The adsorptionrate test, on a solution containing 20 mg/L of boron in deionized-distilled water, was performed for 9 different adsorbentsat room temperature. The adsorbent dosage was fixed at 25giL. Contact times were 1/:10, 1/6, 1,4, 12, 24, and 48 h. Thesuspension, immediately after shaking on a wrist-actionshaker for a given contact time, was rapidly filtered througha 0.45-j.lm membrane filter. pH was not controlled for this setof experiments.

pH Effects. The effect of pH on boron removal was investigated using the four selected adsorbents (Hydro Draco,Filtrasorb, Milwhite, and ALCOA) in three different background solutions: deionized-distilled water (DOW); fourfolddilution of seawater (dil.(1:3)SW); and fourfold dilution of thesimulated geothermal water (dil.(1:3)SGW) each containing20 mg/L of boron. A 48-h contact time to reach approximateequilihrium was selected. To obtain well-distributed pH'8values, different values of initial solution pH were producedby adding HCl or NaOH. However, when the desired pH'8could not be obtained easily by the adjustment of the initialsolution pH, the pH of the suspension was controlled within4 h of initial mixing.

Salinity Effects. The effect of salinity on the'removal ofboron was investigated using seawater (salinity = 33.0%0) andthe simulated geothermal water (salinity = 36.5%.). A seriesof solutions of different salinities was obtained by diluting theoriginal seawater or simulated geothermal water with deionized-distilled water.

Concentration Effects. The effects of various initial boronconcentrations (Cu = 5, 10,20,40,60, 100, and 200 mg/L ofboron) on removal efficiency were investigated in the background solutions of deionized-distilled water, fourfold dilutionof seawater, and fourfold dilution of simulated geothermalwater.

Effects of Other Chemical Species. The effects of Ca(ll),Mg(IIJ, Si(IV), and S041 - on the removal of boron were investigated using 20 mg/L boron in deionized-distilled watercontaining each of the above species. The chemicals used wereCaCle·2H 20 for Ca(lI), MgCI2·6H20 for Mg(1I) , Na2SiO:l'9H20 for SHIV), and Na2S04 for SO,2-.

14

• Hydro Doreo (Act Carbon) 6 ALCOA (Act AluminO) 0 Mllwhlte (Act BlXJlufe)

A FtltrasOfb Ii. Karser I <t pOJrOcef (

• Non' 0 E Mercll (12

[J Nuchar

'0OI----n---~=====-------cJ----

'0L---'----,.LO---.L'S---2.L0---2.LS---3.L0---35'----4.L0---4.LS----'50

Time, hr.

Figure 2. Rate of boron adsorption on various adsorbentsCo :; 20 rng of B/L; background solution was deionized-distilled water: adsorbent dosage = 25 gIL

20

FiltrosorblAc I Carbon)

ALCOA(Ac!. Alumino)

0:--'----;;2-'-~4,----'-...,6~-'----;;8-'--7.IOo.--'0

-'--L_I---L--'_.L-l 0 .~u

,-.--,-,--.--r-,----.-r-,--.--, 60 ::UJ

c~E

40 ~

G-OOWi!r- Oa.oo3lSGW0- Oil.(1:3ISW

Milwhite(Act. BOull.le)

Hydro Dorco(Acl Carbon)

4

u

4

12,-.--,-,----.-r-,----.-r-,----.-.

8

,<D

~i 0'--'---'_-'----'-_-'--'-_·'--'---'_-'----'

u 12,-.--,-,----,--,---,--,-.--,--,---,

~,

pH.q8

Figure 3. Effects of pH46 on the removal efficiencies of boron in deionized-distilled water (DOW) and the fourfold dilutions of seawater (Oil.( 1:3)SW) and simulated geothermal water (Oil.( 1:3)SGW) by various adsorbentsCo = 20 mg Of Sll: adsorbent dosage = 25 gil

Results and Discussiun

(A) Effect of pH on the Leaching of Boron from Adsorbents. The results obtained for boron leached from adsorbents are shown in Figure l. It should be noted that negative values of dC (2).C = Co - C,) in Figure I indicate leachingfrom the adsorbent while positive values of dC indicate removal from the solution. For all of the adsorbents, with theexception of activated alumina (ALCOA), the amount of

boron leached increases with decreasing pH below 6. Withinthe pH range investigated, the amount of boron leached fromevery adsorbent remains approximately constant above pH6. The least leaching for all the adsorbents occurs between pH6 and 9. As shown in Figure I, activated bauxite (Milwhite)produces the largest amounts of boron, followed by HydroDarco (activated carbon).

(B) Ratc of Adsorption. The results obtained for the rateof adsorption are shown in Figure 2. All the adsorbents except


100

HS803 8(OH4

'0

60 $<lIIMy o "lOG

.. 10 °1_

40%,.40

'0

8(OH4

"

Figure 4. Distribution of H3B03 and B(OH),- as a function of pH belowthe total boron concentration of 0.025 M as H3B03 (270 mg of B/L) atthree different salinities (11, 12, 14)

Hydro Darco generally show a high initial rate of boron adsorption diminishing markedly with time. Presumably, adsorption will continue beyond the 48-h contact time at acontinuously diminishing rate. Although further adsorptionis theoretically significant, it is not important for industrialand water treatment applications.

With considerations of performance, availability, andpreference of commercial grade over analytical grade, the

following adsorbents were selected for each group for furtherstudies: Filtrasorb for activated carbons; Milwhite for activated bauxites; and ALCOA for activated aluminas. HydroDarco was the least effective adsorbent among the adsorbentsexamined while Filtrasorb was the best. It is quite interestingto note that the opposite was true of fluoride removal (37).Thus, Hydro Darco was also selected for comparison withFiltrasorb.

(C) pH Effects. The effects of pH on the removal of boronin three different solution backgrounds are shown in Figure3. In addition, the distribution of H3B03 and B(OH)4- as afunction of pH (at three different salinities) below 0.025 M(i.e., 270 mg/L of boron) are plotted in Figure 4 for the purposeof comparison. The data plotted in Figure 4 have been calculated based on published and interpolated pKavalues (9.23at 0%0,8.93 at 10%0, and 8.60 at 40%0) of boric acid (II, 12,14).The data listed in Table II were obtained from Figure 3. Thedata indicate that the optimum pH for boron removal underthe given experimental condition depends on both the background solution and the adsorbent. Regardless of adsorbenttype, however, the optimum pH rose when the backgroundsolution changed from deionized-distilled water to the fourfold dilution of seawater or that of simulated geothermalwater. The variation was not more than 0.7 pH unit for HydroDarco, activated bauxite, and activated alumina. However,it varied as much as 1.8 pH units for Filtrasorb. The shift in

Table II. Optimum pH48 for the Maximum Removal of Boron

ALCOA (act. alumina)Hydro Darco (act. C) Filirasorb (act. C) Mllwhite (act. bauxite)

max max maxbackground optimum removal optimum removal optimum removal

solution pH48 elf., % pH 48 eft. % pH48 eff., %

DDwa 8.0 28 7.8 59 8,0 45dil.(1:3)SWb 8.3 26 8.6 53 8.2 43dil.(1:3)SGWc 8.6 24 9.6 50 86 39

optimump H 48

8,28.68.9

maxremovalell., %

524947

a Deionized-distilled water. b Fourfold dilution of seawater. C Fourfold dilution of simulated geothermal water.

10~----------------,

70~----'---1:'::0:----'---:2:':0=-----'----'3:'-0=----'----,J4 0

Hydro Darco l. ~(Act. Carbon)

J -.

~

"

60

• 50

40

30

Filtrasorb(Act. Carbon) ...

20

~·u

60 -=W~

50 ~----e a:

40

ALCOA 30

(Act. Alumina)

20

20 30 4010o

Milwhile(Ac t. Bauxite)

~8~~

E

.~0.

10a

'"...~

9~

~

kff8~

0- (pH4s )optimum , SGW~" ,sw.- Removal Efficiency, SGW4- ,SW

So linity I 01.0

Figure 5. Effects of salinity on both removal efficiency of boron and optimum pH,. for the removal of boron in the dilutions of seawater (SW) andsimulated geothermal water (SGWj by various adsorbentsCo = 20 mg of B/L; adsorbent dosage =25 giL


Filtrosorb (Act. Carban)

ALCOA (Act. Alumino)

60

~oL~~~~~~ 100.---r--'r--,--,--.,.---,--r--r--,r-~-.

" Milwhite (Act. Boutito)

80

Hydro Dorco (Act. Carban)

DDW(pH 48 =8.20 t O.lO)llil.!I·3)SQWlpH.. =9.00' 0.10)0'.!I'3)SWlpH.. = e.60 • 0.10)

<5 80>oE"a:

20

OL--'-----'-_-'-....L.----'_-'-----'------'_-'----'------.Jo 40 80 120 160 200 a 40 80 120 160 200

C. , mg BIIFigure 6. Effects of initial boron concentration (Ga) on the removal efficiency of boron in deionized-distilled water (DDW) and the fourfold dilutionsof seawater (DiI.(1:3)SW) and simulated geothermal water (Dil.(1:3) SGW) (adsorbent dosage = 25 giL)

optimum pH for the maximum retention of boron by differentsoil materials has been observed by Sims and Bingham (21)and Bingham et al. (27). Sims and Bingham (20,21) reportedthat the maximum adsorption of horon on soil materials occurred at pH 8-9 for hydroxy iron forms and pH 7 for hydroxyaluminum forms, and suggested that the shift in optimum pHresulted from the type of surface hydroxy compounds ofmetals. However, no support for this hypothesis was found.Although the optimum pH depends on both the adsorbent andthe background solution, the maximum removal of boronoccurs when pH is 7.8 and 9.6. Regardless of the difference insuggested mechanisms, the pH range agrees well with the results of other studies (5, 20, 27). For example, the maximumremoval of boron by ion exchange resin was reported to occurwhen pH was between 7.5 and 9.0 (5). The optimum pH forremoval of boron by soil materials was found to range from pH7 to 9 (20, 27).

Hingston et al. (38) reported that adsorption of undissociated acid is unlikely because of direct competition withwater, which is the predominant species in solution. Theyascribed the adsorption of undissociated molecules such asH:IBO:J to proton dissociation at the surface of the adsorbent.The dissociated protons subsequently react with surface hydroxyl groups of neutral sites to form water which is thenreadily displaced by the anion. Thus, the maximum adsorption of the anion occurs most readily around the pKa value ofacid.

It has been suggested that horon in aqueous solution canbe removed not only as borate ion but also as boric acid (J 9-21,28-30). This is supported by the present study results (note:compare the results in Figure :l with the distribution of boronspecies shown in Figure 4). For example, as shown in TableII, Filtrasorb's optimum pH ranges for the removal of boronin deionized-distilled water and in the fourfold dilution ofsimulated geothermal water (salinity = 9.13%0) are pH 7.8 andpH 9.6, respectively. As shown in Figure 4, the fraction ofborate ion at pH 7.8 (for salinity = 0%0) is negligible comparedto that of boric acid, while those at pH 9.6 (for salinity = 10%0)are literally opposite.

Based on the results obtained in this study and the resultsreported by others (27, 29, 39), the adsorption of boron is notonly due to the distribution of boron species, but also to thetype and/or number of active sites that may vary withchanging pH, composition of solution matrix, and surfaceproperties of the solid.

(D) Salinity Effects. Effects of salinity on the removalefficiency and on the pH at which optimum removal occursfor a given salinity are shown in Figure 5. For all backgroundsolutions, the removal efficiency decreases sharply with increasing salinity up to about 8'1'00 for Hydro Darco, 5'1'00 forFiltrasorb, 8'1'00 for activated bauxite, and 10'1'00 for activatedalumina. Above these' salinities the removal efficiency is unchanged. It is interesting that the optimum pH changes withsalinity. It increases sharply with increasing salinity to approximately the same values.

For all adsorbents, the magnitude of the salinity effect onboth the removal efficiency and optimum pH is greater forsimulated geothermal water than seawater. The decrease inthe boron uptake with increasing salinity may be considereda result of competition with other chemical species or ofblocking effects of other chemical species on active sites. Nosalinity effect could be observed above a certain value of salinity. Bingham and Page (28), from the study results of boronadsorption by soil, suggested that sites which adsorb boronare more or less specific, being essentially independent ofother anions. However, it has been reported that monosilicicacid caused a reduction in boron uptake by iron and aluminumoxides (39). The reduction was attributed to either directcompetition between monosilicic acid and boric acid for ad·sorption sites, or by changes in the oxide surface following Siadsorption (39). Results from a study on competition experiments (29) showed that there was possibly an effect due tothe presence of K2S04, but little or no effect was noted whenboron adsorption was studied in the presence of KH2P04• Itis possible that boron as boric acid and/or borate ion competeswith other chemical species for certain types of active siteswhile, for other types of active sites, boron is adsorbed preferentially. Therefore, the lack of salinity effects above a cer·


",o~--_---------------,

H,dro Darco (Act. CCH'llon)

0'"

~

E~ 020

JQOOWlP4-e' 800"01010.0.1 113) SGW (pH •• =I.eo-olol

DOlt II 31S." (~u .8.20 1 0151

oo"L---------------.,----::',c...,mg BII

Figure 7. Freundlich isotherms for adsorption of boron in deionizeddistilled water (DOW) and the fourfold dilutions of seawater (Dil.(1:3)SW)and simulated geothermal water (Dil.(1:3)SGW) on Hydro Darco (adsorbent dosage = 25 gIL)

Milwhile(Acl80Ilai,.)

o DOW (I>tl .... =aoo. OJQ

.coDU II~SGWlpH .. :8101010)

0011, (l 3lsw tplol 4~ • 82010JC»

ooL,----=:.c...-.,--....,...-...."..--,"'o----ee--.c-----,=--=CoWl' mQ 8/1

Figure 9. Freundlich isotherms for adsorption of boron in deionizeddistilled water (DOW) and the fOlW101d dilutions of seawater (Dil.( 1:3)SW)and simulated geothermal water (Dil.(1:3)SGW) on activated bauxite(adsorbent dosage = 25 gIL)

OOOWlpH.. " 780-010)

l:J.0IIU3I SGW IPH•••980 1 0101

DDlt(l3jSW(pHu =860 1 010)

20 4U60 I(lO 2t.\.o

ALCOA (Act. AUrll"g J

DOW (,M .. -8.20*010)

O'lll,j SGWlpM •• =900*0101

Oll(l ,ISW (pH .. : 8,60 1 010)

C...m9 B/I

Figure 8. Freundlich isotherms for adsorption of boron in deionizeddistilled water (DOW) and the fourfold dilutions of seawater (Dil.(1:3)SW)and simulated geothermal water (Dil.(1:3)SGW) on Filtrasorb (adsorbentdosage = 25 gIL)

tain threshold is possibly attributable to the filling of nonspecific sites.

(E) Concentration Effects. The effects of initial boronconcentration in three different background solutions areshown in Figure 6. Regardless of background solution andadsorbent, the removal efficiency (with an adsorbent dosageof 25 gIL) decreases relatively sharply with increasing initialconcentration of boron to approximately 60 mg/L. Above thisvalue, the removal efficiency decreases very slowly with initialconcentration. The removal efficiency of boron by Filtrasorbwas more strongly affected. For example, as shown in Figure6, the efficiency at Co of 5 mg of BIL is about 90%, while at Coof 60 mg/L it is only about 30%. The concentration of boronis thus one of the critical factors in determining the efficiencyof removal.

The maximum adsorption of boron by soils is about 19mmol of B per 100 g of soil (about 2 mg of B/g of soil) (29).This value is comparable to those obtained with activatedbauxite and activated alumina. Although the maximum adsorption value obtained for Filtrasorb is one-half that obtainedfor activated alumina, Filtrasorb is still very effective becauseof its superior removal efficiency for initial concentrations ofless than 30 mg/L of boron.

Equilibrium adsorption isotherms (48 h) at optimum pH,with 5 g of adsorbent in 200 mL of solution, for boron from 5to 200 mgIL are shown in Figures 7 to 10. All the results arefairly well represented by the Freundlich model for adsorption. The adsorption values plotted in these figures were calculated according to the Freundlich equation:


C4•• m9 8/1

Figure 10. Freundlich isotherms for adsorption of boron in deionizeddistilled water (DOW) and the fourfold dilutions of seawater (Dil.( 1:3)SW)and simulated geothermal water (Dil.(1:3)SGW) on activated alumina(adsorbent dosage = 25 gIL)

Co - C'8logq'8 = log--D--= 10gK F + (l/n) logC'8

where q '8 = amount of boron adsorbed per unit weight ofadsorbent (mg/g) at 48 h of contact time; Co = initial concentration of boron in the solution, i.e., at t = 0, mg/L; e'8 =concentration of boron in the solution at 48 h of contact time,mg/L; D = adsorbent dosage, 25 g of adsorbentlL; and nandKF are constants. The concentration and the amount of boronadsorbed by an adsorbent are always presented as mg/L andmg/g units, respectively. Boron concentrations and those ofother chemical species present in waters are traditionallypresented as mg/L unit or ppm. Thus, mass units are likelymore convenient than mole units in the comparison of data.

(F) Effects of Other Chemical Species. The results obtained on the effects of other chemical species examined onboron removal are shown in Figures 11 to 14. As shown inFigure 11, there was an effect on the removal from the presence of Ca(ll) ions. The increase in the concentration of Ca(ll)to a certain value resulted in a decrease in the removal ofboron. Little or no additional effect was found with furtherincrease in the concentration of Ca(lI) above the value. Forexample, the removal efficiency of boron by Filtrasorb decreased with increasing the concentration of Ca(lI) up to 100mg/L. No additional influence of Ca(ll) with a further increasewas found. It is interesting to note that, although there wasan effect of Mg(lI) ions on the removal of boron by Filtrasorb(Figurc 12), little or no effect was noted with other adsorbents.Byrne and Kester (I3) reported that the cations most likelyto show significant ion pairing with boron in seawater are Na+,MgH, and Ca2+ forming NaB(OH),O, MgB(OH),+, and

o Milwhite : pH48 <7.051: 015IACI Boulite)

l::. ALCOA pH48 -973:t 0.03(Acl. Aluminol

• Hydro DOtCO p~s 6 40 :t 0 15

~IA(ICorbon)

.. F,lfrosorb : pl"4e= 1.88:t 0.05~ ~'A_"_C_.,_.._._I ......

ai 40~i>-:::::e:=================~<; 1-.~'"~ 20~

~ '---------------......

oL_'-----'_-L.._-'-_-'-_~~_~_~_..L____.J

o 200 400 600 800 1000

Initiol Cone. of Co. m9 Call

Figure 11. EHects of calcium concentration on the removal efficiencyof boron in deionized-distilled water by various adsorbentsCo = 20 mg of B/l; adsorbent dosage = 25 gil

60

50..ai

40<;

uc

'0~

:~ Hydro Dorco pH-4s!625

W IAct. CorDon)

~20 .. Fllllosorb P~8 '! 7 92

~ lACI. Corbol'l}

cr'0

0 Mllwhile pH_e" 7.03(Att Bou~lle)

£> ALCOA pH",a -; 9.45(Act Alumino)

oL---'-_--'--_..L___'----'-_~_~___:'----l

o 20 40 60 eoInitiol Cone. of Sit mgSi/1

Figure 13. Effects of dissolved silica concentration on the removalefficiency of boron in deionized-distilled water by various adsorbentsCo =20 mg of B/l; adsorbent dosage = 25 gil

o Mdwh.te pH48 = 745 t 0 20(Atl. Bouait,)

A ,Al,.COA pH46 : 9.65:t 005(Atl Alumll>O)

• Hyaro DarcO pH4e ~ 6 40 1015IAcl Corbon}

• F,lIrO<iorb I>H48 ~ 8 25 t 020tAcI CortiOfl)

60

50~..ai

40<;

uc '0~

:~

w~

20

~a: 10

00 400 600 1200 1600 2000

Initiol Cone. of 50",2- ,mg SO~/I

Figure 14. Effects of sulfate ion concentration on the removal eHiciencyof boron in deionized-distilled water by various adsorbentsCo = 20 mg of B/l; adsorbent dosage = 25 gil

• Hydro Dorco pH48 =6.45 t 0.05(Acl, Corbon)

.. Fi1frO$orb . pH48 =8.10 t 0.15(Act. CorboPl)

60

50~..CD 40

<;

~ ;0

:~

w~

20

~cr '0

o Milwhife pH-<4e .. 7 05 t 0 05(ACI Bo,,"ite)

Ii. ALCOA . pH48 ·8.50 t 0.25("",el Alu"'''.,o)

O,L_-'-_--'---_-'-_-'-_---'--_----'-_~_~__'___ _'____o 200 400 600 800 1000

Iniliol Cone. of Ml;J. mq Mgtl

Figure 12. Effects of magnesium concentration on the removal efficiency of boron in deionized-distilled water by various adsorbentsCo =20 mg of B/l; adsorbent dosage = 25 gil

CaB(OH).+, respectively. Thus, the results suggest a changein the solution chemistry or in the surface of the adsorbentfollowing adsorption of Ca(lI) or Mg(lI) ions.

As shown in Figure 13, all the adsorbents except HydroDarco showed effects of dissolved silica on boron removal.McPhail et al. (39) demonstrated that boron adsorption onhydrous oxides of aluminum and iron was decreased byadsorption of 8i. They suggested that the reduced boron adsorption could be caused by either direct competition betweenmonosilicic acid and boric acid for adsorption sites, or bychanges in the oxide surface following adsorption. The competition for sites may occur because the maximum adsorptionoccurs in the same pH range as for boric acid (pK a = 9.2)(39-41). Jepson et al. (41) reported that the isoelectric pointof gibbsite falls with increasing silica adsorption to a limitingvalue of pH 3. Thus, boron adsorption may also be reducedby changes at the surface.

The effect of 80/- on the removal of boron is shown inFigure 14. All the adsorbents, except Hydro Darco, showeda relatively sharp initial decrease in the quantity of boronadsorbed. No progressive decrease was found with increasein the concentration of sulfate ions above 150 mg/L for Filtrasorb and about 200 mg/L for both activated bauxite andactivated alumina. Bingham and Page (28) measured amountsof boron adsorbed hy an amorphous soil from a solution of 50mg/L of boron containing sulfate ions as Na280. in varyingconcentrations up to 0.1 M (about 9600 mg/L of SO.2-). Ad-

sorption was independent of the presence of sulfate ion.8chalscha et al. (29), however, suggested a possible effect onbOron adsorption by volcanic ash soils from the presence ofK2SO•.

For all chemical species examined, removal of boron decreased with increasing concentrations of the chemical speciesonly to certain values, then remained unchanged. This mayindicate at least two different types of sites; one is nonspecificwhile the other is boron specific. Filtrasorb may have morenonspecific sites than other adsorbents.

Summary

All of the adsorbents examined, except Hydro Darco (activated carbon), are capable of removing boron from water tosome extent. Among the adsorbents, ~'iltrasorb (activatedcarbon) is superior to others because of the greater removalefficiency at initial concentrations of boron below 30 mg/L,with an adsorbent dosage of 25 giL.

The optimum pH for boron removal under experimentalconditions depends on both the characteristics of the background solution and the type of adsorbent. The optimum pHshifts to more alkaline pH when the solution salinity increases.However, salinity effects on both optimum pH and on removalefficiency are found only up to a certain limit of salinity fora given adsorbent. At above this value no additional effect onthe removal efficiency was seen. The salinity limits are approximately 5%. for Filtrasorb, 8%0 for activated bauxite, and


100/00 for activated alumina.Boron removal efficiency generally increases with de

creasing initial concentration of boron in the solution. Filtrasorb shows a more pronounced initial concentration effectthan the other adsorbents. Regardless of the characteristicsof background solution, a boron removal efficiency of about90% can be achieved with Filtrasorb (with an adsorbent dosageof 25 gIL) if the initial concentration of boron in the solutiondoes not exceed 5 mglL. The removal efficiencies of horon byactivated bauxite and activated alumina (with an adsorbentdosage of 25 gIL) are less than 70% at the same initial concentration of boron.

Generally, the presence of chemical species such as calcium,magnesium, silica, and sulfate results in a reduction in boronremoval efficiency. However, the effects increase only up tocertain limits, and no additional effect was seen.

Although boron uptake depends on many factors, the pHof the suspension and initial concentration of boron are criticalin determining the boron removal efficiency, especially forFiltrasorb.

The present results indicate that boron can be removedeither as H:IBOa or as B(OH)4-. The numbers and types ofavailable sites are different depending on the characteristicsof the solution and solids. It is likely that some of the sitesresponsible for the removal of boron are activated in contactwith solution. Depending on solution characteristics, e.g.,salinity, the sites being activated on the surface of the adsorbent are, to some extent, either HaBOa specific or B(OH)4specific. For instance, the sites on the surface of Filtrasorb incontact with deionized-distilled water have affinities forH:IBO:h while those in contact with simulated geothermalwater have high affinities for B(OH)4-.

Acknowledgments

The authors gratefully acknowledge the assistance of Dr.J. S. Devinny.

Literature Cited

(I) Donald, C. M., Prescott, J. A., in "Trace Elements in SoilPlant-Animal Systems", D. J. D. Nicholas and A. REgan, Eds.,pp 7-37, Academic Press, New York, N.Y., 1975.

(2) Wilcox, L. V., J. Am. Water Works Assoc., 50(5),650-4 (May,1958).

(:1) Wilcox, L. V., "Determining the Quality of Irrigation Water",Agriculture Information Bulletin, No. 197, pp 1-6, 1958.

(4) Chapman, H. D., "Citrus Industry", Vol. 2, pp 127-289, Universityof California, Division of Agriculture Sciences, 1968.

(5) Waggott, A., Water Res., 3(10),749-65 (1969).(6) Rarnett, P. R, Skougstad, M. W., Miller, K J., J. Am. Water

Works Assoc., 61(2) 61-7 (Feb. 1969).(7) Livingston, D. A., "Chemical Composition of Rivers and Lakes",

U.S. Geologic Survey, Prof. Paper 440-G, 1963.(8) Ataman, G., Chem. Ceol.. 2(4),297-309 (1967).(9) Matthews, P. ,J., Water Res., 8(12), 1021-8 (1974).


(10) Chen, K. Y., Gupta, S. K, Choi, W.-W., Eichenberger, B.,"Chemistry, Fate, and Removal of Trace Contaminants from Lowto Medium Salinity Geothermal Wastewaters", Report to NSFRANN, Environmental Engineering Program, University ofSouthern California, Los Angeles, Calif., Nov. 1976.

(11) Adams, R M., Ed., "Boron, Metallo-Boron Compounds andBoranes", Interscience, New York, N.Y., 1964.

(12) Greenwood, N. N., "The Chemistry of Boron", Pergamon Press,Elmsford, N.Y., 1973.

(13) Byrne, R H., Jr., Kester, D. R, J. Mar. Res., 32(2) 119-27(1974).

(14) Hansson, I., Deep-Sea Res., 20(5),461-78 (1973).(15) Ingri, N., Sven, Kem. Tidskr., 75, 199-230 (1963).(16) Christ, C. L., Truesdell, A. H., Erd., R. C., Ceochim. Cosmochim.

Acta, 31(3),313-37 (1967).(17) Kunin, R, Adv. Chem. Ser., No. 12, 139-43 (197:1).(18) Patterson, J. W., "Wastewater Treatment Technology", Ann

Arbor Science, Ann Arbor, Mich., 1975.(19) Sims, J. R, Bingham, F. T., Soil Sci. Soc. Am. Pmc.. 31(5),

728-32 (1967).(20) Sims, J. R., Bingham, F. T., ibid., 32(3),364--9 (1968).(21) Sims, J. R, Bingham, F. T., ibid., 32(3),369-7:1 (1968).(22) Rhoades, J. D.,. Ingvalson, R D., Hatcher, J. '1'., ibid., 34(6),

938-41 (1970).(23) Bohor, B. F., Gluskoter, H. J., J. Sediment. Petrol., 43(4),945-56

(1973).(24) Harder, H., Sediment. Cevl., 4(2), 15;J-75 (1970).(25) Couch, E. L., Am. Assvc. Pet. Ceol. Rull., 55(10), 1829-37 (Oct.

1971).(26) Grimn, R A., Burau, R. G., Soil Sci. Svc. Am. Pmc.. :l8(6),892-7

(1974).(27) Bingham, F. '1'., Page, A. L., Coleman, N. '1'., Flach, K, ibid., 35,

546-50 (1971).(28) Bingham, F. '1'., Page, A. L., ibid.. 35(6),892-:1 (1971).(29) Schalscha, F. B., Bingham, F. '1'., Galindo, G. G., Galvan, H. P.,

Svil Sci., 116(2),70-6 (l973l.(:10) Hatcher, J. '1'., Bower, C. A., ibid.. 85(6),319-23 (1958).(;Jll Hatcher, J. 1'., Bower, C. A., Clark, M., ibid., 104(6), 422-6

(1967).(;J2) Ellis, B. G., Knezek, B. D., in "Micronutrients in Agriculture."

Mortvedt el aI., Ed., pp 59-78, Soil Science Society of America,Madison, Wis., 1972.

(33) Sigworih, E. A., Smith, S. B.. J. Am. Water Works Assoe.. 64(6),386-91 (June 1972).

(34) Humennick, M. ,J., Jr., Schnoor, J. L.,J. Environ. £og Oiv., PrilLASCE, 100(No. EEG), 1249-62 (Dec. 1974).

(:l5) O'Connor, J. '1'., Badorek, D., Thiem, L., 170th National Meetingof the American Chemical Society, Chicago, Ill., Abstract ENVT-19,Aug. 25-29, 1975. '

(36) Huang,C.-P., Wu,M.-H., J. Water Pollul. Control Fed., 47(10),24:l7-46 (Oct. 1975).

(:l7) Choi, W.-W., Ph.D. Dissertation, Universiiy of Southern California, Los Angeles, Calif., Jan. 1978.

(:18) Hingston, F. ,J., Posner, A. M., Quirk, J. P., Soil &i., 23(2),177-92 (1972).

(39) McPhail, M., Page, S. L., Bingham, F. T., Svil S<-i. SO<'. Am. Prvc.36(3),510-4 (1972).

(40) Huang, C. P., Earth Planel. &i. Lett., 27,265-74 (1975).(41) Jepson, W. B.,.Jeffs, D. G., Ferris, A. P.,J. Colloid lnterface Sci.,

55(2),454-61 (May 1976).

Received for review June 28, 1978. Accepted August 28, 1978. Thisstudy was supported by Grants AER 75-09957 and AER 75-09957AOI from RANN of the Nalional S<-ien<'e Foundation.

Emissions from Pressurized Fluidized-Bed Combustion Processes

Keshava S. Murthyh, James E. Howes, and Herman Nack

Battelle-Columbus Laboratories, Colum.bus, Ohio 43201

Ronald C. Hoke

Exxon Research & Engineering Company, Linden, N.J. 07036

• Results of the comprehensive analysis of emissions froma pressurized fluidized-bed combustion unit (the ExxonMiniplant) are described as an illustration of the methodologyfor comprehensive analysis. The results are discussed in thecontext of the overall environmental assessment of tbe processbeing conducted by the U.S. Environmental ProtectionAgency. The comprehensive analysis of the fluidized-bedcombustion emissions and process streams involved approximately 740 measurements on about 90 samples, usingmore than 40 different inorganic, organic, and physical analytical methods. A brief discussion on the sampling methodsand analytical techniques is also included.

Environmental data acquisition is one of the seven majorsteps (Figure 1) in conducting a complete environmental assessment of emerging energy technologies such as fluidizedbed combustion WBC) of coal (J). The data are acquiredprimarily by comprehensive analysis of emissions. Precommercia I-stage comprehensive analysis (CA) of emissions fromFBC units provides an opportunity for detecting potentialenvironmental problems early in the development of theprocess. The environmental assessment of the process basedon the CA data should assist in the identification and/or development of the most cost-effective control technologies.

A phased approach in three levels is the currently acceptedtechnique for sampling and analyzing emissions. The threelevels of analysis are defined as follows:

• Levell analysis includes comprehensive screening of awide variety of organic and inorganic components. Levellsampling and analysis are designed to rapidly identify thepotential pollutants from a source, and to measure them witha target accuracy factor of ±3. It also identifies all processstreams that may contain four types of pollutants: gaseous,particulates, liquids/slurry, and solids. In addition, level 1st.rategy includes bioassay testing of several effluent streamsto obtain a direct index or est.imate of their toxicity potent.ial.

• Level 2 analysis is based on level 1 results. More accurate,compound-specific analytical techniques are used to pinpointproblem pollut.ants and effluent. streams. Levell data, together wit.h bioassay data, will be used t.o identify the analytical needs of levels 2 and 3.

• Level:1 analysis (not yet defined completely) would include routine continuous monitoring of those pollutantsidentified as specific problems in level 2.

Aset of 12 biological tests was used in level I testing. Thesetests and the samples on which they were used are given inTable I. They are designed t.o test the possible toxicity of awaste st.ream to mammalian, marine, freshwater, plant, andsoil systems. This test protocol provides a fairly good representation of the various biological constituents of the environment that might be exposed to a waste stream. Thebioassays are designed to be implemented quickly and inex-

I Present. address, Rattelle Northwest Lahoratories, Hichland.Wash. 99;\.')2.

pensively, in keeping with the screening nature of level 1t.esting. Their output will permit a relative ranking of wastestreams according to biological hazard, and, together with thechemical and physical data, will provide an overall hazardcharacterization of the waste streams.

The measurement techniques and results presented in thispaper are based largely on level 1 analysis. The samplingmatrix for level 1 (and some level 2 analysis of substances already known as problem pollutants) is shown in Table II. Datapresented in this paper were obtained from the pressurizedFBC facility at Exxon; sampling was conducted in accordancewith Table II. This facility has a 0.32-m diameter reactorwhich was operated at 890°C, 900 kPa, 1.2 m/s superficialvelocity, 40% excess air, 75 kg/h coal feed, and 11.0 kg/h dolomite sorbent feed at a Ca/S molar ratio of 1.25 for the testsreported in this paper.

Experimental

Sampling Methods. The comprehensive analysis programfor the Exxon unit consisted of sampling seven of the ninestreams shown in Figure 2. The nine streams are: (1) coal feed,(2) dolomite feed, (3) second stage cyclone discard, (4) bedreject material, (5) cyclone discard leachates, (6) bed rejectrnaterialleachates, (7) undiluted stack gas, (8) diluted stackgas, and (9) dilution and combustion air. Sampling of thesorbent regenerator unit was not performed since this unit wasnot operated during the tests. Streams 5 and 6 were simulatedin the laboratory since no leachate streams were actuallypresent at the miniplant site.

Five tests were conducted at Exxon from March 28 to AprilI, 1977; the Miniplant was operated continuously for about80 h. Sampling was performed on an around-the-clock basisby two 7-man teams working 12-h shifts. During each test,lasting 5 h, the various FBC streams were sampled by thetechniques given in Table II.

Grab samples of solids from the FBC process streams weretaken periodically throughout each test. The individualsamples were composited to obtain one sample per test. Thegases (CO, CO2, O2, S02, etc.) in the undiluted f1ue gas atstream 7 were sampled continuously for analyses by Exxonon-line instrumentation. Integrated grab samples were alsotaken for CO2, and O2analyses by Orsat. S02 and NO, weresampled by EPA methods 6 and 7, respectively, to providebackup data. The controlled condensation method was usedto sample for SO:/H2S04, and special impinger trains wereused for sampling NH: lo HCN, HC!, and HF.

Continuous sampling of the undiluted flue gas was performed for total hydrocarbon measurements. Grab samplesin glass bulbs were taken several times during each test for gaschromatographic analysis of C,-C6 hydrocarbons and sulfurcompounds.

The primary particulate sampling was performed in the fluegas stream which was reduced to near atmospheric pressureby dilution with air. The source assessment sampling system(SASS) was used to collect samples for chemical and physicalanalysis. In three tests, the stainless steel condenser modulenormally supplied with the SASS unit was replaced with aglass module of similar dimensions. The glass module modification was included in these tests since a preliminary sampling experiment indicated excessive corrosion of the stainless

0013-936XI79/0913-0197$01.00/0 © 1979 American Chemical Society Volume 13, Number 2, February 1979 197

Table I. level 1 Bioassay Matrix

sample type health effects tests ecology effects tests

water and microbial rodent acute cytotoxicity algal static soilliquids mutagenesis toxicity bioassays bioassays microcosm

solids + + + + + +gases plant stress ethylene

particulates + + soil microcosmsorbent + +

Tabla II. Sampling and Analyses to Be Performed in Comprehensive Analysis of FBC Units

system stream or m~~i_al

solid wastestack collec- leachate

sample parllculates tion from solid wastecollection fTiid--iTite device bed coal sorbent collection

species. pOllutanls techniques a analysis melhod b >3Jjrn <3~m gas discard relect teed teed device bed

continuous gasmeasurementsCO2 Cw NOIRc XCO Cw IR or UV c XNO Cw CLc XN02 Cw CL' XS02 Cw NOIRc XO2 Cw PM" X

integrated gasmeasurementsCO2 IG FGC/TC XCO IG FGC/TC XNO, IG+ M7 FGC/TC + M7 XS02 IG +M6 FGC/TC + M6 X()2 IG FGCITC XN2 IG FGC/TC XH2O IG FGC/TC XH2S IG FGC/FPO XCOS IG FGC/FPO XCH3SH-C.H '3SH IG FGC/FPO XC,-C. hydrocarbons IG FGC/FIO XC,-C'2 hydrocarbons IG FGC/FIO XC,-C. chlorocarbons IG FGC/EC XNH3 IG FGCITC XHCN IG FGC/TC Xcyanogen IG FGC/TC XS031H2S0, GT/St ion chromatograph XHCI St titration Xfluoride St SIE X

integrated specimensfor subsequent group anal.inorganic chemicals

71 elements (Li SASS/GS SSMS X X X X X X X Xthrough U)

proximate (fuels) Gs ASTM 03172-73 Xultimate Gs ASTM 03176-74 X X Xsulfur forms (fuels) Gs ASTM 02492-68 Xradionuclides (gross SASS/Gs LBPC X X X X X X

n &/i)organic chemicals

organics by class SASS/Gs LCIIR (total sample X X X X X Xand 8 fractions)

organic compds SASS/Gs LC/LRMS (selected X X X X X Xtractions)

POM SASS/Gs GC/MS X X X X X Xorganic-reduced sulfur SASS/Gs GC/FPO (8 frac- X X X X X X

compounds tions combinedCr C,2 hydrocarbons SASS/Gs GC/FIO X X X X X Xorganic mass SASS/Gs microbalance (8 X X X X X X

fractions)integrated specimens for

subsequent specific anal.volatile, toxic elements

(Be, Cd, Hg, Pb, Se, SASS/Gs AAS X X X X X X X X XSb. Te)

As SASS/Gs colorimetric X X X X X X X X XCI- SASS/Gs colorimetric X X X XF- SASS/Gs distillation/colori- X X X X X X

metric


Table II. continued

system stream or materialsolid waste

stack collee- leachatesample particulates lion from solid waste

collection mid fine device bed coal sorbent collectionspecies, pollutants techniques a analysis method b >31Jm <31Jm gas discard reject feed feed device bed

Na Gs AAS XCa Gs AAS/titration X XMg Gs AAS XCO/- SASS/Gs gas evolution X X X X X XSO/- SASS/Gs titration/ion X X X X X X X X

chromatographySO/- SASS/Gs S02 evolution/ X X X X X X X X

colorimetricS2- SASS/Gs H2S evolution/ X X X X X X

titrationsN02- SASS/Gs colorimetric X X X X X X X XN03- SASS/Gs colorimetric X X X X X X X XC (noncarbonate) Gs combustion X X X Xheating valve Gs ASTM D 20' 5-66 Xparticle morphology Gs LM/SEM X X X Xparticle size Gs sieve ASTM D 410- X X X X

38particle mass SASS/M5 weight x d X

biological assayshealth

microbial mutagenesis SASS/Gs salmonella/ames X X X X X X X Xcytotoxicity SASS/Gs human lung X X

fibroblast (WI-38)cytotoxicity SASS/Gs rabbit alveolar X X X X X X

macrophage(RMA)

acute toxicity SASS/Gs in vivo rodent X X X X Xecological

freshwater algal SASS/Gs algai bottle X X X X X Xfreshwater animal SASS/Gs static X X X X X X

(daphnia)freshwater animal (fish) SASS/Gs static X X X X X Xsaltwater algal SASS/Gs unicellular marine X X X X X X

algaesaltwater animal (grass SASS/Gs static X X X X X X

shrimp)saltwater animal (fish) SASS/Gs static X X X X X Xterrestrial soil SASS/Gs soil microcosm X X X X X X X Xterrestrial plant SASS/Gs stress ethylene X

a Cw. continuous withdrawal through nonreactive line with mechanical filtration; lG. integrated grab sample of gas in glass bulb; GRISt, Goksoyr·Ross coil/specialsampling train; St, separate wet chemical train to collect gas (such as method 6); SASS, source assessment sampling system (train used for suspended particulates,organics, and volatile trace elements); Gs, grab multiple samples riffled to reduce to 100-g representative sample; MS, EPA method 5; M6, EPA method 6; M7,EPA method 7. b NOlA, nondispersive infrared; IA, infrared; UV, ultraviolet; CL, chemiluminescence; PM, paramagnetic; FGC/TC, field chromatograph/thermalconductivity detector; FGC/FPD, field chromatograph/flame photometric detector; FGC/FID, field chromatograph/flame ionization detector; FGC/EC, field chro-matograph/electron capture detector; SIE, selective-ion electrode; SSMS, spark source mass spectroscopy; ASTM, American society tor testing materials standardmethod: LBPC, low background gas proportional controller; LC, liquid chromatography; LAMS, low-resolution mass spectrometry; Ge, gas chromatography; GC/MS,gas chromatography with mass spectrography; AAS, atomic absorption spectroscopy; LM/SEM, light microscopy/scanning electron microscope. C Or acceptableinstrumentation already installed at FBG Unit. d Coarse (> 10 J.l.m) and filter « 1 J.l.m) fractions included.

module during the sampling of the FBC emission. Two testswere performed using the stainless steel module.

Method 5 sampling was used to obtain compliance-relatedmass emission data.

The Balston filter sample of particulates from the undilutedflue gas stream was obtained to study changes in the particulate characteristics or composition that might be caused bythe dilution of the flue gas stream. The dilution air was sampled with a Tenax trap to identify any organics that mightcontaminate the flue gas stream.

Analytical Techniques. Analyses were performed onsamples from three of Exxon's sampling tests. Approximately90 samples were analyzed, using more than 40 differenttechniques. (For details on analytical procedures used incomprehensive analysis, see ref 2.)

To assure sample integrity and representativeness, specialpreparation techniques were needed, e.g., compositing, pulverizing, and aliquoting. After suitable preparation, the

samples underwent several inorganic and organic analyses.The inorganic analysis included determining 71 elements bySSMS, Hg by FAAS, Sb by AAS/GF, and As by colorimetricmethods. The organic analyses comprised several level 2 aswell as level 1 tests. Physical measurements of particles in allSASS and FBC stream solid samples were also taken. In addition, three methods were used to monitor the quality of theinorganic analysis data as follows: (1) the analysis of NBSstandard reference materials (SRM); (2) dynamic spikingtechniques; (3) comparison of results obtained by two differentanalytical methods, spark source mass spectroscopy (SSMS)and atomic absorption spectrometry (AAS).

In general, the sampling methods proved satisfactory, despite some technical problems. Most of the analytical techniques provided acceptable level 1 data. The quality controlprocedures resulted in several useful suggestions for improvements. Though quality control was applied primarilyto inorganic analyses, a broader program to cover organic


CurrentProcess

TechnologyBackground

• Quantified MedIa DegradatIon Alternatl ....es

• Standards 01 Practice Manuals

• Standards De....elopment ResearchOala Base Reports

Figure 1. Simplified block diagram of environmental assessment steps

COOLINGWATER

C--~~---pn--tC~0

o Circled numbers denotestreoms sompled

o COAL ANO J{:;\ LIMESTONE ~-------,o FEED SUPPLY

AUXILIARYAIR

COMPRESSOR

MAIN AIRCOMPRESSOR(t400 SCFM AT150 PSIG)

Figure 2. The fluidized-bed combustion miniplant at Exxon during comprehensive analysis tests

Table III. Analysis of Flue Gasconcn, air MATE,

substances /lg/m3 (ppm) ~g/m3

CO 61734 (53) 55000

CO2 24 X 106 9 X 106

O2 5.5% noneHC 2 196 (3.3) none

H2S04 mist + S03 2079 (5) 1000

S02 74813(28) 13000NH3 501 (0.6) 18000CN 1.2 5000F 10120 (13)

CI 54824 (33) 3000

NO. as N02 148442 (70) 9000

As <2 2Be <0.4 2Cd 0.1 8.2Hg 0.85 50Pb <1.2 150

Sb <17 500Se <1.4 10.8Te <17 100


measured by

on-line instruments

wet chemistry

atomic absorption

Results and Evaluation

Comparisons to MATE Values. To evaluate the signifi-

analyses and other suhjects is under way.

Comprehensive Analysis Result"

Before the results are discussed, some qualifications to thedata presented below should be noted: (1) This is the firstextensive analysis of emissions on a fluidized-bed unit. (2)Steady-state conditions may not have been achieved duringthe CA tests since the sulfur content of the coal varied. Thisresulted in drastic tapering of the S02 concentrations in theflue gas. (3) The regenerator was not operated during CA runsat the Miniplant. However, since the data collection processwas well monitored and controlled, the data are consideredreliable.

Table IV. Organic Compounds in Flue Gas

substances

anthracene/phenanthrene

methylanthracenes

f1uoranthene

pyrene

methylpyrene/fluoranthene

benzo [ c j phenanthrene

chrysene/benz[ ajanthracene

benzofluoranthenes

benz [ a1pyrene

HC > C6-C'2, I'g/m3

HC > C'2, I'g/m3

concn,ng/m3

535

2691.00.2

3.81.00.5

174058

air MATE.ng/m3

483000483000

90 X 106

233 X 106

no data

26.9 X 106

44800897000

20no data

no data

cance of the measured concentration of substances in the effluent streams, the measured concentrations were comparedto the MATE (minimum acute toxicity effluent) values (3).The procedures involved in developing MATE values can befound in ref 3. MATE's are approximate concentrations ofcontaminants in air, water, or land effluents which may evokeminimal significant harmful responses to humans or theecology, within 8 h. In general, types of data chosen to providethe basis for MATE's include threshold limit values (TLV),NIOSH recommendations, lethal dose concentrations, andother toxicity data, drinking water regulations, and waterquality criteria. For a single substance, five specific MATEconcentrations can be defined: two air and two water MATE's(each based on both health and ecology effects) and one landMATE (based on the lower water MATE).

MATE values indicate allowable concentrations of contaminant in effluent streams, and provide a point of referencefor control technology goals. However, MATE's cannot beused as absolute indicators of minimum toxicity since they arestill in the developmental stage.

Emissions in Flue Gas. Samples of the flue gas were collected at about 900 kPa pressure before air dilution, and analyzed. Table III shows flue gas composition measured withon-line instruments and wet chemistry tests.

The lowest concentrations of S02 and NO" in the flue gasare, respectively, 28 ppm (0.l8Ib/ll)6 Btu) and 70 ppm (0.09Ib/lOt; Btu). These are very low in comparison with existingnew source performance standards for coal-fired steam generators: 1.2Ib/lO'; Btu for S02 and 0.7 ib/IO'; Btu for NO".

However, in comparison with the MATE's shown in TableIII, both S02 and NO,. have much higher concentration valuesthan the MATE's allow. In fact, the S02 concentration in theflue gas is about 6 times the MATE value, and the NOx con-

Table V. Inorganic Analysis of Particulate Emissions

is land MATE exc:eeded atsize range land obsd 11100 obsd

substance 1-3.um 3-10.um MATE value value

Volatile and Toxic Elements, I'g/gaAs 45 36 0.1 yes yes

Be 15 11 0.03 yes yes

Cd 2.1 1.3 0.004 yes yes

Hg <0.02 <0.02 0.02 no no

Pb 44 43 0.1 yes yes

Sb 4.0 2.3 0.4 yes no

Se 27 22 0.05 yes yes

Te <0.5 <0.5 3.0 no no

Major Elements, I'g/g

AI 200000 200000 2.0 yes yes

Fe 60000 20000 0.5 yes yes

Si 200000 200000 300 yes yes

K 3000 1500 1720 yes no

Ca 30000 30000 32.4 yes yes

C(total 12000 11000carbon)

Anions, Wt %CI- 0.011 0.007F- 0.031 0.032cOl- <0.2 <0.2SO/- 9.4 8.7SOl- 0.001 0.004S2- <0.03 0.03N03- <0.001 <0.001N02- <0.001 <0.001

a Atomic absorption spectroscopy method used except for As which was determined calorimetrically.


Table VI. Inorganic Chemical Analysis of Bed RejectMaterial

Table VII. Organic Chemical Analysis of Bed RejectMaterials

Volatile and Toxic Elements, p.g/ga21 0.12.7 0.030.44 0.004

<0.02 0.028.0 0.10.8 0.050.5 0.4

<0.5 3.0

202212

4

53

17

<0.2

obsvn

none

<0.1<0.1

landMATEsubstances

Hydrocarbon Content above C-6. p.g/ghydrocarbon according to

boiling point rangeC-7C-8C-9C-l0C-llC-12

>C-12

NONONONONONONO

Reduced Sulfur and Other Compdsreduced sulfur. p.g/g NOother compds detected NO

a ND, no data.

Polycyclic Organic Materials. ng/ganthracene/phenanthrene 14 500others specifically sought Noatotal

yesyesyesnoyesyesyesno

yesyesyesyesyes

obsvnexceedsMATE?

landMATE

2.00.5

3001720

32.4

obsdvalue

Major Elements, p.g/g15000100001500010000

2000001600

substance

AIFe

SiK

CaC (noncar

bonate)

AsBeCdHg

PbSeSbTe

a Atomic absorption spectroscopy method used. except for As which wasdetermined calorimetrically.

centration is 16 times. This fact does not necessarily mean thatS02 and NO. are a problem; but it indicates that the MATE'sate deliberately conservative and may need reevaluationand/or revision.

The concentrations of all the eight volatile toxic elementswere well below the MATE's. Incidentally, arsenic concentration measured by spark source mass spectrography washigher than the MATE's, but the colorimetric analysis, classedas a level 2 technique, showed it to be less than the MATEvalue.

Concentrations of polycyclic organic matter in flue gas givenin Table IV are lower than the air MATE's.

Suspended Particulates in Flue Gas. The particulateconcentration in the flue gas, after passing through two conventional cyclones. but without going through fine particulatecontrol equipment, was about 1.2 g/scf (1.9 Ib/106 Btu) ascompared to the EPA standard of 0.lib/10" Btu. However,if an appropriate third-stage particulate control device thatremoves over 96% of the particulates can be demonstrated, theEPA emissions standard would be met.

The physical properties of the collected dust from the fluegas may be of interest The size distribution and morphologyare: <1 p.m, 9 wt%; l-3p.m, 39wt%; 3-10p.m, 21 wt%; >lOp.m,33 wt %; predominant shape, irregular; evident cleavage, none;structure, 3 phase; color, white, black, red. Thus, 46 wt % ofthe suspended particulates collected by the SOUTce assessmentsampling system's cyclone (4) was less than 3 p.m, and is in therespirable range. The ('( radioactivity averaged about 6 ± 3pCi/g, and {j radioactivity, 30 ± 10 pCi/g.

Table V indicates that the toxic and volatile metal contentin the particulates is of real significance. Since most of these

CIFCOlSO;S032SN02

N03-

Anions. Wt %0.0300.003

15.127.70.0110.005

<0.001<0.001

particulates will be collected as solid wastes by any effectiveparticulate collection system, the land MATE values apply.Of these metals, all but Te and Hg would exceed the landMATE even if the particulates were removed from the flue gasat a reasonable collection efficiency and were considered forland disposal (see Table V). The second "yes" in the MATEcomparison column indicates that the particulates would stillconstitute a land disposal problem even when diluted by afactor of 100 by mixing with nontoxic materials (or some othertechnique) to reduce the toxic metal concentration. Theseconclusions are valid for elemental metals, but are not necessarily true for compounds of these metals.

Emissions in Bed Solids. Table VI shows the inorganicanalysis of the bed reject solids. Several toxic metals exceedMATE values, although their compound form may be lesstoxic than implied by the comparison. The anion analysisindicates the degree of conversion from carbonate to sulfatewithin the bed. (For a complete trace metal composition of thismaterial, see ref 2.) Whether the chemical form in which themetals are present is an unacceptable hazard for simple landdisposal still needs to be determined. The concentration ofpolycyclic organic materials was found to be insignificant, asshown in Table VII. The organic constituents in the bed rejectmaterial pose no environmental problem for land disposal.Table VII also shows the content of hydrocarbons with morethan six carbon atoms; these amounts appear to be fairlylow.

Leachates from Bed Reject Materials. Leachates weregenerated in the laboratory using the spent bed materials(SBM). The 720-h shake method was employed. This methodinvolved shaking:33 g of SBM with 100 mL of triple-distilledwater in a reciprocating shaker for 72 h at 120 cpm. After 72h, the liquid was decanted and saved. A fresh 100 mL of distilled water was again added to the same SBM sample. Thisprocess was repeated 10 times to get 720 h of shaking and 1000mL of decanted leachates. By the same procedure, leachateswere generated from the fly ash samples collected from thesecond cyclone. Both leachates were analyzed for inorganics,using level 1 techniques (SSMS) for elements. Some level 2techniques (wet chemistry or atomic absorption spectroscopy)were employed to determine antimony, mercury, and arsenic.Leachates were also analyzed for anions (SO.2-, SO:\2-, etc.)


Table VIII. Inorganics in Leachates from Spent Bed Material (SBM) and Fly Ash (FA)

substance conen, water.. mg/l MATE, MATEparameter SBM FA mg/L exceeded?

Li 6 20 0,38 yesNa 10.4 52 800 noMg 9.6 6.4 87 noAI 0.8 1.4 1.0 yesCa 460 1000 16.2 yesV 0.1 0.1 0.15 noFe 0.2 0.2 0.25 noNi 0.03 0.03 0.01 yesSe 0.07 0.07 0.025 yesPb 0.05 0.05 0.05 noAs 0.04 0.05 0.05 noCW <0.03 <0.03 0.015 undecidedsol- 1610 1950 250" yespH 12.2 9.0 5-9" yes

aproposed U.S. EPA drinking water standards; no MATE value available.

Table IX. Results of the Biological Testing of FBe Waste Streams

testtest

paramelerfluegas

waste streams

suspendedparticulate.

bedsolids

bedsolids

leachate

AmescytotoxicityRAM

rodent acutetoxicity

aquaticfreshwater

algaldaphniafish

saltwateralgalshrimpfish

terrestrialsoil microcosm

stress ethylene

IJ NT. no toxicity.

+/-

LDsoLDso

ECsoLCsoLCso

ECsoLCsoLCsoranked in

order ofdecreasingtoxic.

% ofincreaseovercontrol

NT(O%)

+596,3000

2

NT"NT

3

NTNT

45%40.9%25.3%

NTNTNT1

by standard wet chemistry. Organics were analyzed by level1 techniques (liquid chromatography separation and infraredanalysis). Significant results of inorganic analysis are presented in Table VIII in comparison with water MATE's (basedon ecological effects). These results show that As, Ca, Ni, Pb,Li, Se, S042-, and Al are present in concentrations equal toor exceeding the MATE's. Hence, these substances should beanalyzed by level 2 techniques in future leachate studies toaccurately establish their concentrations and environmentaleffects. Also, the compound forms in which they are presentshould be investigated.

The results of organic analysis were not as conclusive as theresults of inorganic analysis. Further 1V0rk is needed to determine which specific organic compounds in leachates arepresent in harmful amounts.

Leachate Analysis and the RCRA. The importance of theabove results to FBC waste disposal will be determined bycomparing the leachate analyses with the requirements proposed under the Resource Conservation and Recovery Act

(RCRA). Under Section 3001 of RCRA, waste will be definedas hazardous, if it is inflammable, corrosive, infectious, reactive, radioactive, or toxic. Of these criteria, corrosivity, reactivity, and toxicity are likely to be pertinent to FBC residue.

Based on draft RCRA guidelines, FBC waste will be considered corrosive if a saturated solution of the residue in waterhas a pH of less than 2 or greater than 12. The results in TableVIII showed the leachate from spent bed material to have apH of 12.2 (corrosive). The pH of a saturated solution couldbe expected to be somewhat higher. However, the pH of thefly ash leachate was only 9.0. Therefore, if disposed together,the mixture of fly ash and spent bed materials may not becorrosive.

According to draft RCRA guidelines, FBC residue will beconsidered toxic if its leachate (to be generated by a "standard" method, not yet determined): (a) has a concentrationof any substance greater than or equal to 10 times the drinkingwater standard; (b) has a concentration of any substance


greater than or equal to 0.35 times the lowest oral mammalianLD"o (mg/kg) for that substance, as listed in the NIOSHRegistry of Toxic Effects of Chemiclll Substances; (c) has aconcentration of any substance equal to 10 times the lowest96-h LC.';() (mg/L) for the substance, as listed in the NIOSHRegistry. In these studies, none of the primary drinking waterstandards is exceeded by a factor of 10 by either leachate.However, the results still must be measured against criteriaband c above.

If the MATE values for calcium are similar to the primarydrinking water standards, calcium in leachates may well exceed the allowable standards by more than a factor of 10,thereby causing the FBC residues to be considered hazardous.

The importance ofthe designation "hazardous" lies in thesomewhat stricter disposal requirements likely to be imposed,and the additional permits, testing, and record-keeping required by RCRA.

Bioassay Results. The biological test results for four FBCwaste streams are given in Table IX. The health and ecologicaltests on each stream were performed according to the pilotleveI 1 bioassay program.

The flue gas stream was tested only with the stress ethylenetest. At present, no other level 1 tests are suitable for testinggases. Results indicate the gas was nontoxic. Some caution isassociated with this conclusion because the full quantity ofgas required for the test was not available and the sample hadto be stored for some time before testing. These are due toproblems associated with methodology development.

Several tests were performed on the spent bed solids whichshowed very low or no toxicity in all tests, and would not likelyconstitute a biological hazard in its solid form. However, theleachate from the spent Oed solids showed some toxicity in twoof the tests. The results show that it was nontoxic to mammals(health tests) and marine organisms, but toxic to freshwaterand soil organisms. This stream would likely require furtherstudy to determine its potential biological hazard.

Only the suspended particulates stream gave positive Amestest results. The particulates were mutagenic and thus mayalso be carcinogenic. This stream was also toxic to soil organisms.

Based on the biological tests alone, the relative ranking ofthe four waste streams, in order of decreasing toxicity, is: (1)spent bed solids leachate; (2) suspended particulates; (3) spentbed solids; (4) flue gas. It must be emphasized that the testresults provide only relative data, and the actual hazard tohumans and other organisms can be determined only throughadditional testing.

Summary and Conclusions on Comprehensive AnalysisResults

On Source Emission Data. The major conclusion is:• Comprehensive analysis of emissions from emerging

energy technologies yields useful results for completing theenvironmental assessment of the processes.

Other conclusions are:• Pressurized coal-hurning FBC units can meet existing

new source performance standards for SO~ and NO.. emissionsfrom coal-fired steam generators. Particulate emissions control needs demonstration.

• MATE's for S02' NO.. , CO, and possibly for other substances need reevaluation.

~ Polycyclic organic matter (POM's) in flue gas or otherefnuents from FBC units do not appear to be health/ecologicalhazards. POM's are concentrated in fine particles «3 I'm) asopposed to coarse (>3 I'm) particles in the suspended particulates.

• Though biological assay data are difficult to interpret at


this stage, spent bed material leachate and suspended particulates do show a relatively higher toxicity than flue gas andbed solids. This trend corresponds with the greater thanMATE's concentrations of many volatile and toxic trace elements (As, Ni, Pb, Li, etc.) in leachates from bed materials.These results, therefore, indicate the need for further study.The final interpretation of the bioassay results and theirtoxicity ratings is being considered by the U.S. EPA.

• The results of this study do not imply that fluidized-bedcombustion of coal generates solid wastes of greater or lessertoxicity than other methods of coal combustion, since the solidwastes from other methods have not been subjected to suchcomprehensive analysis. Also, the above results need carefulevaluation and further validation.

To obtain useful reliable data, steady-state operation andan adequate supply of uniform coal and sorbent for the duration of sampling must be assured.

Acknvwledgments

The studies described in this paper are part of the environmental assessment of the fluidized -bed combustion processwhich Battelle is conducting for the U.S. EPA, under theguidance of R. P. Hangebrauck and D. Bruce Henschel of theAgency's Industrial Environmental Research Laboratory,Research Triangle Park, N.C. The comprehensive analysesof emissions were conducted in cooperation with many individuals of Exxon. The authors sincerely appreciate the assistance and support of all these persons.

Nomenclature

CA = comprehensive analysis

FBC = fluidized-bed combustion

SASS =source assessment sampling system

SSMS =spark source mass spectroscopy

AAS = atomic absorption spectrometry

AAS/GF = atomic absorption spectrometry/graphitefurnace atomization

FAAS =flameless atomic absorption spectrometry

POM =polycyclic organic matter

NBS = National Bureau of Standards

SBM = spent bed materials.

SRM = standard reference materials

MATE = minimal acute toxicity effluent

RCRA = Resource Conservation and Recovery Act

NIOSH = National Institute for Occupational Safety andHealth

Literature Cited

(I) Henschel. D. 8.. "The EPA Fluidized-Red Combustion Pr<'Kram:An Updat.e". Fiftb International Conference on Fluidized·BedCombustion. WasbinKton. D.C .. Dec. 1~-14. 1977.

(~I Murt.hy. 1<. S., Howes, .1. K. Nack. H., Hoke, R. C.. "Comprehensive Analvsis of Emissiomt from Fluidized-Bed CombustionProcesses", U.S. EPA Symposium on Process Measurements forEnvironmental Assessment. Atlanta, Ga .. Feb. 1:1-1:;, 1978.

n) Cleland, -J. G., I<in~shury. G. L., "Mult.imedia EnvironmentalGoals for Environmental Assessment", Vol I and ~, Final Reportby Research Triang:le Institute of U.S. Environmental ProtectionA~ency, Contract. No. 68-m-~612. EPA-r,()()/7-77-1:16a and b, Nov.1977.

(4) Hamersma, J. W., et. al.. "IEHL-HTP Procedures Manllal: Level1 Environmental Assessment", ~;PA-()()()/2-76-160a, PI' ~-46, U.S."~nvironmental Protection Agency, Washington. D.C., .June1976.

R('feived fur reL'h'w Ft'bruary /·1, lY7H. AC(,l'plf·d AUMlist 28. 1978.

Free-Radical Oxidation of Organic Phosphonic Acid Salts in Water Using HydrogenPeroxide, Oxygen, and Ultraviolet Light

Theodore Mill' and Constance W. Gould

SRI International, Menlo Park, Calif. 94025

• Photochemically initiated HO radical oxidations of 0.2-3.0M isopropyl methylphosphonic acid (IPA) and methylphosphonic acid (MPA) (as sodium salts) have been carried out at25°C in water solution using 0.01-:l.0 M hydrogen peroxideand oxygen to effect complete oxidations of botb compoundsto phosphoric acid, carbon dioxide, and water. No intermediate oxidation products were found from oxidation of MPA,whereas acetone, acetic acid, and methylphosphonic acid werefound in the oxidation of IPA. From the relative proportionsof these intermediates, the relative and ahsolute rate constantsfor reactions of HO radical with IPA and MPA were calculated. The experiments suggest that rapid and complete oxidation of alkyl phosphorus compounds to simple productsmay be possible but careful control of reaction variables isnecessary to achieve efficient use of H~O".

°C, some source of free radicals is usually needed to initiatethe oxidation. Ozone or hydrogen peroxide is well suited forthis purpose in water, particularly if used with UV light, whicheffects 0-0 bond cleavage to give 0 atoms or HO· radicals(7).

In this work we used hydrogen peroxide and UV light below300 nm to provide the reactive HO· radicals needed to initiatethe oxidative cleavage of these phosphoric acid derivatives.Oxygen was also present to convert carbon radicals to peroxyradicals. Because the HO· radical is extremely reactive towardmost organic H-atom donors (8, 9), it should produce carbonradicals efficiently from MPA or IMP under conditions whereother radicals, such as R02· or RO·, would be ineffective (10).Molecular oxygen should promote the stepwise degradationof IMP via MPA to carbon dioxide and phosphoric acid viaRO~· and RO· radicals and oxygenated intermediates. Thefollowing scheme indicates the probable major reactions involved in oxidation of MPA (in basic solution) (Equations1-7b):

Oxidation with oxygen via free-radical intermediates isan attractive method for rapidly transforming trace amountsof organic compounds found in wastewater to carbon dioxideand water. Several reports have appeared on the use of oxygen,with hydrogen peroxide or ozone as sources of radicals, to remove acetate ion (I) or nitroaromatics (2). Although traceoxidations are rapid and fairly complete, information islacking on the intermediates formed or the efficiency of theprocesses and there appears to be no useful data on oxidationsat high concentrations of cbemicals.

This paper describes the use of hydrogen peroxide, oxygen,and ultraviolet (UV) light to completely oxidize high concentrations of isopropyl methylphosphonate (IMP) andmethylphosphonic acid (MPA). These phosphonic acid derivatives arise from hydrolysis of the nerve agent isopropylmethylphosphonofluoridate (GB):

Neither IMP nor MPA is toxic; however, the possible re-formation of GB from IMP under some conditions has been reported (3). Although further conversion of IMP to MPA ensures against re-formation of GB, complete oxidation to carbon dioxide, water, and phosphoric acid greatly simplifies theproblem of ultimate disposal.

The literature on oxidation of organic phosphorus(V)Cllmpounds is quite limited. Smirnov, Pristenskii, and Filinova(4, .5) report the oxidation of methylphosphonic acid withozone and Co(NO"),, to give a 40% yield of phosphoric acid in9 h. Recently, Benschop and Halmann (6) described the UVirradiation of trimethyl phosphate and oxygen in water. Orthophosphoric acid, CO, and CO2were major products formedby stepwise oxidation of the methyl groups to give dimethylhydrogen and methyldihydrogen phosphoric acids as intermediates.

Since direct reaction of oxygen with most organic compounds is impractically slow at temperatures below 150-200

i·PrO(Me)P(O)F + H2 0

GB

i-PrO(Me)P(O)OH + HF

IMP

tH20

McP(O)(OH), + i-PrOH

MPA

HO· + MePO;JNa2 ~ H~O + ·CH2PO;lNa2 (2)

R· = CHzPOaNaz

HO· + Hz0 2~ H20 + HO~· (3)

R· + O2~ R02• (4)

R02· + H02·~ ROzH + O2 (5)

2R02· - R'CHO + R'CH20H + O2 (6)

R' = OP(ONah

R'CHO + 2HO· +0.50z - CO2 + (NaO)2P(0)OH + H20(7a)

R'CH~OH + 2HO· + O2 ~ CO2 + (NaOhP(O)OH + 2H20(7b)

The stoichiometry of the oxidation of MPA depends onwhether oxygen or H~Oz or both are used.

MePO:1Na2 + 202~ CO2+ Na2HPO, + H20 (8)

MePO;lNa2 +4H20~ - CO~ + Na2HPO, + 5H20 (9)

The oxidation of MPA requires four peroxide/MPA butonly two O~. The most efficient use of peroxide is to initiateReaction 2 and other H -atom transfers from stable intermediates while minimizing Reactions 3 and 5.

The specific rate constant for H-atom transfer to HO· fromMPA (Reaction 2) is probably similar to that for acetic acidor acetone, for which values of about 108 M-I S-l have beenmeasured (9). The principal competing reaction for HO· willbe H-atom transfer from H~02 itself (Reaction 3). This reaction has a rate constant of about 107 M-I S-I (9). Thus, Reactions 2 and 3 are competitive at a 1:10 ratio of MPA to H20 2•

At lower concentrations of MPA, Reaction 3 will compete andthe efficiency of the oxidation process, as measured by theamount of MPA oxidized compared with the amount of peroxide consumed, will decrease. For comparison, the specificrate constants for the same process involving R02• or RO·

00 13-936X179/0913-0205$0 1.0010 © 1979 American Chemical Society Volume 13, Number 2. February 1979 205

Table I. Oxidation 01 MPA Using HzOz and UV Light a

conens, M conversionexpt time, of MPA.

j,H202/j,MPAno. h IMPAIo I.lMPAI IH20210 I.lH2021 %

2B 2 0.17 0.17 1.73 1.58 100 9.3

2 2 0.67 0.38 3.5 1.6 56 4.2

3 2 0.40 0.11 2.1 1.1 28 10

4 1 1.67 0.41 1.7 0.9 24 2.2

5 1 1.82 0.15 0.95 0.95 8 6.3

6 1 1.96 0.25 0.20 0.20 13 0.8

8 1 1.25 0.19 3.9 2.0 15 10.5

7 1 1.00 0.36 5.2 2.9 25 8.11 2 1.00 0.57 5.2 3.9 57 6.8

11 2 1.00 0.44 2.6 1.67 56 3.8

13 1 1.00 0.81 2.6 1.64 61 2.7

14 2 1.00 0.59 2.6 2.6 59 4.4

20 12 0 3.0 0 dark C

21 12 1.00 3.0 0 0 dark22 1 1.00 2.9 0.1 0 Pyrex reaction

tubeII Mixtures flushed with pure O2 and tightly capped before irradiation with a 450-W Hanovia mercury arc lamp, Model l8A 10. b Inilial pH was 8. Measured using

lH NMR (see Experimental section). C Closed cabinet with no visible or UV light.

III,

-- N.tH2P04

MPA

- H3P04(ST ANDARO)

Y...w.,....

Dpm -21.7 0

Figure 1. 3'p NMR of MPA oxidation mixture with H3PO. standardcapillary

radicals are probably 10-7 or 1O-~ as fast as for HO· (10), andwill be important only in the latter stages of oxidation if morereactive oxygenated intermediates accumulate.

ReslIlls

Photooxidation of Sodium Methylphosphonate (MPA).Table I summarizes the results of some experiments on theoxidation of 0.17 to 1.67 M solutions of MPA sodium salt (pHIl) with excess H"O". With a large excess of H"O" (experiment2B), all the MPA was oxidized to carbon dioxide (and inorganic phosphorus) within 2 h; however, almost all the peroxidewas also consumed. The last. column of Table 1 measures tbeefficiency with wbicb H"O~ is used to oxidize MPA. The ratio(:'H~Oj~M PAl is not relater! t.o t.he conversion of MPA, onlyto the number of moles of peroxide needed to oxidize I mol


of MPA. Higher values (low efficiency) were found when theinitial ratio IH~O~]I[MPAIwas high, or when the irradiationt.ime was short. (I h), or both (experiments 28, 2, 3,7, and 8).The lower ratios of ~H~O~/~MPA (high efficiency) wereusually associated with lower initial ratios of peroxide to MPA(experiments 4, 6, and 11-14) as expected from the competition between Reactions I-a. Experiment 6 shows that theprocess is very efficient (0.8) when a large excess of MPA isused.

Table I also shows results from control experiments withperoxide and wit.h and without MPA (in the dark) or withperoxide in Pyrex tubes, which cut off UV light <290 nm, allof which showed no reaction. A few experiments with 0.17 MMPA, 1.7:l M H~O~, and air at pH 6-10 (in increments of 1 pHunit) not. shown in Table I gave very similar results on irradiation for 2 h. Almost. all the MPA was oxidized and 0.08-0.19M H~O~ remained.

More detailed experiments were done on the products ofoxidation from experiments 1,2, and 7-14. Mixtures of 1 MMPA and 1-3 M peroxide with excess oxygen were irradiatedfor 1-2 h; :10-60% of t.he MPA was oxidized. Analysis of thereaction mixt.ures by 'H NMR for MPA and intermediatesshowed only a diminut.ion in the MPA doublet at 1.0 ppm(from Me,Si)' No evidence was found for formation of intermediate oxidized phosphorus acids, such as hydroxymethylphosphonic acid or formaldehyde. ~;xperiment 2 (Tahle I) wasalso analyzed hy :\\ P NMH (Figure I). At. 56% conversion, onlysignals corresponding to NaH)O., and MPA were found andin the same ratio as f()und from the 'H NMR spectrum for thesame mixture.

The virtual absence of intermediates in the oxidationmixt.ures is also shown by an experiment. summarized in TableII in which oxygen, 1 M MPA, and 2.6 M peroxide were sealedin a quartz tube and irradiat.ed for 4 h. Peroxide was entirelyconsumed, and about 54% of MPA was oxidized. Gas analysisshowed that. 97% of the carhon from t.he reacted MPA was inthe fnrm of CO~ and a trace amount of CO. In t.his reaction.about 4.8 peroxides were consumed for each MPA consumed,a fairly ellicien\. process. Gas analysis also showed that additional oxygen was produced hy the direct decomposition ofperoxide.

Photooxidation of Isopropyl Methylphosphonic AcidSodium Salt. Table III summarizes t.he result.s of three ex-

Table II. Photooxidation of MPA with H20 2(Millimoles)a,b

inttlal tinal .;

O2 1.37 2.02 0.65MPA 6.00 2.76 -3.24H20 2 15.60 0 -15.60CO 0.075 0.075CO2 3.032 3.032

balance on C = 96 % c

a Solution volume 6 mL. b Sample sealed under oxygen and irradiated for 4h with 450·W HanDvia mercury lamp. C (CO, + CO)/MPA.

periments with mixtures of IMP (as its sodium salt) and H"O:!.The mixture was irradiated for 2 h, irradiation was stopped,and the reaction was analyzed for peroxide, IMP, MPA, andintermediate organic products. Irradiation was resumed withpart of the same solution, to which was added more H"O", sothat the initial concentration of H"O:! was the same for eachreaction. The process was repeated a third time. In experiment1 Crable HI), 1.0 MIMI' wascompletely oxidized to aceticacid, acetone, CO:!, and MPA in 2 h with 3 M H:!O:!.

Experiment 2, with a portion of the reaction mixture fromexperiment 1 and more H"O:!, shows that 0.66 M MPA partially oxidizes to CO2, and 0.14 M acetone oxidizes almostentirely to AcO- but 0.:~2 M AcO- is largely resistant to oxi·dation. Only in experiment 3 with 0.32 M MPA and 0.32 MAcO- is most of the AcO- oxidized along with MPA.

The formation of both acetone and acetic acid in experiment 1 and oxidation of acetone to acetic acid in experiment2 may indicate that these products are formed by tworoutes.

Table III. Photooxidation of IMP with H20 2(Concentrations in Moles/Liter)

expt 2 expt 3initial (mixture from (mixture from

conditions a expl1 1 + "202) 2 + H202)

liquid vol, mL 3.80 2.09 0.64O2, mmol 2.11 0.66 0.51[IMP] 1.00 trace 0[MPA] 0 0.66 0.32[H20 2] 3.02 3.0 3.0lacetone] 0 0.14 0[acetic acid] 0 0.32 0.32

finalconditions

O2, mmol 0.635 1.926 0.916.l02, mmol -1.47 +1.264 0.41[IMP] 0.01 0 0[MPA] 0.94 0.46 007[H20 2] 0 0 0[acetone] 0.2 0.02 0[acetic acidI 0.46 0.46 0.13CO2, mmol 3.35 0.52 0.36CO,mmol 0.4 0.12 0C balance, % 75 89 119

a Initial pH = 9. Solutions irradiated for 2 h.

based on the known rate constants for reactions of HO, withacetone and acetic acid (8, 9), both of which are products fromthe oxidation oflMP. The ratio ofrate constants for H-atomtransfer from MPA (k t ) and acetate (AcO-) (k l ) is derivedfrom the relation:

which on integration becomes:

(10)(kl/k t ) = In ([AcO-]o/[AcO-j)/ln ([MPA)o/[MPAj) (24)

When the data from experiment 3 Crable 1II) are substitutedinto Equation 24

(k I/k t ) = In (0.32/0.13)/ln (0.:l2/0.07) =0.59

The value uf k 10 for reaction of AcO- with HO·, is 7 X 10' M-IS-I; therefore, k 2 = 1.2 X lOs M-I S-I. Experiment 1 alsoprovides the basis for estimating the reactivity of IMP towardHO· using the reasonable assumption that the rates of oxidation of both IMP and MPA are controlled by simple consecutive first-order processes involving H-atom transfer toHO· radical:

IMP + HO· > Me:!COPX + H:!O

X = [(ONa)(O)(Me)j

Me2COPX + O:! - > Me:!C(-O:!·)OPX (ll)

Me2C(-0:!·)OPX + H02· > Me2C(-02H)OPX + O:! (L2)

MeA·02H)COPX + H20 -> Me2CO + H:!02 + HOPX (L3)

Ill'Me:!C(-02H)OPX - MeC(-O·)OPX + HO· (14)

Me:!C(-O·)OPX + IMP -> Me2C(-OH)OPX + Me2CC)PX(15)

Me:!C(-OH)OPX .-' Me2CO + HOPX (L6)

Me·,CO + 1.50., + 2HO· • MeC(O)OH + CO.,- - (:..t:n~rill Slt>p:-;) -

h,IMP-MPA (25)

+2H:!0 (L7)

Me2C(-0·)OPX • MeC(=O)OPX + Me· (L8)

MeC(-~O)OPX + H20 -> MeC02H + HOI'X (19)

These results also indicate that most if not all CO:! is formedby oxidation of acetic acid via several intermediates, possihlyincluding acetoxy radical:

MeCOOH + HO· -> MeCOO· + H:!O (20)

MeCO:!· . > Me· + CO:! (21)

Me· + UiO:! + HO· - > CO:! + 2H:!0 (several steps) (22)

Other plausible routes from acetic acid to CO:! involving instead initial transfer of a methyl hydrogen can also be written.

Reactivity of Phosphorus Acid Salts toward HO·Radicals. The data in Table HI can be used to estimate therate constants for H-atom transfer from IMP and MPA to HO·

(26)

where k/ =k.[HOJ and k/ =kAHOj. Under these conditionsthe concentration of MPA present at any time, t, is (II):

[MPAI = [IMPlok/ Ir h .,., - e-lt"1 (27)I k/ - k/

Equation 27 can be solved by trial and error for a value ofk/ that satisfies the requirement that IMPAI, = 0.94 Mat t= 120 min and that k/ = 5 X 10-' S-I, as calculated from thedata in experiment I. A value of k/ = 1.1 X 10-" S-I (k:!' /h.I'=0.027) at t = 120 min gives [MPAI =0.91 M. Since k 2 "" :l.6X 10" M-I S-I, k. = l.:l X 1010 M-I S-I. This value agrees quitewell with the value of (2-4) X 100 M-I S-I for the rate constantfor H-atom tranfer from isopropyl alcohol (8,9).

Knowledge of even approximate values (If rate constantsfor HO· radical reactions 'with the organic reactants andproducts in this multistep process is of practical utility in


planning for the most efficient use of expensive oxidant. Forexample, oxidation of IMP to MPA is rapid and efficientcompared with further oxidation of MPA because the mostreactive species is IMP and all the products, MPA, acetone,and acetic acid, are equally unreactive. These results show thatHtOz can be used with UV light and oxygen to oxidize largeamounts of even very unreactive compounds rapidly at 25 ·Cin water.

Experimental

Materials. Methylphosphonic acid was supplied by J.Epstein of Edgewood Arsenal and by R. Swidler of SRI, whohad prepared it by acid hydrolysis of commercial dimethylmethylphosphonic acid. The 99+% pure acid was then recrystallized from acetonitrile. Sodium methylphosphonic acidwas prepared either as a 2.0 M solution by neutralization oras the dry salt. Sodium isopropyl methylphosphonate wassupplied by J. Epstein and used without further purification.

Oxidation of MPA and MP. Solutions of MPA and IMPsodium salts were made up in distilled water; 30% HtOt wasadded in amounts needed to obtain the desired final concentrations of sodium salts and HzOz.

Photooxidations were carried out in 26 mm X 28 em quartztubes. Approximately 4 mL of the desired reaction mixtureofMPA or IMP and HzOz was added to each tube. The tubewas flushed with oxygen for 3 min and stoppered with a serumcap, which was slashed to vent any pressure by the formationof oxygen and COt. Three tubes were clamped to the shaft ofa stirring motor, which was mounted so that shaft and tubesrotated almost horizontally. The center of the shaft was 13 cmfrom the center of a Hanovia 450-W mercury arc lamp, Model79A10, mounted horizontally and water cooled by a quartzcondenser. The lamp was warmed up for 5 min before exposingthe tubes, after which the tubes were rotated at approximately60 rpm for the desired time while exposed to the light.

For gas analysis, quartz tubes fitted with break seals andfilled on the vacuum line were used in the same way.

Analysis of MPA and IMP Reaction Mixtures. Theaqueous reaction solutions containing MPA or IMP wereanalyzed directly by lH NMR using a Varian 100-MHzspectrometer. The large solvent peak (HtO) did not interfere


with peaks from MPA, IMP, acetic acid, or acetone, and noother peaks were found when solutions were scanned from 0to 20 ppm. Solutions were made basic (pH 8) before analysis.

MPA was analyzed to ±5% precision using NMR by comparing the peak height of one of the doublet methyl peaks at1.03 and 1.30 ppm from Me.Si with standard solutions ofMPA. Analysis of IMP was more difficult and less accurate(±15% precision) because of the complex methyl multiplet.:11 P NMR spectra were taken on a Varian spectrometer operating at 40.5 MHz (Fourier transform) using 12 mm o.d.tubes.

Gas analyses on reaction mixtures were done using a vacuum line Toepler pump and furance system described in detailelsewhere (12).

Acknowledgment

The referees made several comments that materially improved the clarity of this paper.

Literature Cited

(I) Bishop, D. ~'., Ind. EnR. Chern., Process Des. Dev., 7, 110(1968).

(2) Koubeck, E., ibid., 14, :148 (197:1).(:3) Epstein, .J., Davis, G. T., Eng, L., Demek, M, M., Envirvn, Sci.

Technv/., 11,70 (1977).(4) Smirnov, V, V" Pristenskii, A. F" Filinova, N. A., J. Gen. Chern.

USSR (EnRI. Trall"/.), :\7,2649 (1967).(5) Smirnov, V, V" Pristenskii, A. F., Filinova, N. A., ibid., 38, 1152

(1968).(6) Benschop, H., Halmann, M.•J., J. Chern. SO('., Perkin Trans. 2,

117.') (1974).(7) Schumh, W. C., Satterfield, C. N., Wentworth, R. L., ACS Mo-

nv!!,., No. 128, Chapter 8 (1955).(8) Walling, C" Al'<'. Chern. Res., 8, 124 (1975).(9) Anhar, M., Neta, P., Int. J. Appl. R"dial. Isvl., 18, 49:J (1967).(10) Hendry, D. C" Mill, T" I'iszkiewicz, L., Howard, J. A" Eigen-

mann, H. K., J. Phys. Chern. Ref. Data, 3,9:\7 (1975),(11) ~'rost, A. A., Pearson, H. G., "Kinetics and Mechanisms", p 15:1,

Wiley, New York, N.Y., 195:1,(12) Mill, T., MOI1Lursi, C., J. Chern, Kind., 5, 119 (197:l),

Rel'eived fvr re"ir'", Jalluary J. /97H. Al'l'epted September I, 1978.This work wa .... IwpfJorted by the Department of the Army, Ed/icw()()dArsenal, Aherdeen Prouinu around, Md., Dr. Joseph Epstein,Technical Officer, under rOlllmel No. OAAAIS-74-C-01SO.

Acid Precipitation in the New York Metropolitan Area: Its Relationship toMeteorological Factors

George T. WoIW1, Paul J. Lioy2, Howard Golub, and Jill S. Hawkins3

Interstate Sanitation Commission, 10 Columbus Circle, New York, N.Y. 10019

• A study which examined the spatial, meteorological, andseasonal factors associated with precipitation pH in the NewYork Metropolit.an Area has been completed. From 1975through 1977,72 events were studied. Among the eight. sitesin the study, there was some sit.e-t.o-site variabilit.y. The meanpH was 4.28 and the lowest seasonal values occurred duringthe summertime. The stormg were classified according t.o typefor each event, and showers and t.hundergllOwers associatedwith cold fronts and air masses yielded the lowest pHs of 4.17and 3.91, respectively. Closed low-pressure systems produeedsomewhat higher values. Air pareel trajectory analyses showedthat these air mass and frontal st.orms were generally agsoeiated with winds from the west and southwest. These are t.hedirections from which high emissions in the Northeast havetheir greatest. impact oil the New York Metropolitan Area.

The inereasing aeidity of precipitation in the northeasternUnited States has been document.ed by l.ikens (1-·4), whoreported a mean pH on the order of 4.0. The effect.s of thisacidity have resulted in fish kills «1-6) and increased stresson vegetative systems (7 ·9). In certain types of soils, increasedhydrogen ion concentrations have enhaneed t.he leacbing ofheavy met.als and caleium int.o surface and ground waters(lU).

The acidity of preeipit.ation is related t.o t.be presence ofat.mospheric pollut.ants, part.icularly sulfates and nitrat.es (1).Evidence has been presented wbich indicat.es t.hat long-rangetransport. of these pollutants, particularly sulfat.es, is a moreimportant factor than locally generated pollutants in thenortheastern U.S. (I. 10. 11).

The purposes of the study reported in t.hig paper are twofold: to cbaracterize the spat.ial and seasonal variat.ions inprecipitat.ion pH in t.he most highly populat.ed area of thenortheast.ern U.S., the New York Metropolit.an Area, and t.oexamine the relat.ionship bet.ween synoptic seale met.eorological factors and preeipit.ation pH. During 1!1'7,,-l976,samples were obtained from 72 individual st.orms at. 8 sit.esshown in Figure I. The site-t.o-sit.e relat.ionships, seasonalvariations, effeets of storm t.ype, and wind direction are discussed. In addition, t.he relat.ionships bet.ween pH and t.hepath of air parcel t.rajeet.ories arriving in New York Cit.y dnringpreeipit.at.ion event.s Me examined.

Experimental

Prior to the onset. of a precipit.at.ion event., clean plagt.icbuckets were placed outdoors in locations which were 2-5U ft.above the surfaee. In most. eases, t.his was approximat.ely U ·2h before or after the event. began. Onee t.he event. terminat.ed,the rain samples were t.ransferred t.o Nalgene or glass serewcapped boWes which had been t.horoughly cleaned and rinsedwit.h distilled wat.er and then dried. The int.erval bet.ween thist.ransfer varied considerahly, from a few minutes to as muchas 8 h if t.he precipitation ended dming the night.

------------~--~

J Present addrexs, ~:llvif'(,nlllel1t:1Sdenc~i~~rt.ment.(;eneralMotors Research I.abl)ratories, Warrt>n, Mil'h. 4BO!JO.

2 Pre:-;ent address, Institute of r~llvirollllltmtalMedicine, New YorkUniversity Medieall'enter. New York. N.Y. 100\6.

:1 Present address, Fred C. H"ut Asso(·iates. ;)'1.7 Madison Ave., NewYork, N.Y. 10022.

Snow was collected in t.he same manner, then covered withplast.ic wrap and allowed to melt in the bucket.. The meltedsamples were then transferred to the Nalgene or glass bottles.

All samples were kept under refrigeration until they wereanalyzed the next day. Weekend samples were analyzed onMonday. The pH was det.ermined with a Corning pH meter(Model 10) after the samples were allowed to r3ach roomt.emperature. The inst.rument was standardized with certifiedbuffer solutions of pH 4.0-7.0. In cases where the pH of thesample was less than 4.0, the instrument was restandardizedwit.h a buffer solution of pH 3.0.

Results

Site-to-Site Variations, The mean pH values at each siteare shown in Table I. The mean values were calculated usingthe averal(e hydrogen ion concentrations and weighted according to t.he amount of precipitation per storm.

The distribution of the weighted hydrogen ion concentrations for individual sites was log normal. The standard deviations of t.he hydrogen ion concentrat.ion are expressed aspH values and they are shown in Table I. The standard deviation for the individual sites ranged between 0.20 and(J.n

The mean pH for all siteg was 4.28 with the mean pH forindividual sites ranging from 4.25 to 4.64. In New Jersey andat adjacent sit.es in New York (Bronx and Manhattan), thevariat.ion of the means (4.25-4.34) was much smaller. To theeast. and nort.heast of the city, in Port Chester and Queens, t.hepH values were considerably higher.

The frequency distributions for all sites which reported dat.afor more than 5U% of the storms are shown in Figure 2. All sitesshow a predominant number of the observed pH values bet.ween 4.0 and 4.74 with the range 4.25-4.49 heing the mostcommon,

Seasonal Variations. A pronounced seasonal variation isobserved in Figure :3. At all sites except Manhattan, theminimum pH occurred during July-September while themaximum occurred during October·-December. 1<'01' all sites,t.he mean increase from summer t.o autumn was 0.41 pH unit.111 Manhattan, however, the minimum pH occurred in .January· ·March and gradually increased throughout. the year.

Effects of Storm Types. Precipitation events were classified int.o eight cat.egories which are shown in Table II. TypesI t.hrough 4 are t.ypical frontal type low-pressure syst.ems witha well-defined center (i.e., closed isobars). Types 1 and2 aredistinguished hy t.he area over which the cyclogenesis occurred. Continental low systems, type 1, originated somewhereover Continental North America. A type 2 storm has a marit.ime origin, either over t.he Gulf of Mexico or the AtlanticOeeal1. Types :3 and 4 are distinguished by the storm pathrelative to New York City. A low-pressure system which passesto t.he north or west. of the city (type 3) keeps the New Yorkarea in t.he warm sector of the storm and is generally accompanied hy southeasterly winds. In type 4 storms, the city is inthe cold sector of the storm which most frequently producesnortheasterly winds across the Metropolitan Area as the stormpasses to the south or east. of the city. Types 5 through 7 aredescribed in Table II. Type 8 includes storms which could notbe classified into any of the first seven categories.

It. appears that continental storms have a slightly lower pH

0013-936XI7910913-0209$01.00/0 © 1979 American Chemical Society Volume 13, Number 2, February 1979 209

SEASONAL VARIATION OF PRECIPITATION pH

IN THE NEW YORK METROPOLITAN AREA

NEW YORK

•6

I·NEW

2 •

TRENTON

------.-r------~

CONNECTICUT

J. Cilldfl(JII, f'U- ~"h"l·lJa.H

2. JlI.... <.:at'l,V.a)'. NJ- ~uhllrhan

J 1I':ll1lllnl, .'/J- !-<urllurl,<l,ll4 Ilronll, NY- U,.I,al.[l ~\,UllUtt~lI, NY~ "I"ban

h. Illf:h POlllt, ""J- Tur,jlCl11('''Jl~, ~)" .IrhallPVI t (j'l<;lCI". N\

'.6

• 0 JFM AMJ JAS aND

21 443

22 4.35

26 439

17 4.39

16 4.175 3.911 5.16

6 4.31

no. meanobsd pH

description of dominant stormsystl:tm

closed low-pressure system which formedover continental N. Arner .

closed low-pressure system which formed inGulf of Mexico Or over Atlantic Ocean

closed low which passed to WorN of N.Y.G.

closed low which passed to SorE of N. Y.G.

cold front in absence of closed low

air mass thunderstorm

Hurr ieane Belle

unclassified

34

567

8

type

site mean pH SO no. obsd range

Caldwell. N.J. 432 0.26 50 3.35-5.60Piscataway. N.J. 4.25 0.36 64 3.57 -5.50Cranford. N.J. 4.34 0.34 48 344-5.95Bronx. N.Y. 4.31 0.37 57 342··5.75Manhattan. N. Y. 4.29 0.25 39 3.80-·5.50High Point. N.J. 4.25 0.30 25 3.74-490Queens. N.Y. 4.63 0.35 20 398-5.28Port Ghester. N.Y 4.60 0.19 21 4.00-5.10

all sites 4.28 032 72 3.50-5.16----- --- ._--_ .._-- ---_._-----

Table II. Storm Type Classification

Table I. Mean pH Values in the New York MetropolitanArea (1975-1917)

MUNTHS OF THE YEAR (19751hrolJqh 1~77)

Figure 3. Seasonal vaJiation of precipitation pH in the New York Metropolitan Area

\ H l I' ~_ ~ G tl

::l!t""<It,,20

'0o -_. ----.--~--

,~ H l () t. ~ G H

:~w'0

10

o ----1\ H ( I' t t u H

KEY" ..1."-3 ~',O. 1\-") ;'-3 74, (~],7~)

3.99. 11-4-424, 1->4.25-4.49~ ~4 ;,-4 ; 4. (,"4 -.;)- 4 ~9.

H~5.00 (pI! r.lnl{cs)

ABC IJ f; F G tl

pH

30

.4. H lilt. t t, II

MASUA n A'I.... y

10

Figure 1. Sampling site locations for precipitation study

::U~'\I""""""20

10

o -----,.-

cr 50

Figure 2. Distribution of pH values observed at each sampling site

than the maritime storms. The path of both types of storms,however, appeared to have no noticeable effed on tbe pH.

Lower pH values were observed during showers and thundershowers associated with cold fronts. The lowest pHs were

ubserved during air Illass type showers and thundershowers.

On August 9 and lO, 19iG, the higlll'st pH values recordedthroughout the 2·year lJl'riod were observed at most of thesites. This precipitation was the result of Hurricane Belle


40 80 120 160 200 240 280 320 360

SURFACE WIND DIRECTION IN DECREES

Figure 4. Mean pH values for all sites vs. wind direction

Discussion

Maximum pH values occur during the autumn monthswhile the minimum values occur during the summer months.This should be expected if most of the acidity is due to sulfates. Two studies conducted in the northeastern U.S. haveshown evidence of a summertime sulfate maxima and an autumn sulfate minima (13, 14). Under the intluence of a highpressure system, evidence has also been presented demonstrating the association of high atmospheric sulfate levels withthe photochemical smog process (15, 16) which exhibits thesame seasonal variation.

In addition to the higher summertime sulfate levels in theatmosphere, there is another factor which may contribute tothe lower summertime pHs. The lowest pHs were associatedwith cold front and air mass type precipitation events. Theseoccur much more frequently in the summer months. Of the21 events of this type, 13 occurred during the summer months.

In contrast, only one of the 43 types' 1 and 2 storms occurredduring the summer.

It was also noted that lower pHs occurred on west orsouthwest winds. Of the ten events which occurred onsouthwest or west surface winds, six were associated withfrontal or air mass type storms. In most cases examined bytrajectory analysis, frontal or air mass type events were associated with southwest, west, or west northwest trajectories,while cyclonic events were associated with south or east trajectories.

Conditions which are most conducive for air mass typeshowers or thundershowers generally occur within the backside or return flow around a high-pressure system. This is alsothe part of the air mass which, in the summertime, experiencesthe highest concentrations of photochemically producedpollutants includinl( sulfates ([5-18). Precipitation associatedwith cold fronts generally occurs when the heavier cold airbehind the front lifts the warmer less dense air preceding thefront off the ground. This warmer air is generally the trailingedge of the backside of a high-pressure system. As a result,both the air mass and frontal type events occur generally ina polluted air mass.

All storms with southwesterly or westerly wind directionsand/or trajectories produced lower pHs than those associatedwith other directions. This is probably due to accumulationof sulfur oxides, nitrol(en oxides, and hydrocarbons from thehil(h emission density areas which exist in the Midwest andWashington, D.C. to Boston, Mass. corridor (12,18). Easterlytrajectories are probably associated with high pHs for threereasons. The first is the influence of the maritime environment. Aerosolized sea salt would tend to neutralize the acidity.This was dramatically illustrated during Hurricane Bellewhich produced the highest observed pHs. The second is thefact that trajectories traveling over the ocean have less opportunity to travel over high pollutant emission density areas.In addition, these storms have lifetimes on the order of days,while the air mass and frontal types have lifetimes on the orderof hours. Since the highest rates of pollutant scavenging occurat the onset of the precipitation, short-lived storms containmore acidic pollutants.

Figure 5. The variation in precipitation pH according to the sector fromwhich an air parcel approached the New York Metropolitan Area.

-'----,----

~

-

I--

'.6

4.~

...'.3

•. 2

x~ '.1...

3.'

3.8

whose eye passed approximately 30 miles east of New YorkCity.

Effect of Surface Wind Direction. The mean pH for allsites as a function of wind direction is shown in Figure 4. Winddirection was classified into seven categories which were selected on the basis of upwind sources. Before occurring in NewYork City, northeast winds traveled over New England, eastwinds over Long Island, southeast winds over the AtlanticOcean, south winds over the Chesapeake and Delaware Bays,southwest over the Philadelphia-Camden area, west overcentral and northern Pennsylvania, and northwest over NewYork State.

The data indicate that the highest pHs occurred on northeast to south winds with the mean pH being 4.37. Lower pHs(mean 3.95) occurred on southwest to northwest winds. Thelowest mean value, 3.82, occurred on westerly winds.

Effects of Air Parcel Trajectory Path. Using wind datafrom the National Weather Service's upper-air observationnetwork, air parcel trajectories were calculated for the surfacelayer (here taken to be from 400 to 1400 m). The calculationprocedures have been described elsewhere (12). Since trajectories which terminated in New York City were availableevery 6 h, the trajectory selected during any given storm wasthe one which best corresponded to the period of heaviestprecipitation.

Trajectories for approximately 25% of the precipitationevents were available and were plotted on a map of thenortheastern U.S. The wind direction sector from which theair parcel approached the New York City area was analyzedand the results are summarized in Figure 5. Trajectories fromsouthwest and west had the lowest pHs, while trajectoriesfrom the east and the north resulted in the highest pHs.

Volome 13, Number 2. February 1979 211

Limitations

In the study, a number of procedures were used to minimizeerrors which could arise from sampling and storage. Samplinghuckets were placed out as close to the onset of the precipitation event as possible. This reduced and in many caseseliminated the dry deposition of material into the co·llector.Similarly, the samples were removed from the bucket as soonas possible after the event. terminated.

Stored samples were refrigerated to reduce any chemicalor biological activity which might have altered the pH.

There was no apparent relationship between the pH andthe length of time (up to 72 hl the samples were stored.Therefore, the authors think no significant changes occurredin the pH during storage.

After approximately a dozen events, samples were split andhalf were stored in Nalgene bottles and half in glass bottles.The mean difference between the t.wo was less than ±0.01 pHunit.

Another source of error was the deposition of leaves, insects,and soot in the collector during the event. These samples wereincluded in the analysis only if the difference between the pHof the contaminated sample and the mean pH of the samplescollected at the ot.her sites during the same event was less than1.00 pH unit.

Conclusions

The mean pH of precipitation falling on the New YorkMetropolitan Area during the 2-year study was 4.28. Thelowest mean pH occurred during the summer months and thiswas 4.12.

Precipitation events associated with cold fronts and airmass type showers and thundershowers produced the lowestmean pHs of 4.17 and 3.91, respectively. Both storm typeswere generally associated with the back side of a pollutedhigh-pressure system.

Well-defined low-pressure systems which affected the NewYork Metropolitan Area resulted in mean precipitation pHsof about 4.40. Since these storms are generally accompaniedby easterly winds off the Atlantic Ocean, the air parcels haveless opportunity to accumulate pollutants from high pollutantemission density areas than the air mass and frontal storms.The latter are generally associated with west or southwestwinds which passed over polluted areas in the Midwest andWashington, D.C. to Boston, Mass. corridor. In addition,frontal and air mass type storms generally have a lifetime onthe order of hours, while low-pressure syst.ems exist for days.Since scavenging of pollutants by the precipit.ation would bemore pronounced during the initial phase of the storm, the


longer the lifetime of the event, the less polluted the ambientaIr.

Acknowledgments

The authors are grateful to Mr. Perry Samson of the NewYork State Department of Environmental Conservation forproviding the air parcel trajectories. The authors also thankthe following members of the Interstate Sanitation Commission who assisted in the collection of samples: WilliamEdwards, Konrad Wisniewski, Robert Angrilli, Frank Filippo,Kenneth Piontek, and Michael Nosenzo. Special acknowledgment is given to Dr. Peter Coffey of the New York StateDepartment of Environmental Conservation and Dr. JamesGalloway of the University of Virginia for their helpful comments.

Literature Cited

(1) Likens. G. E., Chem. Eng. News, 54,29 (1976).(2) Galloway, .J. N., Likens, G. E., Edgerton, E. S., Science, 194,722

(1976).(:l) Likens, G. E., Bormann, F. H., ibid., 184,1176 (1974).(4) Likens, G. E., "The Chemistry of Precipitation in the Central

Finger Lakes Region", Tech. Rep. No. 50, Cornell Univ. Water Res.Center, Ithaca, N.Y., OclI972.

(5) Barr, T. E., Cnffey, P. E., "Acid Precipitation in New York State",Tech. Paper No. 4:1, N.Y. State Dept. Environ. Conservation, Albany, N.Y., July 1975.

(6) Schofield, C. L., Ambio, 5,228 (1976).(7) Reuss, ,J. 0., "Chemical-Biological Relationships Relevant to

Ecological Effects of Acid Rainfall", E.P.A. -660/3-75-0:12, U.S.E.P.A., Corvallis, Ore., June 1975.

(8) Baruch, S. B., "Acid Precipitation, a Literature Review", EdisonElectric Institute, New York, N.Y., Julv 1976, draft.

(9) Tamm, C. 0., Ambia, 5,2:15 (1976)..(10) Oden, S., in Proceed. Coni'. on Emerging Environmental Prob

lems-Acid Rain, EPA-902/9-75-001. U.S. E.P.A. Region II, NewYork, N.Y., Nov 1975.

(11) Ottar, B., Ambiu, 5,20:3 (1976).(12) Wolff, G. '1'., Lioy, P. ,J., Meyer, R. K. Cederwall, R. '1'., Wight,

G. D., Pasceri, R. E., Taylor, R. S., Environ. Sci. Technul., 11,506(1977).

(I:JI Hidy, G. M., Tong, E. Y., Mueller, P. K., "Design of the SulfateRegional Experiment", EPRI EC·12[), 81ective Power ResearchInstitute, Palo Alto, Calif., 1976.

(14) Hitchcock, D. R., J. Air Pol/ut. Cunlrol A.,soc., 2(;, 210(1976).

(15) Lioy, P. .J., Wolff, G. '1'., Czachor, ,J. S., Coffey, P. E., Stasiuk,W. N., Romano, D., J. Environ.. Sci. Heaith, Part A. 12, 1(1977).

(16) Wolff, G. '1' .. Lioy, P. ,J., Leaderer, B., Kneip, T. J., Bernstein,D., Ann. N. Y. Acad. Sci., in press (1979).

(17) Wolff, G. '1'., Lioy, P. ,J., Wight, (;. D., Meyers, R. E., Cederwall,R. '1'., Almos. l!.'nviron .. 1\ (1977).

(18) Wolff, G. '1'., Lioy, P. ,J., Wight, G. D., in Proc. Mid-Atlantic Sect.A.P.C.A. Conf. on Hydrocarbons, New York. N.Y., April 1977.

/leceived (or review Augusl /.5, /977. Accepted September 7, /978.

Toxicity of Copper to Cutthroat Trout (Salmo clarki) under Different Conditionsof Alkalinity, pH, and Hardness

Charles Chakoumakos

Department of Chemistry, University of Maine at Farmington, Farmington, Maine 04938

Rosemarie C. Russo and Robert V. Thurston"

Fisheries Bioassay Laboratory, Montana State University, Bozeman, Mont. 59717

• Median lethal concentration (96-h LCoo) values for acutecopper toxicity to 3-10-g cutthroat trout (Salmo clarki) havebeen determined for nine different combinations of alkalinity,hardness, and pH. Equilibrium calculations were performedon the copper LC50 values; s'even different soluble species ofcopper were considered: Cuz+, CuOH+, Cu(OHlz0, Cuz(OHjz2+, CuHC03+, CuCOi, and Cu(CO:1jzz-. The acutetoxicity of copper was inversely correlated with water hardnessand alkalinity. At a given alkalinity, hardness determined theLC50; at a given hardness, alkalinity determined the LCr,o. Ata given alkalinity and hardness, the concentrations of thecopper species were determined by the pH of the water. Underthe conditions tested, Cuz+, CuOH+, Cu(OHjz0, andCUz(OHjzz+ were toxic forms of copper to cutthroat trout;CuHC03+, CuCO:1o, and Cu(CO:1lzz- were not toxic. Resultsof 1196-h copper toxicity bioassays on 1- to 26-g rainbow trout(Salmo gairdneri) under uniform water chemistry conditionsare also reported.

A variety of environmental factors influence the toxicityof copper to fishes (1, 2). Among these factors are pH, hardness, alkalinity, and inorganic and organic complexation. Thework of several investigators (3-9) indicates that organicallybound copper is nontoxic and copper toxicity decreases as thecopper(ll) ion is chelated. Consequently, the toxicity of copperto fishes is attributed to the inorganic forms of copper.

It is now recognized, as noted by Lloyd and Herbert (10),that copper is more toxic in soft water than it is in hard water.Alkalinity and hardness are usually directly related. Stiff (11)hypothesized that if copper(II) ion were the toxic form ofcopper and if the copper carbonate complex, noted by Scaife(12), were relatively nontoxic, then the difference in toxicityof copper between soft and hard water would be related to thedifference in alkalinity, rather than the hardness, present inthose waters. In support of this, Andrew (13) stated that bicarbonate alkalinity has a major role in limiting copper toxicity in natural waters. Alkalinity is directly related to pH (14);because a relationship can be established between alkalinityand the copper(II) ion activity, pH is also related to the copper(II) ion activity.

Although it is generally accepted that the copper(I1) ion istoxic to fishes, it is not the only toxic form of copper. Shaw andBrown (9) concluded that CuH and CuCO:1o are the toxicforms of copper to rainbow trout (Salmo gairdneri). Pagenkopf et al. (15) reported that Cuz+ is toxic and CuOH+ maybe toxic. Andrew (13) stated that toxicity is directly relatedto the ionic activity of the cupric ion and not to its inorganiccomplexes. However, in a more recent study (on Daphniamagna), Andrew et al. (16) state that copper toxicity is directly related to activities of CuH , CuOH+, and CUz(OHjzz+.Howarth and Sprague (17), in work on rainbow trout, alsoconcluded that Cuz+, CuOH+, and CU2(OHjz2+ are toxic.

Stiff (18) applied an analytical scheme to differentiate thechemical states of copper into Cu2+,CuCOi, and Cu(organic).Maney and Allen (19) developed a mathematic model to dedetermine the concentration of each species in the coppercarbonate system. Various computer programs (20, 20 are

0013-936X/79/0913-0213$Ol.00/0 © 1979 American Chemical Society

available for evaluation of the equilibrium relationships topredict the speciation of metals in aqueous systems.

This paper reports on a series of bioassays on the toxicityof copper to cutthroat trout (Salmo clarki) under differentconditions of alkalinity, hardness, and pH; no copper toxicitystudies have previously been reported for this species.

Experimental

Nine acute copper toxicity flow-through bioassays on cutthroat trout were conducted at the Montana State UniversityFisheries Bioassay Laboratory, located at the Bozeman(Montana) Fish Cultural Development Center (FCDC), U.S.Fish and Wildlife Service. Test fish, obtained from FCDC,were a west slope strain reported to be free from any possiblehybridization. The source of water for the bioassays was anatural groundwater spring located at FCDC. This water hada hardness of ~200 mglL as CaC03, alkalinity of~175 mg/Las CaCOa, and no other appreciable constituents (Table I).To reduce the hardness and/or alkalinity this water was firstpassed through cation and/or anion exchange resin columns(Culligan Water Conditioning Co., CH-l and CS-2), and thenmixed with untreated spring water to achieve the desiredhardness and alkalinity for each test. In tests in which eitherhardness or alkalinity were to be increased to levels over thoseof the mixtures, reagent grade calcium chloride or sodiumbicarbonate was added with capillary flow meters or fluidmetering pumps. Bioassays were conducted in nine differentwater combinations (Table II) in a 3 X 3 experimental designwith three concentrations (high, medium, and low) each ofalkalinity and hardness similar to the classification developedby the U.S. Geological Survey (22).

Reagent grade copper(II) chloride in demineralized wateracidified with concentrated hydrochloric acid was used as thetoxicant. The test solution was delivered by a proportionaldiluter (dilution factor = 0.75) having the basic design ofMount and Brungs (23) at a flow rate of 500 mL every 2-3 minto each of six copolymer plastic tanks: five test and one control.The water volume of each tank was 62 L.

Copper concentrations in test tanks were determined according to the cuprethol method (24) using 10-cm cells.Copper was measured on nonfiltered samples; however, a series of copper analyses was conducted on 0.45-l'm filtered andnonfiltered samples of the test waters used in the bioassays.From these analyses appropriate factors (Table III) wereobtained so that the concentrations of copper measured onnonfiltered samples could be converted to dissolved copperas defined by the 0.45-l'm filter.

Total alkalinity was determined as in "Standard Methodsfor the Examination of Water and Wastewater" (25) withmethyl purple as the indicator. Total hardness (EDTA), calcium (EDTA), nitrate nitrogen, and ammonia nitrogen weredetermined according to analytical procedures described in"Standard Methods" (25). Nitrite nitrogen was determinedaccording to the U.S. EPA (26). Magnesium was calculatedfrom total hardness and calcium hardness (25). Dissolvedoxygen was measured using a Y.S.!. Model 54 meter, temperature with a calibrated mercury thermometer, and pH witha Beckman Phasar-l digital meter. Colorimetric measure-


Table I. Chemical Characteristics of the UntreatedDilution Water Used in Bioassays a

alkalinity, as CaC03 176 Ca 53hardness, as CaC03 199 Mg 36pH 8.0 Na 4.0temp,OC 9.8 K 0.64

AI <1sp equiv conductance, Ilmho/cm, 328 AS,llg/L 1.5

25°Ctotal org C 3.3 Cd <0.005turbidity, NTU 1.7 Cr <0.005NH3-N 0.00 Cu 0.008N02-N 0.00 Fe 0.03N03-N 0.23 Hg,llg/L <0.05CI- 0.44 Mn 0.003F- 0.4 Ni <0.005PO.3- <0.1 Pb <0.01sOl- 10.0 Se,llg /L 0.8

Zn 0.01

a All values in milligrams/liter unless otherwise noted.

ments were made using a Varian Model 635 ultraviolet-visiblespectrophotometer. Organic constituents were not detectedwhen measuring nitrate nitrogen at 275 nm.

A chemical profile of the untreated dilution water is presented in Table 1. For each 96-b bioassay, each tank wasmonitored on an average 01'3 times for copper, 5 times for pH,

alkalinity, and hardness, and 2 times for calcium, dissolvedoxygen, temperature, ammonia nitrogen, nitrate nitrogen, andnitrite nitrogen. A summary of test tank water chemistry datais given in Table II.

Sixty fish were used for each test, 10 per tank. Fish wereacclimated to the dilution water in the test tanks for 2-3 daysbefore introduction of toxicant. Prior to the tests, fish werefed a commercial salmon ration three times daily, but were notfed during the acclimation or test periods. Fish were weighedcollectively at the beginning of each test and were measuredindividually for total length as mortalities were observed orat the conclusion of each test. Fish mortalities, as evidencedby complete immobilization and lack of respiration, were recorded at 4-h intervals for the first 36 h and at 12-h intervalsthereafter.

The median lethal concentration (LCw) values and their95% confidence intervals were calculated from the experimental data using a computer program developed for thetrimmed Spearman-Karber method (27); toxicity curves werecomputer-generated using LCw and time values from eachtime of mortality observation.

Speciation of the LC"o copper values was accomplishedusing the computer program COMICS (20). This programhandles only homogeneous equilibria in solution and wasconsidered adequate within the copper concentration and pHrange of these bioassays. The copper species selected as beingmost important were Cuu , CuOH+, Cu(OHjz°, CU2(OHjz2+,CuHCO:J+, CuCO:\o, and Cu(CO:Jh2-. The chemical equilibriaconsidered in these calculations are presented in Table IV.The ionic strength calculated for the most concentrated test

Table II. Water Chemistry Conditions for Acute Copper Bioassays on Cutthroat Trout

high alkalinity medium alkalinity low alkalinity

hardness/alkalinity a H/H M/H LlH H/M M/M LIM H/L M/L LlLtest no. 391 378 453 412 370 379 424 413 425total hardness, mg/L

CaC03av 205 69.9 18.0 204 83 31.4 160 74.3 26.4(range) (202-208) (66.0-75.0) (15.0-25.4) (165-224) (80-88) (30.0-34.0) (128-190) (50.4-96.2) (23.0-30.0)

total alkalinity, mg/LCaC03

av 178 174 183 77.9 70 78.3 26.0 22.7 20.1(range) (173-188) (142-222) (150-270) (74.4-80.0) (66-72) (58.0-114) (24.6-28.0) (21.0-24.6) (19.0-20.4)

pHav 7.73 8.54 8.07 7.61 7.40 8.32 7.53 7.57 7.64(range) (7.69-7.77) (8.27-8.77) (7.62-8.65) (7.50-7.78) (6.60-7.70) (8.22-8.57) (7.32-7.60) (7.39-7.76) (7.38-7.79)

total Ca, mg/Lav 49.8 18.4 4.8 64.7 20.4 7.9 57.5 24.7 6.0(range) (48.1-50.5) (17.0-20.1) (4.1-5.6) (51.7-72.6) (19.6-22.5) (7.2-8.9) (45.1-67.0) (17.2-32.5) (5.6-6.5)

total Mg, mg/Lav (calcd) 19.6 5.8 1.5 10.3 7.8 2.7 4.0 3.1 2.8

a H :::; high, M =medium, L:::; low. Other parameters (averages and ranges over all bioassays): dissolved oxygen, 7.7 (6.7-8.9) mg/L; temperature, 13.7 (12.3-15.7)

°C: ammonia nitrogen, 0.05 (0.00-0.17) m9/L; nitrate nitrogen, 0.05(0.00-0.20) mg/L; nitrite nitrogen. all values 0.00 mg/L.

Table III. Multiplication Factors for Conversion of Nonfiltered to O.45-JLm Filtered Copper Concentrations asMeasured by the Cuprethol Method

hardness/alkalinity a H/H M/H LlH H/M M/M LIM H/L M/L LlLhardness, mg/L CaC03 195 70 25 192 83 31 154 74 27alkalinity, mg/L CaC03 160 174 169 72 70 78 20 23 20pH 7.0 8.5 8.5 7.0 7.4 8.3 6.8 7.6 7.0unfiltered Cli concns, 0.34- 0.11- 0.01- 0.12- 0.04- 0.02- 0.04- 0.03- 0.01-

mg/L 1.28 0.40 0.08 0.23 0.28 0.16 0.16 0.11 0.03factor 0.92 0.94 0.89 0.82 0.87 0.86 0.78 0.79 0.74

a H :::; high. M :::; medium, L :::; low.


Table IV. Equilibria for Copper Test Water Solutions Table V. Acute Copper Toxicity to Cutthroat Trout(28) under Different Conditions of Alkalinity and Hardness. (10 Fish/Tank)

reaction log Keq

H+ +OW <=" H2O 14.0 fish size 96-h LCso

H+ +col- <=" HC03- (K2) 10.33 test wI. length, (95% C.I.),no. 9 em alkalinity hardness mg/l CUtalal a

2H+ +col- <=" H2C03 (K, + K2) 16.68391 4.2 7.4 high high 0.367 (0.319-0.424)

Ca2+ + H20 <=" CaOH+ +H+ -12.7378 3.2 6.9 high medium 0.186 (0.172-0.202)

Ca2+ + H+ +COl- <=" CaHC03+ (1.0 + K2) 11.33453 9.7 8.8 high low 0.0368 (0.0350-0.0387)

Ca2+ +col- <=" CaC030 3.15Mg2+ + H20 <=" MgOH+ + H+ -11.42 412 4.4 8.1 medium high 0.232

Mg2+ + H+ +C032- <=" MgHC03+ (0.95 + K2 ) 11.28 370 2.7 6.8 medium medium 0.162 (0.148-0.176)

Mg2+ +col- <=' MgC030 2.88 379 3.2 7.0 medium low 0.0736 (0.0672-0.0805)

Cu2+ +H20 <=' CuOH+ + H+ -7.7 424 5.2 8.5 low high 0.0910 (0.0832-0.0996)Cu2+ + 2H20 <=' Cu(OHj,° + 2H+ -14.32 b 413 4.4 7.7 low medium 0.0444 (0.0403-0.0489)2Cu2+ + 2H20 <=' CU2(OHj,2+ + 2H+ -10.3 425 5.7 8.9 low low 0.0157Cu2+ + H+ + C032- <=" CuHC03+ 12.3 c

Cu2+ +COl- <=" CuC030 6.75a CUtalal as measured by cuprethol on OAS-JIm filtrate.

Cu2+ + 2col- <=' Cu(C03)/- 9.92

a Constants determined at 18-25 °C and corrected to zero ionic strength.b Constant from Vuceta and Morgan (29). C Constant from Childs (30).

water was 5.38 X 10-:1 M. The equilibrium constant, log K 2,

for the bicarbonate-carbonate system calculated with thiscorrection is 1.0.20, as compared to the uncorrected value of10.33. Considering the variability of equilibrium constantsavailable in the literature, this difference was considerednegligible and the equilibrium constants for the reactionspresented in Table IV were used without correction. The othervariables introduced into COMICS included pH and the molarconcentrations of total inorganic carbon, calcium, and magnesium. Total inorganic carbon (moles/liter) was calculatedfrom bicarbonate alkalinity and pH using the followingequations:


The 96-h LC50 values and their 95% confidence interval(C.I.) end points for the bioassays are presented in Table V,and the toxicity curves for these bioassays are shown in Figure1; LC50 values for time periods other than 96 h can be estimated from these curves. The curves illustrate that the 96-htest period was sufficient to attain an asymptotic LCso, alsoknown as the incipient LC50 (31).

Fish size data are also presented in Table V. Although thetest fish were all obtained from the same pool, the tests wereconducted over a 3-month period during which fish grew insize prior to testing. We have no data relating the susceptibility of cutthroat trout of different sizes to copper toxicityunder uniform water chemistry conditions, but in 11 separatebioassays which were under uniform water chemistry conditions we have studied this relationship using 1- to 26-g rainbowtrout as the test fish. These data are presented in Table VI.There was a small but significant effect on the susceptibilityof the rainbow trout to copper toxicity based on fish size; thelarger fish were slightly less susceptible than the smaller fish.The correlation coefficient for the relationship between fishweight and the observed LC50 values was 0.68 (P = 0.(09), andthe equation of the regression line was LCso = (0.1266)·(1.0374)weight. Howarth and Sprague (17) have recently reported that lO-g rainbow trout were 2.5 times more resistant

Table VI. Acute Copper Toxicity to Rainbow Trout ofDifferent Sizes, under Uniform Water ChemistryConditions a

no.fish size 96-h LCsofish

test p" length, (95% C.I.),no. tank wt,g cm mg/L Cutolal b

128 20 0.169 (0.148-0.193)496 20 4.9 0.0853 (0.0767-0.0950)403 10 2.1 6.0 0.0833 (0.0748-0.0928)503 20 2.5 6.1 0.103 (0.0961-0.111)169 20 2.6 0.274 (0.222-0.337)136 20 4.3 0.128 (0.101-0.162)141 20 9.4 9.2 0.221 (0.201-0.243)236 5 11.5 9.9 0.165 (0.137-0.198)233 5 18.7 11.8 0.197 (0.152-0.254)166 10 24.9 13.5 0.514 (0.434-0.610)160 10 25.6 13.4 0.243 (0.210-0.281)

a Water chemistry data averaged over all tests (averages with ranges in parentheses): pH 7.84 (7.77-7.91); alkalinity, 174 (173-176) mg/L GaGO,: hard

ness, 194 (192-196) mg/L GaGO,; calcium, 55.1 (49.7-61.4) mg/L: magnesium

(calculated), 13.7 mg/L; dissolved oxygen, 7.9 (5.6-9.6) mg/L; temperature,12.8 (11.8-13.9) °G: ammonia nilrogen, 0.07 (0.00-0.27) mg/L; nitrate nitrogen,

0.12 (0.00-0.31) mg/L; nitrite nitrogen, all 0.00 mg/L. b CUtalal as measured bycuprethol on 0.45-J,lrn filtrate.

to copper than 0.7-g trout. Considering the narrower range offish weight (3-10 g) in our cutthroat trout bioassays (TableV), it was assumed that fish size in our experiments was notsignificantly related to susceptibility to copper toxicity.

The copper LCso values presented in Table V verify thelong-standing observation that the toxicity of copper to fishesis inversely correlated with the hardness of water. Results ofthe COMICS equilihrium calculations using the copper 96-hLC,.o values (in molarity) are presented in Table VII, andpercent distributions of the copper species are given in TableVII!. Hardness and alkalinity determined the magnitude ofthe copper LC"o value. The estimated partial correlation between the copper LC,.o value and hardness, holding alkalinityfixed, is 0.882 (900/0 C.!. = 0.571-0.972); the estimated partialcorrelation hetween the copper LC50 value and alkalinity,holding hardness fixed, is 0.756 (900/0 C.!. = 0.246-0.938). Theeffect of alkalinity on the LC"o may be due in part to its effecton copper speciation, but cannot be explained entirely on thisbasis. Alkalinity and pH independently control the speciationof copper.


O.B

0.6

TEST

(~91)\\

,,,

,,

(412)------------ HIM

3

--- H/H

Hordn...JAlhlinity

{424',, •

(379)~;__ - - - __ u h_

u

__ nn U U _u • H/L

~~ -~~~(42!U__ t~~

{37"\\

{37al" \,"--..~--=-- - -- --- - --- --M/H

- - - - - - - - - - - - - W/M

0.0

...g.."... 0.4,...E0lI'l...-'

0.2

2

TIME, DAYS

Figure 1, Toxicity curves for copper bioassays on cutthroat trout (H = high, M = medium, L = low)

Table VII. Metal Speciation for Copper 96-h LCse Values for Cutthroat Trout (Concentrations in Moles/Liter)

hardness/alkalinity a and test no.

H/H391

M/H378

L/H453

HIM M/M LIM412 370 379

H/L424

MIL413

L/L425

CUT b (Xl0")CaTe (X 104 )

MgTe (Xl04 )

HC03- d(Xl04 )

inorganic C (X 104)

pH

C032- (Xl0")Ca2+ (Xl0")CaOH+ (Xl0")CaHC03+ (Xl0")CaC030 (X 10")Mg2+ (Xl0")MgOH+ (X lOB)

MgHC03+ (X lOB)

MgC030 (Xl0B)

Cu2+ (Xl0B)

CuOH+ (Xl0")Cu(OHj,° (X lOB)

CU2(OHj,2+ (X 108)

CuHC03+ (X lOB)

CuC030 (Xl0B)

Cu(C03),>- (Xl0B)

57812.48.0735.637.17.73

8711180001.274110146077 80015.924005148.789.41

1210.1112.844305.54

2934.592.3934.835.48.54

5510413002.86140032102230029.46759310.3192.211830.006120.10198.88.06

57.91.200.61736.637.38.07

2000113000.26440931858902.6319189.10.3130.73320.60.0006760.10635.11.03

36516.14.2415.616.47.61

2891580001.282390644417006.4656391.413.911.31110.1611.972260.964

2555.093.2114.015.27.40

162501000.251692115317003.0239039.018.59.2655.80.1082.381690.404

1161.971.1115.715.98.32

1510190000.792294406108008.591491240.3851.6180.50.003240.055632.80.733

143

14.31.655.205.547.53

80.71420000.96172416216400

2.1174.510.012.182166.70.08480.57755.10.0658

69.96.161.284.544.817.57

78.0613000.45427567.5127001.8051.07.545.474.0536.10.02070.22924.00.0277

24.71.501.15

4.024.237.64

81.7149000.13059.717.2

115001.9040.97.101.581.3814.40.002380.05907.260.00878

a H == high, M = medium, L = low. b CUr =CUtotal as measured by cuprethol on 0.45-J,tm filtrate. C CaT +MgT = hardness. d HC03- =alkalinity.

The most abundant forms of soluble copper over all theconditions tested were dissolved copper(II) carbonate,CuC03o, and copper(II) hydroxide, Cu(OH)z°. The amount

of copper(II) ion dramatically increased as the alkalinity andpH decreased, and a more subtle, but parallel, behavior wasexhibited by CuOH+ within the pH range tested. In contrast


'" '"

0.02

';-;;---+.;__--:~--~:;:__--~----'''''_:~--_::':;__-___c_:!7--__:!c 2(°"1 22+- e.,

0.0 I 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6

pH

Figure 2. 96-h Leso copper species distribution diagram for bioassays on cutthroat troutRegression equations: log [Cu2+1 = 13.6762 - 1.692pH (P= a 001); log ICuOH+-Cu} =5.8700 - 0.691pH (P =0.074); log (Cu{OH),°-Cu] =-0.8204 + 0.307pH(P= 0.384); log (Cu,(OHI,2+-Cul =8.9548 - 1.385pH (P= r..(74): log ICuHC03+-Cui =7.9767 - 1.117pH (P= 0.072): Jog [CuC030-Cuj =2.4379-0.118pHIP =0.830): log [CuICO,)," -Cu I =-12.2673 + 1.457pH (P =0.11): log [CUT1= 1.8412 + 0.040pH (P =0.926)

to these four species, the amounts of CuAOH}z2+, CuHCO~+,and Cu(CO:1}z2- were very small. Within the pH range tested,the concentration of CU2(OH}z2+ increased with a decreasein alkalinity. The concentration of CUHCO;I+ increased witha decrease in pH. Cu(CO:1)i- was more abundant at high pHand high alkalinity.

Interpretation of the results of the experimental tests reported in this paper, along the above lines of reasoning whichlead to prioritizing chemical species in order of relative tax·icity, is constrained by the variation of pH among the testsconducted. However, pH was relatively constant in the threebioassays conducted at high hardness coupled with a high,medium, and low alkalinity (Table VIII; tests 391, 412, and424). These data show that as the proportions of carbonatespecieg decreased, the median lethal concenLration of copperalso decreased; as the proportions of Cu2+ and the hydroxylspecies increased, the LC,.o decreased. This behavior elimi-

nateg CuC030 as a toxic form of copper, supporting the hypothesis of Stiff (J I) and the findings of Howarth and Sprague(17), but in disagreement with the conclusions of Shaw andBrown (9); it also eliminates CuHC03+ and CU(C03)22-. Itcorroborates the widely held view that Cu2+ is toxic and alsoimplicates CuOH+ and Cu(OHjz° as toxic forms. The dataindicate that CU2(OHjz2+ may also be toxic, as has recentlybeen reported by Andrew et al. (J6) and Howarth and Sprague(J 7); however, the concentration of CU2(OHjz2+ is two to fourorders of magnitude smaller than Cu2+, CuOH+, andCu(OH}z°, so its acute toxic effect may be negligible by comparison. The evidence from this study that CuOH+ is toxic tofishes is in agreement with the conclusions of Pagenkopf etal. (1,5), Andrew et al. (16), and Howarth and Sprague (17).The present work further suggests that Cu(OHjz° may alsobe toxic to fishes.

Examination of the data in Tables VII and VIn shows that


Table VIII. Percent Distribution of Copper Species for 96-h LCso Values for Cutthroat Trout

hardness/alkalinity a and test no.

H/H MIH LlH HIM MIM LIM HIL MIL LIL391 378 453 412 370 379 424 413 425

CUT b 578 293 57.9 365 255 116 143 69.9 24.7alkalinityc 178 174 183 77.9 70.0 78.3 26.0 22.7 20.1hardness c 205 69.9 18.0 204 83.0 31.4 160 74.3 26.4pH 7.73 8.54 8.07 7.61 7.40 8.32 7.53 7.57 7.64

Cuz+ 1.5 0.1 0.5 3.8 7.2 0.3 8.5 7.8 6.4CuOH+ 1.6 0.8 1.3 3.1 3.6 1.4 5.7 5.8 5.6Cu(OH),o 20.9 62.4 35.6 30.4 21.9 69.4 46.6 51.6 58.3Cu210Hj,z+ 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.0 0.0CuHC03+ 0.5 0.0 0.2 0.5 0.9 0.0 0.4 0.3 0.2CuC030 74.4 33.7 60.6 61.9 66.3 28.3 38.5 34.3 29.4Cu(C03j,z- 1.0 2.8 1.8 0.3 0.2 0.6 0.0 0.0 0.0

a H ;;:; high, M ;;:; medium. L = low. b CUr = C~OlaJ as measured by cuprethol on G.4S-pm filtrate; in moles/liter X 108. e Alkalinity and hardness in milligrams/literasCaC03 ·

(1) at constant alkalinity it is the pH that determines therelative distribution of Cu2+, CuOH+, and Cu(OHhO; (2) ata constant pH, it is the alkalinity that determines the relativedistribution of Cu2+, CuOH+, and Cu(OHhO; (3) the highestconcentrations of Cu2+ and CuOH+ occurred at the low pHsand low alkalinities; (4) the concentration ofCu2+ is sensitiveto changes in pH; (5) the percents of CuH and CuOH+ are thesame at pH 7.7; above pH 7.7 CuOH+ is the predominant ofthose two species, whereas below pH 7.7 Cu2+ predominates;and (6) the proportion of Cu(OHhO increases with increasingpH. To illustrate these observations in a more generalizedmanner, the data were used to construct the copper speciesdistribution diagram shown in Figure 2. In this figure, the LCwconcentrations for each test of the six copper species CuOH+,Cu(OHhO, CU2(OHh2+, CuHC03+, CuCOao, and Cu(C03h 2are expressed as their concentrations of CUi the sum total ofthese is the LC50 as total dissolved copper.

In summary, hardness and alkalinity control the medianlethal concentration of copper toxic to cutthroat trout. Themost important copper species causing toxicity within the pHrange tested are Cu2+, CuOH+, and Cu(OHhO The concentration of each of these species varies with pH and alkalinity.Lower pHs favor Cu2+; higher pHs favor CuOH+ andCu(OHhO Lower alkalinities favor all three of thesespecies.

It is concluded that the critical factors regarding coppertoxicity to fishes are not so much which copper species aretoxic, as are the controlling roles of hardness, alkalinity, andpH. To ensure the protection of aquatic life, it is recommendedthat consideration be given to establishing water quality criteria for copper not only on the measure of total copper, butalso based on a stepwise scale dictated by the pH, hardness,and alkalinity of a given aquatic environment.

Note Added in Proof

The constants used in these calculations were the bestavailable in the literature. Recent unpublished data (W. G.Sunda, personal communication,l978lraises some questionconcerning the formation constant for Cu(OH}z°. The calculations upon which the toxicity conclusions reported aboveare based have been redone using the alternate value for theformation constant for Cu(OHho. The effect of this is to reduce Cu(OHho from a major to a minor species in the distribution of constituents, but the relative concentrations of allspecies,Cu(OHhOincluded, as a function of alkalinity, hardness, and pH, remain unchanged. Since the toxicity conclusions are based entirely upon trends in the concentrations of


the various chemical species, these conclusions are valid regardless of which constant may ultimately prove to be correct.We wish to thank K. Emerson for assistance with recalculationof the data for comparison with our initial findings.

Achnowledgment

The authors wish to acknowledge the many helpful suggestions and contributions of D. E. Armstrong, F. M. Morel,D. K. Harriss, K. Emerson, and R. W. Andrew in discussionsduring the research or preparation of the manuscript. Wethank M. A. Hamilton and S. M. Hinkins for statistical help,G. K. Pagenkopf for adapting COMICS to the MSU computer,F. M. Morel for processing our data by MINEQL for comparison to COMICS, R. J. Luedtke for assistance with conductingthe bioassays, and K. Wang and V. T. Brice for performingcertain water analyses. The research reported in this paperwas taken in part from C. Chakoumakos' M.S. Thesis, University of Wisconsin Water Chemistry Laboratory (D. E.Armstrong, thesis committee chairman).

Literature Cited

(I) u.s. "PA, "Quality Criteria for Water", Office of Water andHazardous Materials, U.S. Enviroomental Protection Agency,Washingtun, D.C., 1977,256 pp.

(2) Natiunal Academy of Sciences, "Medical and Biulogic Effects ufEnvironmental Pollotants: Copper", Committee on Medical andBiologic Effects of Environmental Pollutants, National AcademyufSciences, Washingtun, D.C., 1977, 115 pp.

(3) Grande, M., Adv. Water Pvllut. Res., 3(1),97-111 (1967).(4) Sprague, J. B., Nature (London), 220(5174), 1345-6 (1968).(5) Wilson, R. C. H., J. Fish. Res. Roard Can., 29(10), 1500-2

(1972).(6) Zitko, P., Carson, W. V., Carson, W. G., Bull. Environ. Contam.

Toxicvl., 10(5),265-71 (l97:l).(7) Biesinger, K. K, Andrew, R. W., Arthur, J. W., J. Fish. Res. Board

Can.. 31(4),486-90 (1974).(8) Illack, J. A., Ph.D. Thesis, University uf Michigan, Ann Arbor,

Mich., 1974, 129 pp.(9) Shaw, T. L., Brown, V. M., Water Res., 8(6),377-82 (1974).(10) Lluyd, R., Herbert, O. W. M., J. Inst. Public Health Eng., 61,

132-43 (1962).(II) Stiff, M. J., Water Hes., 5, 171-6 (1971).(12) Scaife,J. F., Can. J. Chem., 35, 1332-40 (1957).(13) Andrew, R. W., in "Toxicity to Biota of Metal Forms in Natural

Water", R. W. Andrew, P. V. Hodson, and D. E. Konasewich, Eds.,International Joint Commission, \Vindsor, Ontario. 1976. PO127-43,

(14) Stumm, W., Murgan, J. J., "Aquatic Chemistry", Wiley, NewYork, N.Y., 1970,58:1 pp.

(15) Pagenkupf, G. K., Russo, R. C., Thurston, R. V., J. Fish. Res.Board Can., 31(4),462-5 (1974).

(16) Andrew, R. W., Biesinger, K. E., Glass, G. E., Waler Res., 11(3),309-15 (1977).

(17) Howarth, R. S., Sprague, J. 8., ibid., 12(7),455-62 (1978).(18) Stiff, M. J., ibid., 5,585-99 (1971).(19) Maney, K. H., Allen, H. E., EPA Ecol. Res. Ser., EPA-600/3

77-037, U.S. Environmental Protection Agency, EnvironmentalResearch Laboratory-Duluth, Duluth, Minn., 1977, 110 pp.

(20) Perrin, D. D., Sayee, 1. G., Talanta, 14,833-42 (1967).(21) Morel, F. M., Morgan, J. J., Environ. Sci. Technol., 6(1),58-67

(1972).(22) Hem, J. D., U.S. Geological Survey Water-Supply Paper 1473,

2nd ed, U.S. Government Printing Office, Washington, D.C., 1970,363 pp.

(23) Mount, D. 1., Brungs, W. A., Water Res., 1(1),21-9 (1967).(24) American Public leIealth Association, American Water Works

Association, and Water Pollution Control Federation, "StandardMethods for the Examination of Water and Wastewater", 13th ed,American Public Health Association, Washington, D.C., 1971,874pp.

(25) American Public Health Association, American Water WorksAssociation, and Water Pollution Control Federation, "StandardMethods for the Examination of Water and Wastewater", 14th ed,

American Public Health Association, Washington, D.C., 1976, 1193pp.

(26) U.S. EPA, EPA·625/6-74-003, Methods Development andQuality Assurance Research Laboratory, U.S. EnvironmentalProtection Agency, Cincinnati, Ohio, 1974.

(27) Hamilton, M. A., Russo, R. C., Thurston, R. V., Environ. Sci.Techno/., 11(7),714-9 (1977); correction, 12(4),417 (1978).

(28) Smith, R. M., Martell, A. E., "Critical Stability Constants", Vol.4, Plenum Press, New York, N.Y., 1976,257 pp.

(29) Vuceta, J., Morgan, J. J., Limnol. Oceanogr., 22(4), 742-6(1977).

(30) Childs, C. W., in "Proceedings 14th Conference on Great LakesResearch", pp 198-210, 1971. Int. Assoc. Great Lakes Res.

(31) Sprague, J. 8., Water Res., 3,793-821 (1969).

Received for review February 21, 1978. Accepted September 7, 1978.This research was funded by the U.S. Environmental ProtectionAgency, Environmentol Research Laboratory-Duluth, ResearchGrants R800861 and R80:J950, and National Science FoundationGrant No. OCE74-24317.

Chemical Speciation of Heavy Metals in Power Plant Ash Pond Leachate

Thomas L. Theis· and Richard O. Richter'

Department of Civil Engineering, University of Notre Dame, Notre Dame, Ind. 46556

• Soil attenuation of heavy metals from industrialleachatesis dependent upon many factors. Data in this paper are basedon field measurements from an active power plant fly ashdisposal site and are organized via a thermodynamic approachwhich is facilitated by computer solutions to the equilibriumsituation. Results for the site studied show that adsorptiononto hydrous iron and manganese oxides is the major solubility control for cadmium, nickel, and zinc while precipitationof discrete phases controls for chromium, copper, and lead.The partitioning of heavy metals between solution andparticulate phases is most affected by pH, p(FeOOH),p(MnOx ), and P(S042-).

The mobilization of undesirable materials into the environment through activities related to coal combustion hasrecently been given considerable attention (1-4). These materials include heavy metals, trace organic compounds (suchas polynuclear aromatic hydrocarbons), large amounts ofdissolved solids, and waste streams of extreme acidity or al·kalinity. A pathway of some interest is leaching from fly ashand/or S02 scrubber sludge disposal sites. It has been shownthat leachates from these areas can contain significant levelsof heavy metals, sulfates, and total dissolved solids (5).

Once a leachate containing various substances enters thesoil environment, it is desirable to know the types and extentof interaction which occur between leachate and soil particles,that is, the "natural attenuation capacity" of a specific soilcomponent fot a given leachate constituent. In the case ofdissolved ions, these interactions will take the form of precipitation of a discrete solid phase or adsorption onto particlesurfaces. Soluble complexes, if they are formed to an appreciable degree, will also affect these mechanisms.

In this study, data gathered from an active fly ash disposalpond will be presented and analyzed with the aid of a chemical

I Present address, Department of Civil and Environmental Engineering, Washington State University, Pullman, Wash. 99164.

0013-936X/79/0913-0219$01.00/0 © 1979 American Chemical Society

equilibrium computer model so as to provide a realistic as·sessment of the subsurface reactions which various heavymetals have undergone since the initial construction of thefacilities. Although the interactions among several soil andleachate components may be chemically rather complex, andare, of course, specific to the site studied, they are consideredtypical of the reactions which occur in a subsurface leachingzone. The site reported on here is viewed as representative ofsystems of generally wide environmental interest.

Site Description

The site from which data were gathered is a 735-MW coalfired power station located in a dunal area adjacent to LakeMichigan. There are two primary fly ash disposal ponds whichare operated on an alternating basis, i.e., while one pond isbeing actively loaded the other is allowed to dry and the ashis removed and deposited elsewhere. A schematic diagram ofthe site is shown in Figure 1. Numbered circles refer to boringsmade as part of this study. This layout was constructed andput into operation in early 1974. Each pond has a capacity ofapproximately 62 000 m:l (16.5 MG). Under normal operatingconditions, the station produces between 310 and 360 metrictons/day (340-400 tons/day) of fly ash. This is sluiced to oneof the ponds where it is allowed to settle. The normal hydraulicloading is 0.125 m:l/s (2.85 mgd). The supernatant is recycledwith make-up water added to account for losses throughevaporation and seepage. Calculations indicate a seepage rateof approximately 0.044 m:l/s (l mgd).

The site is underlain by a well-drained dunal sand with aneffective size of 0.18 mm and coefficient of uniformity of 1.5.The void ratio is approximately 0.5. The ponds are maintainedat a constant head of9.6 (:1I.5 ft) above the lake. The naturalgroundwater level is located 3 to 6 m (10-20 feet) beneath theponds. The leachate zone drops quickly toward the lake butextends 150-200 m (500-650 ft) in the opposite direction. Atthis point (the approximate location of boring 13 for pond 1in Figure 1) there is a confluence of pond leachate with naturalgroundwater and the flow returns toward the lake.

During the major portion of this study, only pond 1 wasbeing actively loaded with ash; thus, much of the data pre-


COAL STORAGEPILE

14

15

21

jFigure 1. Layout of field study site; approximate scale, 4700:1

sen ted in this paper pertain to this area of the site. [t shouldbe noted that boring numbers 2, 3, to, 18, 13, and 15 are 10'cated linearly along a flow path from pond I, thougb boring15 is located outside the leaching zone.

Experimental Methods

Field. A series of sampling wells was located at the positionsof the borings in Figure 1 during the summer of 1976, about2.5 years after initiation of disposal activities. Wells were 10·cated at depths of 1.5 to 2.5 m (5-8 ft) beneath the prevailingwater table. Soil samples were taken at each 0.5-m intervalalthough only samples at the groundwater interface wereanalyzed as part of this study. Samples for soluble metals weretaken periodically.

Laboratory. Soil samples were analyzed for total heavymetals after a strong acid digestion by atomic absorptionspectrophotometry (6). Other leachate constituents weredetermined by procedures outlined in "Standard Methods"(7). A more detailed account of both sampling and laboratoryprocedures can be found in previous references (5,8).

Computer Analysis. Analysis of soil and leachate data wasfacilitated through application of the computer model ItE1l~;(~L2 (9). It was assumed that equilibrium conditions arereasonable approximations for relatively slow movinggroundwater systems over long time periods. The model iscapable of thermodynamically speciating a chemical systemgiven a set of input data. This includes complex formation,oxidation-reduction, precipitation-dissolution, and surfacesorption reactions. The adsorption routine used was that ofthe solvent-ion interaction model which requires specificationof specific chemical free energies of adsorption of a givensorbate-sorbent combination apart from coulombic or sol-


vation effects (10). These were either determined in the laboratory, found in the literature, or estimated.

The general procedure for the application of the programwas to input total concentrations of heavy metals and sorbingmetal oxides plus the chemical composition of the leachateas determined analytically on soil fractions and well samples.In this manner, a present day assessment of the past contributions of various attenuation mechanisms at each boringcould be made. The geometry of the borings around pond 1provides a convenient distance parameter from which to determine the effects of changing soil and leachate propert.ies.

Results

The power plant burned high sulfur coal mined in southernIllinois throughout the study period. This resulted in highsulfate concentrations in the fly ash pond leachate on the orderof 500-1000 mg of SO./L. In contrast, alkalinities in theleaching zone were small, generally less than 10 mg/L asCaCO". A reversal of these concentration trends took placeat the point of confluence of the leachate and the naturalgroundwater. Figure 2 gives a represent.at.ive graphic presentation for heavy metal profiles. The peaks of many of themetals in Figure 2 occurred periodically and were shown tocorrelate with variations in ash loading to the pond. Theyrepresent chemical perturbations moving t.hrough the leachingzone (5).

An examination of the analyses from a typical volume of soiland water from the leaching zone (boring 18) reveals that lessthan 1% of the total for any metal exists in a soluble form, t.herest being associated in some manner with t.he solid phase.These results are given in Table I. For a system such as thisone in which soil accumulations of metals are a recent event,

5000

ffASY §4000 I g.lOOO ',rr.-{ POND No 1 i

Metel Prohll'!: Oct 18. '76, ! Well Numbtrs ~~ 2,3,10,13,15,18 '0 E

i 300 Bz0 0

~ ~~~~~t.!,f_6 i=..

II:4~I- Elevation

~ 2 wU II:z

°i8 Pb

-'

~Ni 0, c, z

:>~ -:....Zn 0

~AsII:

a I '"~ ~ Pool?:! 200 300 400 500 600

( Lokel DISTANCE, meltrs

Figure 2. Trace metal profile vs. distance for Oct 18. 1976 (after Theiset al.; see ref 5)

Table I. Particulate and Soluble Metals in Soil-WaterSystem at Michigan City a

particulate. soluble. %metal ~g/g 1l-9/ 9 soluble b

As 4.12 29 0.28

Cd 0.48 3.4 0.28Cr 13.0 12.0 0.04

Cu 12.6 275 0.87

Pb 8.8 50 0.23

Ni 24.4 410 0.67Zn 26.2 480 0.73

pMe SOluble (pred)

Figure 3. Total soluble metals measured in the field vs. total solublepredicted metals from calCUlation; data for Jan 4, 1977

Table II. Total Iron and Manganese Values aroundPond 1 (~g/g)

boring Fe Mn

2 2820 30.83 3360 41.1

10 1680 22.3

18 2470 36.213 2930 57.315 2690 52.1

Table III. Oxide Properties Used in This Study a

• Data for Det 18. 1976 sampling date at well no. 18. Data for other wells and

dates do not differ substantially. I) Computed using an average void ratio of0.5.

,,-FeOOHMnO,Si02

zpc

5.5 (11)2.25 ( 13)2.0 (12)

85 (II)

280 (14)0.013 (11)

14 (12)32 (12)

4.3 (12)

it is likely that they are present as a surface form which ischemically sensitive to even slight changes in solution chemistry. This could be expected to affed the part.itioning of ametal between solution and solid phases.

In this study, the major sorbing sinks for heavy metals wereassumed to be oxides of iron. manganese, and silir.a. The totalamounts of iron and manganese found in the "'aching fieldaround pond 1 are given in Table II. In sit.u determinat.ionsof the oxide properties were not made; rather the representative values given in Table III for all three oxides were used.Combination of the information in Tables II and III yieldedoxide dat.a which were specitic for the location of each boringin the leaching field. As indicated previously, adsorption datafor each metal oxide combinat.ion apart from elect.rostatic andsolvation effects (~Go"h,'m) must he given. Values used in thisstudy are given in Tahle IV.

As a measure of the degree of correspondence between tieldand computer data, the tot.al soluhle measurerl metal concent rat ions were compared with those predicted. Results aregiven in Figure ~. Points falling within the dot led lines arewithin 0.;; log unit of the actual concentration. Points fallingbelow the line indicate greater solubility predict.ed thanmeasured. The modeling of chromium is seen to give resultsgenerally higher than measured. It is possihle that thechemical free energy of adsorption for this metal onto ironoxide was underestimated, thus accounting for the discrepancy.lt may, however, he due t.o a lack of agreement aboutthe speciation of chromium. Modeling st.udles suggest thatconditions favor the format.ion of appreciahle amounts ofsoluble Cr(OH)4-(aq). The formation of this species at the lowconcentrations of total Cr measured and neutral pH valuesis regarded as a slow reaction; thus, the equilihrium modeling

a Numbers in italics in parentheses refer to references under Literature Cited./:! Specific surface area, m2/g_ C Dielectric.

Table IV. Specific Chemical Free Energies Used inThis Study a (kcallmol)

a-FeOOH MoO. 5102

Cd -6.0 (15) -4.85 (12) -6.54 (13)Cr -5.4' -4.85 (12) -7.00 (10)

Cu -5.4' -5.17 (13) -7.98 (12)

Ni -6.0' -4.25 (13) -6.54 (11)Pb -5.4' -4.85 (12) -6.50 (12)Zn -7.4(15) -4.85 (13) -6.54 (13)

a Italic numbers in parentheses refer to references under Literature Cited.tJ Estimated.

of this metal may be limited by kinetic considerations. Mostot.her points below tbe line of Figure 3 are predictions forboring 15 which was outside the leaching field. The soilchemistry characterization here is not considered as thoroughas at. other locations.

The computer-simulated speciation of specific metals asa function of distance is given in Figures 4a through 4d forchromium, copper, lead, and zinc, respectively. The resultsfor cadmium and nickel were qualitatively similar to zinc.Leacbate data for one sampling date were used; however, thespeciation pattern changed very little for other sampling dates.For most metals free aquo and sulfato complexes are seen todominate in the pond liquor. The hydroxo complex ofchromium(lII) is the major soluble form for this metal. When


('. ( BO!tIlC) 18 ' 384 J

II N,

____-.._. _~..1.

i Pb-- ?:.C,----;> :cd---_.... : Cr ln1

I----i------;::rIIIIII

.•. ..:...1 ..4

jib

~

" 61,

pea". moles IlIter

siderably lower than the solid phase concentrations in accordwith the measurements ~iven in Table l.

It is interesting to examine the effects which leachate andsoil variables bave on the soluble metals in solution. Fi~ures5a and 5b ,how predicted solubLe metal concentration as afunction of suLfate and carbonate in soLution, respectively.Sulfate ion, S04"-' forms weak complexes with all of themetals studied; however. since it is a common component ofaqueous power plant waste streams, the effect of these complexes on attenuation in the soil should not be i~nored. Atypical sulfate concentration in the leachin~ field is indicatedin Figure 5a. In this system it appears that sulfate has no appreciable solubilizin~ effect althou~h concentrations onlyslightly higher. above approximately 10-" M, could be expected to increase the proportion of the soluble metals. Thus,althou~h the presence of hi~h sulfate alone may be comparatively unobjectionable in these waters. the accompanyin~

effect of beavy metal solubilization could be more serious.Cbromium is relatively unaffected by sulfate due to thedominance of hydroxo complexes at tbis pH (7.0).

The effect of carbonate on t.he solubility of t.he metals inFigure 51> is less obvious. Chromium(\lI) does not form a,table carbonate and '" is not affected. The carbonates ofnickel and cadmiulll do not form under tbe conditions present.and zinc carbonate affects soluble zinc at total carbonateconcentrations approachin~ 10- 1 M. Carbonate interacts withboth lead and copper by forlllin~ bot.h soluble complexes andprecipitat.es. Above 10-" M total carbonat.e. copper precipitates as malachite wbile soluble lead actually increases dueto the formation of a carbonate complex. PbeO}'- At highercarbonate levels. lead carbonate be~ins to precipitate whilesoluble copper increases as the negatively charged Cu(CO,,)/complex forms.

Figure 5. Predicted variatIOn of total soluble metals with (al sulfate and(b) carbonate as the determining parameter

I--1

!~

~

400

4UO

40G

400

- Po

- Po·foe

;00

500.~

couUI~ I ANC[

UISfAI......:t, (l,elel~

,DO

4 r' -,.._-- .,. J-

6i,

lbl4 ,

\

co"_-L-

: Cuso;\01

o :Ov

P"rl;:)

J r-"., ¥,,,~t1-- ~--rL~--

,-',S0~ I ---

o·

10;) ~;,)O ~00Pona tll':::iTAt'oCE.,

j a

~r'

61 \.:rUI'1,"2

u 7j

C'_~L

,00 '00

Pvl\(j

Figure 4. Metal speciation around pond no. 1 vs. distance: (a) chromium:(b) copper: (c) lead: (d) zinc

the leachate stream enters the soil environment, several reoactions occur. Zinc, cadmium, and nickel are attenuatedpredominantly by adsorption onto the iron oxide, manganeseoxide playin~ a lesser rol~. In contrast, the solubilities ofchromium. copper, and lead are controlled by discrete precipitates while adsorption is of diminished importance.Leachate conditions favor the formation of lead and chromium hydroxides in the immediate pond area. Copper precipi·tates as the basic carbonate, malachite, in spite of the low alkaLinities. When inor~anic carbon concentrations increase dueto the presence of natural groundwater, the model predictslead carbonate will form. In all cases, soluble metals are con-


--i~';;";;:;;;1

c,

l __

6 7pH

'[.-'--

l_. 4 ~(Boronq 18' 2.5) \

'1I

~ l ,\ Nt , :

~ 51 I

]LlI

i~:I

:------------~ I [Cr \ Pb I .z

III

i 7 1

ICdI

]IIIIII

9[-1 I_ 1 __ L-l. __L _, 4 , 2

pSi, hectares/liter

pFe,heCIQreS/1i1er

pMn, heclares/I,Ier

Zo

- ,~

~ 6~L c,~

~ 7~ '-Pb

I8r

I I,9~ __ .---"-__'----.1.---'-

5 4 3 2

'rc4 ~

zn.i

:0

~51

Cd

- C",

~tc'

"E~

II

8r9 L ..-L_---'-__L...__JL...J

, 4

In either case, the partitioning of metals between the solubleand particulate phases is strongly influenced by solution pHand to a lesser extent by complex forming ligands such assulfate and carbonate. This offers an explanation for the relatively wide variation in soluble metals shown in Figure 2 andpreviously related to chemical perturbations moving throughthe system.

The comparatively large sorptive capacity of maganeseoxide is especially noteworthy and may warrant considerationas a control procedure for seepage type ponds such as the onestudied. For this site, it is unclear whether the iron andmanganese oxides found at various locations were presentnaturally or are being deposited from the fly ash. In the lattercase, it is possible that certain fly ashes are capable of providing this ameliorating effect, a factor which should probablybe taken into account when assessing various control procedures. The purposeful use of these oxides for heavy metalattenuation would depend upon maintaining an oxidizing soil

Figure 7. Sensitivity of predicted total soluble metals to changes insorbing surface areas: (a) silica; (b) manganese oxide; (c) iron oxide

The results imply some interesting possibilities with respectto heavy metal containment in ponded fly ash disposal sites.The removal of chromium, copper, and lead through a precipitation mechanism depends upon the solution chemistryof the leachate/soil system and so it could be expected to heoperative for all times as long as conditions are favorable.Unless the metal oxides in the soil are replenished, however,it is to be expected that the adsorptive capacity of the systemcould eventually be exhausted, depending upon the quantitiespresent initially, and those metals which are controlledthrough this mechanism (in this study, cadmium, nickel, andzinc) may migrate more freely.

Figure 6. Sensitivity of predicted total soluble metals as pH varies

Discussion

The effect of solution pH is shown in Figure 6. This variablebrings about the most noticeable changes in soluble metals,affecting both the extent of adsorption and degree ofprecipitation. In general, higher pH results in greater adsorptionwhile lower pH results in less adsorption and less precipitation. Chromium solubility increases at pH values above 7.5due to the formation of soluble hydroxo complexes such asCr(OH).,-, and, in fact, the line for chromium in Figure 6represents a hydroxide solubility diagram. It sbould be notedfor the other metals that the dominant attenuation mechanisms change as solution conditions chan;;e; thus, for example,lead sulfate exerts the major control on lead solubility at pH5 while the stoichiometry of the copper precipitate cbangesfrom malachite to cupric bydroxide, Cu(OHb at pH 9.

The changes in soluble metals as the quantities of soilcomponents vary are shown in Fi;;ures 7a, h, and c for silica,manganese oxide, and iron oxide, respectively. Silica exertsonly minor effects at very high surface areas per unit volume.In the model, this is due primarily to the low dielectric valueof silica which brings about a correspondingly high oppositional energy of solvation for adsorption of the metal cations.The effects of both iron and man;;anese are more pronounced.Surface areas of manganese approaching 10-1 haiL begin toexert an influence due to the lar;;e sorptive capacity of thisoxide; however, the amounts measured in the field were generally insufficient to bring about this effect, so that manganeseoxide adsorptive controls are secondary to adsorption into ironoxide. Figure 7c indicates that major effects due to iron become apparent at surface area concentrations higher thanmanganese. Field measurements suggest that this oxide ispresent in quantities sufficient to control cadmium, nickel,and zinc (Figure 4d). In comparing Fi;;ures 7b and 7c, theobservation can be made that manganese oxide, if present inlarge enough quantities, is capable of hecoming the dominantsink for all the metals studied, while iron oxide has only aminor influence over those metals which form discrete precipitates, that is, copper, chromium, and lead.


environment. Our studies of ash disposal ponds have shownrather consistently that oxidizing conditions prevail in theactive leaching zone.

In reviewing these results, it must he stressed that many ofthe trends indicated are derived from the anticipated thermodynamic behavior of the various components in the system.They are, however, based upon field measurements and arein general accord with observations made of heavy metalpartitioning in the soil/water environment. It is felt that theinformation presented is a reasonable assessment of the attenuation mechanisms which are operative. This studysuggests that the suhsurface reactions between heavy metalleachate constituents and soil components are generallycomplex. Nevertheless, knowledge of these reactions is viewedas important in the overall evaluation of the pollution potential of a leachate/soil system.

Literature Cited

(1) Davison, R L., Natusch, D. P. S., Wallace..1. It, Evans, C. A.,Environ. Sci. Technol .. S, 1107 (19741.

(2) Kaakinen, ,J. W., .Jorden. R. M., I.awasani. M. H.. West, H. K.ibid, 9,862 (197;;).

(:l) Theis, T. L., Wirth,.J. L.. ibid .. 11,1096 (1977).(4) Fisher, G. L., Prent.ice, B. A., Silherman, D.. Ondov..1. M., Bier-

mann, A. H., Ragaini, R. C., McFarland, A. R, Environ. Sci.Techno/., 12,447 (1978).

(f,) Theis, T. L., West.rick, ,J. D., Hsu, C. L., Marley, J. J., J. Waterr'ol/ul. Control Fed.. 511,24;;7 (1978).

(6) Bernas, B., Anal. Chern., 411,1682 (1968).(7) "Standard Methods I'or the Examination of Water and Waste

waters", 14th ed, APHA. Washington, D.C., 197;;.(8) Theis, 'I'. I,., Marley,,1. .J., J. 1'0,"'''' IJiv.. Am. SOl'. Civil EnM.. in

press.(9) McDuff, R. E., Morel. F. M. M., "Description and Use of the

Chemical Equilihrium Program REIJRQL2". Tech. Itep. EQ·7:1-02.California Institute of Technology. Pa~adena,Calif., una.

(10) .James. R. 0 .. Healy. T. W.. J. Col/oid In/erfoc" Sci., 411,6"(1972).

(11) Hichter, It. 0., Theis. T. L., presented at the 17;;th NationalMeeting of the American Chemical Society, March 1:)~1;), 1978,Anaheim, Calif., Ahstract ENVR-U22.

(l:z) Vuceta, ,J., Ph.D. Thesis, Calil'ornin Instit.ut.e of Technology.Pasadena, Calif.. I97ti.

(I:ll Murray, J. W., Geochim. Cosmo"him. Acta. 39,505 (1975).114) .Ienne, E. A., Adv. Chem. SeT'.. No. 73, ;):J7 (1968).(1;; I Forhes, E. A., Posner. A. M., quirk, .J. P.. J. Soil Sci. 27, l,,4

(197ti).

/{('{"('i!,(,d for review May 22, 1!17H. Accepted SeptlJmher IR, 1978. Thisre .... earch li'as sUPfJ()rtf'd hy (;rant N/). /<';Y-7(-)-.'-.,'-(J2-:2727 from lhpIJitJision of Riomedic(li and /';nL'ironmental Nes('arch of the Department of Ener};,\'.

An Approach to Estimating Probabilities of Transportation-Related Spills ofHazardous Materials

Charles A. Menzie

EG&G, Environmental Consultants, 151 Bear Hill Road, Waltham, Mass. 02154

• An approach to estimating probahilities of transportation-related spills of hazardous materials is described. Theapproach involves, first, determining accident rates for appropriate modes of transportation and, second, determiningthe fraction of accidents that result in spills. Spill probabilitiesare then estimated from equations based on the Poisson distribution. Estimates of spill probabilities are presently limitedby the nature of the statistics. However, the MaterialsTransportation Bureau (Department of Transportation) isnow recording more details on accidents involving spills ofhazardous materials, and, therefore, more precise andmeaningful estimates of spills can be obtained as this database develops. An example is presented on how the approachmay be used to estimate spills associated with chemical plantoperation. However, the approach may also he used in determining probabilities of spills for whole classes of chemicals,or within certain geographical areas. Such information couldhe used to design more appropriate hazardous materials spillprevention, countermeasure, and control plans.

Transportation-related spills of hazardous materials contribute to the overall environmental impact of chemical plantoperations. Spills may occur during shipment of raw materialsto the plant, shipment of products from the plant, or disposalof waste materials. Impacts of transportation-related spillsmay be more severe than spills which occur at. t.he plant sit.ebecause transportation-related spills often occur in noncontainment areas where the spilled material can escape intowater bodies or affect terrestrial biota. Such spills can occuranywhere along the transportation route and thus impactenvironmentally sensitive areas or impose public safetyproblems if the spills occur in populated areas.


EG&G, Environmental Consultants recently completed acomprehensive assessment of the environmental effects of anew chemical plant which included an assessment of theprohahility of transportation-relat.ed spills. In approachingthe prohlem of est.imating spill probabilities, it was found that,with the exception of radioactive materials and water transport of oil, little puhlished information on estimating spillprobabilities existed. Therefore, the available statistics werereviewed and a simple approach to estimating transportation-related spills was developed. The objective of this paperis to outline the approach utilized and to give an example ofits application. Limit.ations to the method are also discussed.

Estimation of Probabilities of Transportation-RelatedSpills

In order to estimate the probabilities of transportationrelated spills of hazardous materials, it is assumed that suchspills are independent events t.hat. occur randomly with respect to the distance (or mileage) over which the material istransported. The prohability of a spill occurring between themileage distance I and 1+ .::.1 will be as follows:

proh la spill occurs bet.ween I and I + .::./1 = ,,'::'1 (1)

where v = the average number of spills per mile.The numher of spills, n, occurring over some distance I. is

a discrete random variable, and, if Equation 1 is satisfied, thenn will he Poisson distributed with parameter ,'I.:

("I.)"P(n) = ----;:;T" e-"1. (2)

The Poisson distribution (Equation 2) is, in effect, a binomial distrihution for a large numher of independent events

0013-936X/79/0913-0224$01.00/0 © 1979 American Chemical Society

Table I. Summary of Data Relating to Transport of Chemicals Associated with the Operation of a HypotheticalChemical Plant

capacity of length of frequency of milesmode of transport. transport. shipment transported

transported chem origin destination transport. vehicle roule, miles (annually) (annually)

raw materials

chlorine Brunswick, plant site freight car 17 000 gal 325 150 48750Ga. (tank car)

caustic solution Brunswick, plant site freight car 16 000 gal 325 300 97500Ga. (tank car)

methyl mercaptan Houston, plant site freight car 20 000 gal 700 160 112 000Tex. (tank car)

isobutyraldehyde Pt. Lavaca, plant site freight car 20 000 gal 600 200 120 000Tex. (tank car)

acetaldehyde Bay City, plant site freight car 20 000 gal 540 260 140 400Tex. (tank car)

muriatic acid Moundsville, plant site truck 40 000 Ib 350 500 175 000W.Va. (tank truck)

final products

product A plant site Axis, freight car 20 000 gal 300 80 24 000(flammable liquid) Ala. (tank car)

product B plant site La Porte, truck 40 000 Ib 750 350 122500(corrosive) Tex. (truck load)

waste materials

hazardous waste pian! site waste disposal truck 40 000 Ib 50 380 .19 000(corrosive) site (truck load)

(transportation trips) that result in only a small number ofoccurrences in one of the two possible binomial classes (spilloccurrence vs. no spill). It has been used by others to estimatespill probabilities related to transportation of radioactivematerials (I) and oil (2). Tbe Poisson distribution was usedto determine tbe probability of one or more spills occurrin!<in a given time interval, the most probable number of spills,and the number of spills boundin!< the interquartile range, i.e.,the middle .50% of the probability curve.

If L is taken as a random variable representin!< the numberof miles between consecutive spills, and assumin!< thatEquations 1 and 2 apply, then L obeys an exponential distribution with the parameter I':

g(L) = probability density function for L = I'e-,·J· (3)

Note tbat any or all of Equations 1,2, and :l may be taken ascharacterizin!< Poisson-type spill occurrences since it is possible to deduce anyone of the relations startin!< with anyother.

The mean spill rate is defined as the expected number ofspills occurring over a distance interval of len!<th unity, andis denoted by v. The expected distance between spills may hecomputed from Equation :l to be:

EILI = l/., (4)The average number of years between spills (recurrence interval) is estimated from:

(Ii)

where R = recurrence interval (years), .' =average number ofspills per mile, and 0 = avera!<e number of miles per year. Notethat the reciprocal relation between mean spill rate and meandistance between spills is one of the implications of the Poisson assumption for spill occurrence, and may not hold true forother types of spill distributions.

Rail and bighway transportation routes and frequencieswere identified for the chemicals being considered. The distance of each transportation route was determined and multiplied by transportation frequency to obtain tbe number ofmiles that each cbemical will be transported during a particular time interval (e.g., I year, 10 years, or operating life of

chemical plant).Historical accident rates for cbemicals transported by rail

were ohtained from "Accident Bulletin-Summary andAnalysis of Accidents on Railroads in the United States" (:3-6)and "Yearbook of Railroad Facts" (6). Accident rales forhighway transportation were determined from" Accidents ofLarge Motor Carriers of Property" (7). Records of highwayaccident rates were available from the Rureau of Motor Carrier Safety for only the period 19G6 to 1970.

Historical transportation-related spill rates of hazardousmaterials were determined by multiplying the historical accident rate by F" the fraction of accidents resultin!< in spills.F, is dependent upon accident severity and integrity of thecontainer in which the chemical is transported. Unfortunately,little historical information was available on spills of specificchemicals from railroad frei!<ht cars or trucks. Therefore, F,was estimated from spill records for general classes of chemicals having similar physical and chemical properties (dataprovided by Materials Transportation Bureau, U.S. Department of Transportation) and a model developed hy the U.S.Nuclear Regulatory Commission for use with radioactivematerials (I). F, as estimated by the former method refersonly to spills causing more than $100 in property damage.

Application of the Method

A hypothetical chemical plant is used to illustrate how themethod of estimatin!< spill probabilities mi!<ht be applied. Theplant receives shipments of six raw materials, produces andtransports two products, and disposes of hazardous waste ata nearby waste disposal site (Table I). All materials aretransported by either rail (frei!<ht ear) or truck. The distanceschemicals are transported annually ran!<e from 19000 milesper year for hazardous waste to 17" 000 miles per year in thecase of muriatic acid, a raw material.

The average accident rate for freight cars operatin!< in theUnited States during 1972 to 1974 was estimated to be 1.8 X10-'; accidents per freight car mile ('rable II). The avera!<eaccident rate for trucks was 2." X 10-1; accidents per t.ruck miledurin!< 1966 to 1970 (Table III). Since the accident rate fortrucks was relatively constant during 1966 to 1970, the average


Table II. Accident Rates of Freight Cars Operating in the United States during 1972-1974

yearfreight trainaccidents a

freight caraccidents b

'relght carmiles c

accident rate.freight car

accidents per

freight car mile

1972 4653 46530 30.309 X 109 1.5 X 10-6

1973 5792 57920 31.248 X 109 1.8 X 10-6

1974 6592 65290 30.729 X 109 2.1 X 10-6

average 5658 56580 30.429 X 109 1.8 X 10-6

a Number of freight train accidents was determined from data provided by the Federal Railroad Administration Office of Safety (3-5). Number of reported accidentsinvolving collisions of two freight trains was doubled to reflect the fact that two trains were involved. b It was estimated (8) that an average of ten freight cars wasinvolved in a train accident. Therefore, the number of freight car accidents was approximately 10 X number of freight train accidents. C Number of freight car mileswas obtained from data provided by the Association of American Railroads (6).

Table III. Accident Rates of Trucks Operating in theUnited States during 1966-1970

yearaccident rate, a

accidents per truck mile

Table V. Percentages of Accidents InvolvingHazardous Materials Transported in the United Statesduring 1966-1972, by Categories of AccidentSeverity·

55.00

36.00

7.00

1.60

0.28

0.11

0.0085

0.0015

100.0000

% of accidents

50.00

30.00

18.00

1.80

0.18

0.013

0.006

0.001

100.000

freight car truck

I

II

III

IV

V

VI

VII

VIII

total

category 01 accidentseverityb

a Data are taken from "Draft Environmental Statement on the Transportationof Radioactive Material by Air and Other Modes" ( 1). b Categories of accidentseverity are defined in terms of increasing crush and force and duration of fire(1).

suitable for estimating spill probabilities of other chemicalmaterials. According to the second model, spills of hazardousmaterials are not expected in the first or lowest category ofaccident severity (Table V). Since this category represents 50%of all freight-car accidents and 55% of all truck accidents,probabilities of transportation-related spills of raw materialsand final products transported by freight cars and trucks are,respectively, 0.50X and 0.45X probabilities of accidents. Spillprobabilities generated by use of USNRC's second modelcorrelate reasonably well with probabilities obtained byextrapolating spill percentages for general classes of chemicalsto similar raw materials, final products, and hazardous wastes(Table IV).

Probabilities of transportation-related spills of cbemicalsassociated with operation of the hypothetical plant are pre-

2.4 X 10-6

2.4 X 10-6

2.5 X 10-6

2.4 X 10-6

2.7 X 10-6

2.5 X 10-6

1966

1967

1968

1969

1970

averageII Accident rates were obtained from data provided by the Bureau of Motor

Carrier S.fety (7).

accident rate for those years is likely to be representative ofpresent and future rates.

Percentages of transportation-related accidents that resulted in spills causing more than $100 in property damagein the United States during 1972 to 1976 are presented inTable IV for classes of chemicals exhibiting similar physicaland chemical properties as the raw materials and final products. Since accidents resulting in spills are more likely to bereported than accidents in which no spills occur, percentagesappearing in Table IV probably overestimate real spillfrequencies.

In an evaluation of radioactive materials, the U.S. NuclearRegulatory Commission (J) estimated spill probabilities forfreight-car and truck transportation by categories of accidentseverity. Estimates of spill probabilities were based on twoconceptual models. One model assumes that materials aretransported in special containers placed in freight cars andtrucks. Since these containers are more durable than containers used to transport nonradioactive materials, spillprobabilities generated by this model probably underestimatethe likelihood of spills of other, nonradioactive materials. Thesecond model assumes that radioactive materials are shippedin containers of limited durability and, therefore, it is more

Table IV. Percentages of Transportation-Related Accidents Resulting in Spills Causing More Than $100 inProperty Damage in the United States during 1972-1976, by Chemical Classes·

52.0

51.0

37.0

27.0

% accidents resulting Inspills causing>$100 prop.

damagechem for which

data apply

methyl mercaptan, isobutyraldehyde. acetaldehyde. product Acaustic solution

muriatic acid, product B, hazardous wastechlorine

mode oftransport.

tank cartank cartank trucktank car

class 01 chem

nonflammablecompressed gasII Analysis is based on Hazardous Material Incident Reports filed with Material Transportation Bureau (computer printout of reports was obtained from the Materials

Transportation Bureau. U.S. Department of Transportation). Only full tank cars and tank trucks were considered in the analysis.

flammable liquidcorrosive material

226 Environmental Science &Technology

Table VI. Probabilities of Transportation-Related Spills Involving Chemicals Associated with the Operation of aHypothetical Chemical Plant

spill probability

lile of plant (50 years)no. 01 spills

1-year boundingperiod, most probable no. interquartlle

transported chern mode of transport. 1 or more spills 1 or more spills 5 or more spills of spills range

raw materials

chlorine freight car 0.023 0.694 0007 0-2(tank car)

caustic solution freight car 0.086 0.989 0.463 5 3-6(tank car)

methyl mercaptan freight car 0.100 0.995 0.601 6 4-7(tank car)

isobutyraldehyde freight car 0.106 0.996 0.660 6 4-7(tank car)

acetaldehyde freight car 0.123 0.998 0.784 7 5-9(tank car)

muriatic acid truck 0.149 0.999 0.906 8 6-10(tank truck)

final productsproduct A freight car 0.022 0.675 0.006 0-2

(flammable liquid) (tank car)product B truck 0.107 0.996 0.667 6 4-7

(corrosive) (truck load)waste materials

hazardous waste truck 0.017 0.585 <0.001 0-2(corrosive) (truck load)

all materials combined 0.540 0.999 0.999 39 35-44

sented in Table VI. To demonstrate how estimates are obtained, consider the case of the raw material chlorine. Theparameter vL for 1 year is 48750 miles/year X (1.8 X 10-6

accident/mile) X (0.27 spill/accident) = 0.02369; vL for 50years is 50X the above, or 1.1846. So, in Table VI, the probability for one or more spills in 1 year is 1 - exp(0.02369) or0.02341. For 50 years, it is 1 - exp(1.1846), or 0.6491. For 50years, using Equation 2 and vL = 1.1846, the probabilities ofzero, one, two, three, and four spills are, respectively, 0.3059,0.3623,0.2146,0.0847, and 0.0251. So the probability of fiveor more spills of chlorine is 1 - 0.9926, or 0.0074. It is seen fromthe above probability estimates that one is the most probablenumber of spills.

During a I-year period, the probability of one or moretransportation-related spills associated with operating thehypothetical plant ranges from 1.7% for hazardous waste to14.9% in the case of the raw material muriatic acid. For allmaterials combined, there is a 54% chance that one or morespills will occur in a I-year period. During the expected life ofthe plant (50 years), the probability of one or more spills is58.5% for hazardous waste and increases to 99.9% for muriaticacid. The most probable number of spills of a raw materialranges from one for chlorine to eight for muriatic acid. For thefinal products A and B, the most probable number of spills isone and six, respectively, and, for hazardous waste, one spillis the most likely number. The interquartile range is used toindicate the number of spills that bound the middle 50% of theprobability curve. For individual chemical materials, the rangeis zero to two spills for chlorine, product A, and hazardouswaste. The range increases to six to ten spills for muriatic acid,and for all materials combined, the interquartile range is 35-44spills.

The spill recurrence intervals for chemicals associated withthe plant are presented in Table VII. To demonstrate howthese were calculated again consider the case of chlorine. FromEquation 5 the recurrence interval (R) for spills of chlorineis 1/0.02369 or 42.2 years. For raw materials, recurrence in-

Table VII. Recurrence Intervals for TransportationRelated Spills Involving Chemicals Associated withOperation of a Hypothetical Plant

spill recurrencetransported chern mode of transport. Interval, years

raw materialschlorine freight car 42.2

(tank car)caustic solution freight car 11.2

(tank car)methyl mercaptan freight car 9.5

(tank car)isobutyraldehyde freight car 8.9

(tank car)acetaldehyde freight car 7.6

(tank car)muriatic acid truck 6.2

(tank truck)

final productsproduct A freight car 44.5

(tank car)product B truck 8.8

(truck load)waste materials

hazardous waste truck 56.9(corrosive) (truck load)

all materials combined 1.3

tervals range from 6.2 years for muriatic acid to 42.2 years forchlorine. Recurrence intervals for products A and Bare 44.5and 8 years, respectively. A recurrence interval of 56.9 yearsis obtained for hazardous wastes. When all materials areconsidered together, a spill is expected to occur once every 1.3years.


Discussion

The approach outlined above provides a relatively simplemethod of arriving at estimates of spill probabilities. The essential features of the method include first determining accident rates for appropriate modes of transportation and,second, determining the fraction of accidents that results inspills. Spill probabilities are then estimated from equationsbased on the Poisson distribution.

Fractions of accidents that result in spills were estimatedfrom data provided in Spill Incident Reports filed with theMaterials Transportation Bureau. Reporting of spills ofhazardous materials to the Bureau was initiated in 1972 andrelatively few statistics have been obtained on spills of specificchemicals. For example, during 1974-1975, only 11 spills ofchlorine were reported. The relatively small data base for individual chemicals reflects both the short duration over whichthese statistics have been recorded as well as the general lackof knowledge regarding reporting of spills during the first fewyears following initiation of the reporting requirement.

To circumvent the problem of too small a data base for individual chemicals, data for whole classes of chemicals havingsimilar characteristics to the individual chemicals wereused.

Prior to 1977, data recorded by the Materials Transportation Bureau on spills of hazardous materials did not includeinformation on the volume of materials spilled. The magnitude of the spill could be judged only from the resulting costs.In the approach outlined in this paper, spills were considered"significant" when they resulted in damage and clean-up costsexceeding $100. This is a relatively low cost and using thisfigure as a criterion will overestimate the probabilities of spillsthat result in significant adverse environmental effects. Theproblem of judging the magnitude of a spill and its associatedimpacts from the cost of a spill will be alleviated in the futuresince the Materials Transportation Bureau has begun torecord additional details, including spill volumes, on reportedtransportation-related spills. As this data base develops, moreprecise and meaningful estimates of spill probabilities can be

NOTES

obtained.This paper provides an example of how the method may be

employed to estimate probabilities of spills associated withthe operation of an individual chemical plant. The methodalso could be applied to estimate probabilities of spills occurring in a particular region (e.g., state) or for a particularchemical (e.g., chlorine) transported throughout the country.Regional and chemical-specific information on the probabilities of transportation-related spills could be used to helpdesign hazardous materials spill prevention, countermeasure,and control plans.

Literature Cited

(1) U.S. Nuclear Regulatory Commission, Draft EnvironmentalStatement on the Transportation of Radioactive Materials by Airand Other Modes, U.S. NRC Office of Standards DevelopmentDocket No. PR-7I, 7:l (40 FR 2:1768), 1976.

(2) Slack, J. R., Smith, R. A., "An Oilspill Risk Analysis lor the SouthAtlantic Outer Continental Shelf Lease Area", U.S. GeologicalSurvey Open File Report 76-6,5:1, 1976.

(:J) Federal Railroad Administration Office of Safety, "AccidentBulletin-Summary and Analysis of Accidents on Railroads in theUnited States for Calendar Year 1972", U.S. Department ofTransportation, 1972.

(4) Federal Railroad Administration Office of Safety, "AccidentBulletin-Summary and Analysis of Accidents on Railroads in theUnited States for Calendar Year 1973", U.S. Department ofTransportation, 1973.

(5) Federal Railroad Administration Ofl'ice of Safety" "AccidentBulletin-Summary and Analysis of Accidents on Railroads in theUnited States for Calendar Year 1974", U.S. Department ofTransportation, 1974.

(6) Association of American Railroads, "Yearb<Xlk of Railroad FacLs",Economics and Finance Department, Association of AmericanRailroads, Washington, D.C., L.C. Card No. A66-7305, 1975.

(7) Bureau of Motor Carrier Safety, "1970 Accidents of Large MotorCarriers of Property", Federal Highway Administration, U.S. Department of Transportation, 1972.

(8) Clarke, R. K., Foley, J. T., Hartman, W. T., Larson, D. W.,"Severities of Transporlation-Related Accidents", Sandia Laboratory Report SLA-74-0001, 1976.

Received for review May /2, /978. Accepted September /8. /978.

On the Degradation of 2,3,7,8-Tetrachlorodibenzoparadioxin (TCDD) by Meansof a New Class of Chloroiodides

Claudio Bolre+. Adriana Memoli, and Franco Alhaique

Cattedra di Chimica Fisica, Centro di Chimica del Farmaco, Facolta di Farmacia, Universita di Roma, Rome, Italy

• A new method for the decomposition of2,3,7,8-tetrachlorodibenzoparadioxin (TCDD) and other substances containing ether bonds together with aromatic rings is describedin this note. The reaction requires the use of chloroiodidesobtained from different quaternary ammonium salt surfactants and does not need the presence of light. Experimentshave been realized with pure TCDD and with samples fromthe contaminated area of Seveso, Italy. A possible mechanismfor the observed reaction is discussed.

This work describes the cleavage of ethers by means of anew class of compounds in micellar solution. This group of


substances shows interesting application in the field ofpharmaceutical chemistry because of its antibacterial activityand at the same time is of interest because of its possible applications in the field of environmental sciences as inactivatingand decontaminating agents of toxic substances containingone or more ether groups in their molecules.

Although more detailed and complete data will be given ina forthcoming paper, great interest in the results obtained in2,3,7,8-tetrachlorodibenzoparadioxin (TCDD) (structure 1)degradation experiments, together with an urgent need fordecontamination techniques (1-6), prompted us to report onthis subject.

Molecular degradation of TCDD has been realized bymeans of chloroiodides (7-12) obtained from quaternary

00 13-936XI79/0913-0228$01.0010 © 1979 American Chemical Society

Oh lh 7h

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80

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Jv~ ~ t~j Y20

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~ 0 g 5i.< .<

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YY0X§Q 0 I "C~ ,I lei?

1 '--~! ~ Or: ' I~- 0 "~/

T'" (CH1 )'6

H,c ~ ·CHJ CHJ

R

II "'

ammonium salt surfactants, Among other derivatives, themost interesting and promising results have been obtainedwith alkyldimethylbenzylammonium (benzalkonium) cblnroiodide and 1-hexadecylpyridinium (cetylpyridinium)chloroiodide (structures II and III, respectively).

Experimental

All surfactants and reagents were of analytical grade. TCODwas a pure sample supplied by Rochester University, Rochester, N.Y. UV measurements were carried out with a PerkinElmer-Hitachi 200 spectrophotometer, using quartz cellshaving a path length of 10 mm. IR spectra were realized bymeans of a Perkin-Elmer 521 spectrophotometer.

Chloroiodides have been prepared by treating an aqueoussolution of each surfactant, containing a slight excess of iodine,with gaseous chlorine which was bubbled through the reaction

mixture for several hours. The products, obtained as yellowprecipitates, were slightly soluble in water and more solublein ethanol or metbanol, from whicb they have been crystallized(mp 80-82 °C for benzalkonium derivatives and 72-74 °C forcetylpyridinium chloroiodide). In both cases elementalanalysis was in accordance with the formulas shown instructures" and IlL (For benzalkonium chloroiodide, theratio between nitrogen, iodine, and chlorine has been considered.) The principal IR absorption peaks are at 700, 730,765, 1400, IIlOO, 2840,2910,2940,3020, and 3060 cm- l forbenzalkonium derivatives and 730, 695, 785,1480, 1491l, 1640,2880,2945, and :l080 cm- 1 for cetylpyridinium derivatives.

The low soluhilities in water of these new substances canbe increased by the use of micellar solutions, and the samesurfactants, used for the preparation of the chloroiodide derivatives, have been used for this purpose (i.e., benzalkoniumchloride was the solubilizing agent for benzalkonium chloroiodide, while cetylpyridinium chloride micelles solubilizedcetylpyridinium chloroiodide).

As far &S TCDD cleavage is concerned, the following experimental conditions have been used: 10 mL of a benzenesolution containing 10 I'g/mL of TCDO was vacuum evaporated and the residue was treated with 10 mL of a 0.1 M cationic surfactant aqueous solution containing 50 mg of chlof()iodide derivative. The test solutions were kept in a darkplace at room temperature and checked periodically for UV


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~ 8 ~ ~Figure 2. (a) UV spectrum of TeDD in a O. 1 M cetylpyridinium chloride soiution containing 0.5 % cetylpyridinium chloroiodide, at different times.(b) UV spectrum of xanthene in a 0.1 M benzalkonium chloride solution containing 0.5 % benzalkonium chloroiodide. at ditferent times

absorbance; appropriate blanks containing all reagents exceptTCDO were prepared as references. Results are reported inFigures 1 and 2a where it is possible to observe the variationof the spectrum as a function of time: the maximum relatedto TCOO decreases while decomposition products appear.Several substances are formed from the decomposition ofTCOO, such as chlorophenols, phenols, and 2-phenoxychlo«,phenols, whose compositions have not yet been determined.

In order to verify, hy means of another analytical method,TCOO decomposition by treatment with chloroiodides, asample solution, prepared as described above, was diluted,after 24 13, with 50 mL of water and then extracted six timeswith 60-mL portions of methylene chloride. The organicphases were collected together and evaporated under reducedpressure; the residue was then tested for a quantitative determination of TCOO by means of the method propo ed byCamoni's research team (/3). An LKB 9008 instrument wasused for this purpose. When benzalkonium chloroiodide inbenzalkonium micelles was used as reagent, it was found that71% ofTCOO was decomposed, and an even higher yield forsuch decomposition reaction (92%) was reached when cetylpyridinium chloroiodide in cetylpyridinium chloride was used.


These dat.a have been obtained by means of mass spectrometry measurements.

Experiments for TCOO de/(radat.ion have also been att.empted with soil samples from the contaminated area ofSeveso, Italy. Two different effects must be considered in thiscase: t.he solubilizing propert.ies of surfactant micelles l",wardTCDO, previously described (/4), and the decomposit.ionreaction related to the presence of chloroiodide. In order toverify the peculiar properties of test.ed chloroiodides, appropriate blanks have been prepared by treatment of tbe soil witba solution cont.aining surfactant micelles witbout chloroiodides. Preliminary result.s, obtained with IOO-g soil samplescontainin/( an average amount 01'23 /-Ig ofTCOO, showed tbat19.8/-1g ofTCOO was still present after treatment for 24 h with100 mL of a 0.05 M benzalkonium cbloride solution as solubilizin/( agent (14), while only 11.0 /-I/( has been detected when0.2% benzalkonium chloroiodide was added to the micellarsolution. Therefore, although a lower yield has been obtainedif compared with t.he experiments obtained with pure TCDD,as could he expected because of the presence of many othersubstances besides TCOO in soil samples, the loss of :18% ofTCOD can be ascribed t.o t.he decomposition reaction catalyzed by benzalkonium chloroiodide.

It is interesting- to point out that the same reaction has beenrealized using otber substances containing ether /{roups andstructural similarities to TCDD, such as xanthene and benzofuran. Results with xanthene are reported in Fig-ure 2bwhere the disappearance of xanthene absorption maximumis evident. (The maximum related to tbe benzene ring- due todecomposition of xanthene is hidden by the backg-round andthe absorption of benzalkonium chloride.)

Dis(,U.'isi(}f7

We may conclude that tbe observed micellar catalysis canbe applied in many cases in which the cleavage of an etberlinkage is needed; furthermore, such a reaction can be realizedwithout the direct use of hydrog-en iodide in strong-Iy acidicsolutions, at room temperature, in aqueous media, andwithout irradiation (/4, 15), which makes it more feasible fordeC(lnt.aminatillll pnlcesses.

[n our experi mental wnd itions II-II interactions betweenthe aromatic moiety of sufactants and benzene ring-s of testedethers can be assumed; this is further supported by the facttbat the use of surfactants without aromatic ring- syst.ems intheir molecule leads to no appreciable decomposition ofet.hers. We may tberefore presume that hydrog-en iodide,which sJowly solubilized within micelles from chloroiodides,finds TCDD nearby or otber aromatic ether molecules arrang-cd in an appropriate way so that the cleavage takes placein an easier and faster way related to such specific interaction.In fact, a worthwhile feature of this micellar interaction is an

increase in i(ldide Cllilcenl rat ion alld a parallel det:ft'dse ()f l,t>pH unit values. 1- cOllcentratioll, \'dli<:h changed from 1U 1"0

to 10-:1 M, was checked by means of a poknt iomd ril' met hodusing an Orion selertivt' eh... t:ll"ode. Thel't'fort', thl' IIH:·dlallislll

of the cleavage of ether bonds by lIll'ans uf l'hlol'Ullldides canbe assimilated to tlw well-known'JIIe whil'h direl'lly involvesbydrogen iodide.

I,i/cralurl' Cited

(I) Kearney, P.l ' .. Woolstlll. E. A., ISl"lI:-.et:. A. 1<.. Ht:llillg.l . :-; .. f:flV.Health. 1'l'1..... p.. a, :!I;~ II~rj:~J.

(1) Grihhll"'. (;. \V .. (·!tt'l1Ii .... /n· . .t7, 1;-) {l~r;.l,l.

(:0 Hav, A.. NC/Illf'f' (I,tlm/uri l. :!ti:!, tj:tli (IVitil.(4) Hay, A., ibid., 21i7, :IX4 11~771.(fl) Ha~'. A., ibid., 24iX, :~~);-) (ID771.(()) Walsh,.!..S.-i"".-", t!J7,lllli4ll~i7J.

17) Filhol, .J., J. 1'1/(/,.11I., 2,;, .1:\" II ~:I!JI.

IH) Wells, Weeler, I'etlfield. A,,1. J Sci., H, ·L! (1"!J2l.I~) Wyekoff, H. W. (;.,-J. Alii. (,II"", S"e. ~2, IIUU II!J2UI.(iO) Mooney. H. C.I... X. 1\·ri.... I(lfllJ~,.., ~JS. ;{~·I (IV:fi').(t J) Mtloney. H.C. 1... ibid., !IX, :\7, (l~:m.(12) Corwell. C. I)., Yamasaki, H. S.. J (,11 .. ,,<. 1'11.1'-' .. 27, IUtiO

(1957).(l:H Camoni. l..Di Mun'io, A.. J!ulIlt:COr\'H. I),. Vt'rguri. I. .J. ('hrcJ

mat of.Ir. , 15:J. ~;l;{ (IB7HI.(14) Hot.re. C., Memoli. A.. Alhaique. F.. 1',;11/'/1'11/1. :,:it:i. 'I'n:Juwl.. 12,

;l;{[) (19tH); tl.S. Patent Pl:nding No. ti:tV;-)~ti t;wup Arll 1nit ~Uh,

Aug :n, 1977.(If,) Croshy. D. (;., Wong. A. S.. I-'Iinllllt:r, .1. H.. \VtJ\,bllll. K A.,

S ..iffICe, L7:1,748 ( I~i1 l.

Re('cived for rl!uil!lC Murch I:J. IV7H. /\ct't'/Jll'd Au~{(.... l 8. IY7K.

A Comparison of Time and Time-Weather Models for Predicting ParathionDisappearance under California C~nditions

Herbert N. Nigg* and Jon C. Allen

University of Florida, Institute of Food and Agricultural Sciences, Agricultural Research and Education Center, P.O. Box 1088,Lake Alfred, Fla. 33850

• Time and time-weather models for predicting parathiondisappearance on California Valencia foliage were compared.The time-based first-order disappearance model explained67% of tbe residue data variation for 7 dilute application experiments and !);)tUJ of the residue data variation for 7 !owvolume experiment.s. The time-weatber first-order disappearance model considerably improved predictive accuracyt.o 8:1% for both experimental series. Utilization of pesticidedisappearance models which incorporate weather conditionsis suggested for harvest-t.ime and worker reentry regulationsand for reducing dependence on environmental monitoringst.udies.

The health hazard posed hy residues of organophosphorothionate parathion (O,CI-diethyl ()-p-nitrophenyl phosphorothionate) to ag-ricult.ural field workers who enter treatedfields bas received wide attention (I). The major source ofintoxicant. appears 1.0 be the dislodgeable foliar residuessorbed to particulate maUer, primarily dust, on the leaf surface. Field workers are wrrently protected from acut.e exposure to organopbosphorus residues by regulations wbich denyreent.ry into treated fields or g-roves until a specific time interval after pesticide application has elapsed. However, t.beselargely toxicologically based reg-ulations bave not been completely successful in the central valley of California (2) andthis lack of success remains unexplained. Beyond more

0013-936XI79/0913-0231$01.00/0 © 1979 American Chemical Society

stringent regulatioll$, three approaches 10 l·irnlillvelll addit.ional worker illnesses have heen suggested. \V(Jl"kt.~r 1"l't'1l1I'y

regulations det.ermined h.v mat hemal it:allllodelillg bi:l:,ed 011

the known toxil'o!ogy and envil'ollmt.~f1ti:t1 hdli:t\'jUI' of orgaIlophosphorus insediddes have beL'1l slIggt:sleu (:; 6). A J't.

cent report stresses fit'ld monittll'ing with purtable equipllll'1l1for actual residue levels hefore worker rteotr.\' ((;). A thirdapproach utilizes the predil:lioll of pe:->t it:idl:' len' Is Hli h-afsurfaces t.hrough the USt:' of \vealhl'r IlhldeJ:-. \If pt':-.ticidl· ht·havior (7, X).

The purpose of lhis sl ud)! was 10 dl'tl'l'Il1ille if the di:-.appearance of parathion frtllll ('alifol'llia Ol'ilJlgt- l"oJiagl' l'uuJd beaccurately descrihed with a first ·ordt'r Illodd l'llIpl".\·illg aweather-dl'pendent rale nJellicient.

f;xperimenta/

Experimental design, applicatioll rllctiludtllog~·.:-.aJllplillg,analytical meth(Jd()log.v~and the residue data !I,H'l' bel'lI previollsly report.ed (/). The first-ordt·1' wt.:'atht:1' t!l:l.t\ Illudd.staUstin;, heating-dt'grt.>e·day t l'allsflJl'lllalioll. iJlld nlll!JJutel'

programs have also heen previou:-.ly I'eported (7. tI).

Ihscu ........ioH

The y,'par-round cmpirit·allHodt·l:-; i1lu:-.tl'attd in Figun.:s 1and ~ show that th~ liSt:' of a tilllt, \\"t':ltI1l:'1' lllt/dd til I>l':-.t il'id~rli!;appearanre for (~aliforllia parat ilion data illlpl't/\'ed the It:!.values nJnsiderably. FllJ' b"lb the dilut" ;lppli,·"li. '" ( I'Ll) kl.

Volume 13. Number 2. t-ebludry 1~7~ 231

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Table I. Matrix of Individual Correlations betweenParathion Concentrated Application 8 and CumulativeEnvironmental Variables

cumulative rainfall,In.

cumulative time,days

-0.821 b

0.985

1.00

1.000 -0.755 b

1.000

-0.099

0.456

0.434

1.000

a 11.2 kg of active ingredientlha in 15.0 kllha. b P < 0.01.

healingparalhion degree days

Table II. Matrix of Individual Correlations betweenParathion Dilute Application 8 and CumulativeEnvironmental Variablescumulalive rainfall.

in.cumulative time.

days

-0.743 b

0.985

1.000

-0.668 b

1.000

1.000 0.063

0.456

0.434

1.000

a 11.2 kg of active ingredient/ha in 0.93 kLlha. b P < 0.01.

heatingparathion degree days

of diluent/ha) and the low·volume application (0.93 kL ofdiluentlha), 83% of the variation observed was correlated withthe time-weather data. For the 15.0 and 0.93 kL/ha applica·tions, time alone explained only 67 and 55% of the residue datavariation, respectively. These results are very similar to thepreviously described Florida citrus foliage ethion residuedisappearance model where 94% of the variation was explainedby the time-weather model and 57% by time alone (7), and theFlorida citrus foliage models for parathion where 90% of thevariation was explained by the time-weather model and 30%by time alone, and for carbophenothion, where 93% of thevariation was explained by the time-weather model and 47%by time alone (8).

These data analyses for California parathion data illustrateseveral additional important considerations in using weatherplus time to predict pesticide disappearance. Time was themost highly correlated individual variable (Tables [ and II)with California data, whereas in Florida, rainfall, air tern·

perature, and solar radiation were generally the most highlycorrelated variables. This supports the supposition of Nigget al. (9) that time would probably be the most importantenvironmental parameter in an empirical weather modelunder stable weather conditions. It was difficult to correlateCalifornia pesticide disappearance to cumulative rainfall dueto the lack of any significant amount of rainfall. It should benoted, however, that individual correlations with rainfall were+0.063 and -0.099 (Tables [ and II), suggesting no effect onpesticide disappearance. The sign of the coefficients is positivefor hoth rainfall and heating-degree·days in the multiplecorrelation equations (Figures 1 and 2). This can lead to apredicted increase in pesticide residue under certain weatherconditions. For the October 1974 data, with 2 in. of rainfall,an increase was in fact predicted, but a decrease occurred. Apossible solution to this problem in modeling pesticide dis-


Table III. Time Model Half-lives of Parathion onCalifornia Orange Leaves

11.2 kg of active ingredienl/hadilute application coned application

expl slope T1I2. a days R slope 1112. days '---,,--1 -0.13 5.3 -0.97 -0.08 8.7 -0.98

2 -0.11 6.3 -0.97 -0.10 6.9 -0.98

3 -0.07 9.9 -0.87 -0.06 11.6 -0.96

4 -0.04 17.3 -0.86 -0.06 11.6 -0.98

5 -0.09 7.7 -0.96 -0.10 6.9 -0.99

6 -0.12 5.8 -0.91 -0.09 7.7 -0.96

7 -0.11 6.3 -0.91 -0.06 11.6 -0.83

X -0.095 7.3 -0.078 8.9

a T1I2 = O.693/sI0pe.

appearance has been suggested (9). Theoretical pesticidedisappearance models incorporating hoth chemical parameters and environmental parameters would also circumvent thisinaccuracy.

The variation in half-li\'es of parat.hion on California orangeleaves illust.rat.es the possible inaccuracy of a time-basedmodel (Table III). The current approach sets tolerances basedon a monitoring study at harvest time. If the factors affectingpesticide disappearance change in a suhsequent year, residuelevels may be out of tolerance. This inaccuracy of the timemodel has been partially circumvented by Cunther et al. (I)with a split-time model which describes the init.ial rapid lossof pesticide as "disappearance" bebavior and the slowersubsequent residue loss as "persistence" behavior (J). Thispractice has not been accepted for tbe purpose of setting tolerances, and it is of little general predictive value for use inmodel development.

Tbe time and time-weatber estimates of organopbosphateresidue behavior presented here represent the combinationof seven separate experiments. This approach seeks to accurately predict pesticide levels under any set of weather conditions. Although the weather transformation of the firstorder rate equation was accurate for Florida experiments,these California data illustrate possible inaccuracies inapplying this model. The California weather-time modelsuffers from a lack of variation in t.emperat.ure and rainfall.Thus, another physical factor either separate from or confounded wit.h t.emperat.ure and rainfall may account for thevariation in half-lives between experiments (Table Ill).

Bot.h the time and time-weat.her models sbow some init.ialinaccuracy (note point spread in figures). This inaccuracy hasbeen previously noted (3) and is probably due to vaporization,leaf penetration, runoff, and other short-t.erm processes.Models of organophosphate disappearance from leaf surfaces

may ultimately include explicit vaporization and hydrolysismodels as well as weat.ber variables.

Regardless of tbe predictive model used, its utilizationshould he simple t.o apply without higher mathematics andit should he field t.est.ed. Once field testing is completed, utilization of pesticide disappearance models should improvepest management decisions, barvest-time regulations, andworker safety reentry regulations and should reduce thecurrent dependence on expensive and endless monitoringstudies.

The data presented show that an empirical time-weatherpredictive model of California pesticide disappearance wasabout twice as accurate as time alone. Pesticide disappearancemodels which utilize the physical factors causing pesticidedisappearance could he put into practice by requiring theaccumulation of rainfall, average temperature, or a combinatiun uf rainfall and temperature data, and in some cases,time, before reentering pesticide-treated fields. The adoptionof field-tested weather models of pesticide disappearancewould be more reliable than the current regulations used inprotecting field workers reentering pesticide-treated cropsand would take into consideration variations in pesticidedisappearance due to regional climatic differences.

Acknuwledgments

Residue data and critical comments were provided by Drs.Y. Iwata, F. A. Gunther, and C. A. Smith, University ofCalifornia, Riverside. The technical assistance of J. Towne andS. Wells is acknowledged.

Literature Cited

(I) (;unther, F. A., Iwata, Y., Carman, G. E., Smith, C. A., ResidueRec'.. 67, 1-I:J9 (1977).

(2) Knaak ..J., Calif. Department or Food and Agriculture, personal('ommunicalion, 1977.

(:\1 Serat, W. F., Arch. Environ. Conlam. Toxic,,! .. I, 170-81I L97:\I.

(41 Serat, W. F., Hailey,.J. B.. Rull. Envirvn. ('ontam. Toxie"I.. 12,682-86 (1974).

1',) Serat. W. F., Arch. Environ. Contam. Toxicol., 7, 1 (1978).16) Smith. C. A.. Gunther. F. A., Adams, J. D., Bull. Environ. Contam.

Toxicol.. 15, :l05-10 (1976).17) Nigg, H. N., Allen, .J. C., Brooks, Ii. F., Edwards, G. J., Thompson,

N. 1'., King, It W., Blagg, A. H., Areh. Environ. Cuntam. Toxicol.,6,257-67 11977).

(8) Nigg. H. N., Allen,.J. C., King, ll. W., Thompson, N. P., Edwards,G../.. Hruoks, R. F., Hull. Environ. Contam. Toxico/.. 19, ;>78-88119781-

(9) Nigg, H. N., Allen../. C., Hraoks, Ii. F., Proc.lnt. Soc. Citricult ..2, in pres,; 119781.

lIe...·ioed for revi,'''' May 22. 1978. Accepted AUllust 25. 1978. Thispaprr i.'i Flurida AJ,!ric.:ultural Experiment Station,.; Journal SeriesNo. 12(J~. Supported in part by special funds from the Center forEnvirullmelltall'rograms, Univer..,ity of Florida, Gainesviflp. Fla.,and EPA (;rant No. 8MIiJJ020.


CORRESPONDENCE

SIR: Let me offer a few comments on the recent note hyLonneman, Seila, and Rufalini (I) concernin~ the import.anceof terpene emissions from vegetation in the generation ofamhient ozone levels. Air samples were collected in twoFlorida oran~e groves at ahout noon in May 1976. While cit.rustrees have heen shown to emit various monoterpenes (CI(jH II;)

at this time of year (2-4), GC analyses conducted 4-,5 daysafter sample collection failed to detect any CI(j terpenes. Theauthors have thus concluded that "the amount of naturallyemitted hydrocarbon is low" and that "these low levels cannot.possibly contrihute to the production of significant levels ofozone" in the area studied.

The data presented hy these authors do not provide strongsupport for either of these two conclusions. When dealing witha photochemically ~enerated pollutant such as ozone, amhientprecursor concentrations do not provide a good index of eithermass emis ions or relative importance among precursorsources. This fact is easy to overlook, since most smogchamber studies have been batch reaction systems. [n suchsystems, the amounts of reactants can be expressed on eithera concentration or a mass basis. It is the mass of reactantinjected into these systems which determines the initial concentration. The basic nature of photochemical ozone ~en

eration adds further insight. In the critical reaction process,organic compounds function as NO oxidizing agents througha chain reactiun sequence of hydrocarbon oxidation andfree-radical formation, while NO is involved in a cyclic oxidation-photodissociation sequence. Thus, the practice ofdescribing hatch reaction smog chamber studies in terms ofinitial reactant concentrations obscures the essential significance of hydrocarbon mass emissions.

Real world smog systems involve essentially continuousreactant injection. In such real atmospheres, low amhientconcentrations of a precursor compound could indicate eitherwell-diffused emissions from isolated, high concentrationpoint sources; cumulatively high mass emissions from widespread but individually minor emission sources; or high reaction rates regardless of source concentration. Thus, thestudy described by Lonneman et al. must he evaluated interms of two interrelated hut distinct issues: whether a si~

nificant ambient C IIl terpene concentration should have beenexpected in the first place, and whether natural terpenecompounds playa significant role in atmospheric photochemical reactions.

[ have approached the issue of expected ambient terpeneconcentrations by using the following simple spherical volume,steady-state model derived by analogy to the traditionalsimple box model:

terpene emission rate X canopy diamcanopy concn =

. canopy vol X wind speed

In May 1977, Zimmerman (2,3) measured a terpene emissionrate for Florida orange trees of 3.1I'g/(g·h) on a foliage dryweight hasis. Since no data on tree size were reported hyLonneman et aI., I have used data from some California citrustrees (5). A 29-year-old orange tree (4.72 m tall, with a trunkdiameter 01'27.2 cm) had a crown circumference of1,s.7 m anda foliage biomass of ahout 450 kg (fresh weight). Data fromthree 10-year-old orange trees indicated that foliage drywei~ht averaged 50% of foliage fresh weight.

Figure I illustrates expected steady-state canopy terpeneconcentrations for this 29-year-old orange tree as a functionof wind speed. Inherent model assumptions are a uniformlaminar wind flow, free air movement through the canopy,"clean" air unaffected by upwind trees, and no chemical re-


actions. A terpene molecular weight of 1:16.24 and a temperature 01'25 °C are also assumed. Fi~ure 1 indicates that windspeeds over 2.7 m per s (;'.2 miles per h) would produce acanopy terpene concentration of less than I pph 111.:34 ppbC(parts per billion of carbon) I. Lonneman et al. do not reportany wind speed measurements. They do note that sampleswere taken ouL,ide the tree canopy (a few inches to 10 ft fromthe (.rees) at noon on a day when the mixing depth was greaterthan 2000 m. All of the key assumptions inherent. in my simplemodel are violated by real world conditions. It. seems mostreasonable to me that the model overestimates t.he ambientterpene concentration expected in the collected air samples.

The aut.hors note t.hat ambient ozone levels at the time ofsample collection were about 45 ppb. They also note that 50%pump losses of ozone were experienced. Tests with knownterpene samples (5-25 ppbC) indicated no pump losses andexcellent stora~e characteristics. Test conditions are not explained in much detail. It would have been quite informativeif additional terpene storage tests had been conducted usingan air plus 20-25 pphO" mixture to simulat.e actual samplestora~e conditions.

As reco~nized hy the authors, monoterpenes react rapidlywith ozone under both light and dark conditions (6-9). Rateconstants for terpene-ozone reactions have been reported insome studies (8, 9). Those presented in ref 9 were used byLonneman et al. to estimate potent.ial terpene storage lossesfrom reaction with ozone. These rate constants were determined from flow system experiments havin~ reaction timesran~ing from 4 s to 4.5 min. Reaction rates determined in bo~h

refS and 9 were based on systems having terpene concentrations si~nificantly in excess of ozone concentrations. This iscertainly not the expected condition for the air samples analyzed hy Lonneman et al. [t is also noteworthy that, wheredeterminations could he made by Grimsrud et al. (9), terpeneto ozone loss ratios ranged from 0.47 to 1.5; loss ratios of 0.7to 1.4 were reported for myrcene, limonene, and If-pinene.

Thus, with an initial ozone concentration of 20 times theexpected terpene concentration, I am not surprised by thefailure of I,onneman etal. to detect any Cit> terpenes after 4-5days of sample stora~e.

The si~nificanceof terpenes to photochemical smog reactions can hest he jud~ed by their contribution to the reactiveor~anic emission inventory for an appropriate geographic area.Zimmerman (2,3) has estimated that terpenes from naturalvegetation account for 68% of t.he total reactive organicemissions in the St. Petersburg-Tampa area. While availableemission inventory data for that area need significant refinement, this estimate clearly indicates that t.erpenes are amajor hydrocarhon source in the area studied by Lonnemanet al. Terpenes are highly reactive with ozone, as previouslymentioned. These chain and cyclic olefins are also hi~hly readive in the typical photochemical system (7-/5), hein~ someof the most reactive compounds yet tested. It should also benoted that the ozone-terpene reaction can lead to free-radicalformation, either directly or by photodissociation of resultantaldehydes and ketones (16). Thus, even the daytime scavengin~ of ozone hy terpenes can lead to suhsequent downwindozone generation. All thin~s considered, Zimmerman's terpeneemission estimates seem easy to reconcile with low ambienlterpene concentrations.

One final factor needs to be reco~nized in assessing thesignificance of terpenes to photochemical smog reactions.These reactions will not proceed unless 0 or NO~ sourcesare also present. While I have not fully investi~ated the lit-

00 13-936XI79/0913-0234$OI.0010 © 1979 American Chemical Society

Literature Cited

Jones & Slokes Associates, Inc.2321 P StreetSacramento, Calif. 95816

Robert D. Sculley

SIR: Lonneman et al. (I) recently presented data concerning the abundance of natural hydrocarbons in the Floridaat.mosphere and advanced the conclusion t.hat natural sourcesare not significant. Our review of this paper indicates lhat.hecause of limitations in their sampling, storage, and analytical systems, this conclusion is not justified and furtherwork is required to determine the t.rue abundance of naturalemissions.

Contrary to the authors' reasoning as to why terpenes andother natural organic compounds were not detected in thefield samples, our calculations indicate that because t.hesecompounds are not stable under the condit.ions imposed bythe samplin~and slorage system, substantial concentrationscould have existed in the ambient atmosphere. The sampleswhich best indicate such storage loss are those taken in theorange grove, samples C-2 and G-:l. Based on the authors'assumption that the emissions in the orange grove shouldinclude the volatile constituents of orange oil Icomposit.ion>97% d-limonene, 1-:l% myrcene, and a trace of ,,-pinene (2,:1)) one would expect to lind d-limonene and possibly myrcenein the samples. However, calculations of the d ·limonene andmyrcene storage loss in the Tedlar bags in the same manneras used hy the authors for ,,-pinene show that in the 5 h allotted for reaction with ozone, 98.7% of the d·limonene and99.98% of the myrcene would have been destroyed. Thesecalculations are based on ozonolysis rate constants of 0.016and 0.031 ppm- 1S-I for d-limonene and myrcene, respectively(4).

Obviously, there is a very high probability that these import.ant terpenes were completely destroyed by storage in theTedlar bag-s and were never delivered to the GLC for analysis.Our calculations also show that the initial bag concentrationsof these terpenes could have been as high as 77 ppbC (partsper hill ion or carbon) d -limonene and 90 ppbC myrcene.Considering that substantial losses of these terpenes wouldalso be expected durin~ sampling when ozone was also present,it is evident that very high ambient concentrations or theseterpenes could have existed.

Another prohlem with the storage loss position taken hy theauthors is the fact that no data were presented for the terpenelaboratory storage test. Based on the ozonolysis rate given, itis assumed that ,,-pinene was used in this test. Ripperton,Jeffries, and White (5) have reported that ,,·pinene reactsmuch faster with ozone than calculated by the first-order kinetics used by the authors. Ripperton and co·workers postu·

(9) Crimsrud, Eo P., Westberg, H. H., Rasmussen, R. A., lilt. J. Chem.Killel., Symp, No. I, 18:l-9;; (1975).

(l0) Went, 1'. W., Pro('. Noll. Amd. Sti. U.S.A., 51, 1259-67(l964).

(11) Went. F. W.. Slemmons, D. H.. Mozingu, H. N., Pme. NaIl. Acad.S6. USA .. 5K, 69-74 (1967).

{l21 Hil,p,rton, L. A., .Jeffries, H. E., Worlh,.J. H.. EIIl'irull. S6.T"d",,,/., 5,246-8 (1971).

(I:lj Lillian, D., Ad". Chem. Ser.. No. 113, 211-18 (19n).(14) Stephens, Eo H., Price, M. A., in "Aerosols and Atmospheric

Chemistry", G. M. Hidy. Ed.. Pll 167-81, Academic Press, NewYork. N.Y., 1972.

(1,,1 PiUs,.1. N., Winer, A. M., Da","II, K H., L1uyd, A. C., Doyle, G..J .. in "International Conference Oil Photochemical Oxidant Pol·lutioll and Its Control, Proceedings", R. Dimitriades, J1:d" Vol. It,Pil 687 -70·1, EPA 600/:1-77·00Ib, 1977.

(H)) Haagen-Smil, A. tJ., Wayne, L. G., ill"Air Pollution'\ A. C. Stern,Ed., :lrd ed, Vul. I, PI' 2:15-88, Academic Press, New Yurk, N.Y.,1976.

10O+---,----r-,---r-..,----r-,----,----r-r

o 23456789

WINO SPEEO, METERS PER SECOND

Figure 1. Effect of wind speed on expected canopy concentration 01monoterpenes

30

(J) LOlllleman. W. A., Seila. R. L., Bufalini, .J. J., Ellviron. Sci.,/,,'('hllo/., 12,4;;9-6:\ (1H78).

(2) Zimmerman, P.. "Pwn"dllres for Conclucting HydrocarhonEmission Inventories of Bio/.{enic Sources and Some Results ofRecent Investigatiuns", presentf'd at EPA Emission Inventory/I'aclor Worksholl, Ralei~h. N.C., :;eplI977.

(:1) Zimmerman, P., "T'he Determination of Hiog:enir HydrocarbonEmissions", presented at Pacific Nort.hwestern InternationalSection. Air Pollution Control Association MCE'ting:, Nov 1977.

(4) Zimmerman. P., Air Pollution Research Section, Wa~hingt()n

State University, Pullman, Wagh., private communication.(5) Turrell, F. M.. Carber. M..J., .Jones, W. W., CCH'll"r, W. C., YounK.

It H.. Hi/Kardia. 39,428-45 (1969).(6) Wenl, F. W., Pm('. Natl. Acad. Sci. US.A., 46, 2l2-21 (1969).(7) Groblicki, P. J .. Nehel, G..1., in "Chemical Reaclions in Urban

Atmospheres", C. S. Tuesday, Ed., Ill' 241-67, American Elsevier,New York, N.Y., 1971.

(8) Ripperton, L. A., ,Jeffries, H. Eo, Wbile, 0., Adv. ('hem. Ser., No.113,219-:n (1972).

erature on natural NO and NOz sources, I remain skepticalof their significance for two simple reasons. Natural hack·ground ozone levels, while suhject to argument as to sources,are clearly low. There is also abundant evidence of visihle in·jury to vegetation produced by relatively low ozone levels.Thus, I can only conclude that photochemical smog is clearlya product of modern technology. In this rel(ard. the NO andN02 produced by combustion processes may he at least asimportant as hydrocarhon emissions from anthropog-enicsources. I would also conclude that while terpene emissionscan be a significant hydrocarbon source (and need to he reco~ni7.ed when formulating- smog control strategies), this doesnot in any way mean they are "the cause" of observed smoglevels.

25

z0CD0:

'"UcD 20a.a.

i0

>='"0:t- 15z<oJUZ0U

<oJZ

10<oJa.0:<oJt-

0013-936X/79/0913-0235$Ol.00/0 © 1979 American Chemical Society Volume 13. Number 2, February 1979 235

~~-~---_._-~---------

Table I. Volatiles from Oranges. Reprinted with Permission from Journal of Food Science (29 (6), 790-5(1964»; Copyright 1964 by Institute of Food Technologists

Kenneth H. LudlumBruce S. Bailey

Literallire Cikd

(II Lonneman, W. A., Seila, H. L.. Bul'alini, .J. .J., Environ. Sri.'/hhnol., 12, 4[,9-~6:1 (1978),

(2) Kirk-Othmer. "Encyclupedia of Chemical Technology", 2nd ed.Vol. l4, W;ley, New York, N.Y., 1967.

(:1) Swisher, H. Eo, IJrul! ('osmel. Ind., 90(4).41;' (1962),(4) Coffey, P. K, Westberg, H. , "International Conference on Oxi

danlS 197H-Analysis of Evidence and Viewprinl.s. Part IV. Issueof Natural Organi" Emission'-·. Heport EPA 600/:1~77~IIH, Research Triangle Park, N.C~. Oct 1977.

(,,) Hipperl.on, L. A., .lelTries, H. Eo, White, 0., Adl'. Chem. Ser.. No.11:1(1972),

(6) Polasek, .J. C., Bullin, .1. A., /'nl'iron. S"i. 'l'I'"hno/.. 12(()),708(1978),

(7) Denyszyn, H. B., Hardison, D. 1", Harden..1. M., McCau!(hey, ,I.F. t Sykes, A. L. t "gvaluatioll of Various Hydrocarbon SamplingDevices", presented at NBS Symposium (Hl Trace Or~anicAnalysis,Gaithershurg, Md., April 10-1:1. H178.

(81 Schultz, T. H.. Teraniski. R., McFadden, W. H., Kilpatrick, P.W., Corse,.I..J. Food S"i., 29,790 (1964),

(9) Zimmerman, P.. "Procedures for Conducting Hydrocarbon~:mission Inventories of Hiogenic Sources and Some Results ofReeent Investigations", Washington State University Report toEPA ~;l11ission Invent.ory/Factor Workshop, Haleigh, N.C.. Sept1:1-1;'.1977.

SIR: The correspondence of Sculley a!(rees in general wit.hthe conclusions made in our paper (Envi.ron. Sci. Technol.,12,4;;9 (1978)). Alt.hough usin!( a different approach, Sculley

Environmental Protection DepartmentTexaco Inc.P.O. Box 509Beacon, N.Y. 12508

C III hydrocarbons. Tahle I (from ref. 8) lists over 30 compounds which might he expected to be present in the orange!(rove amhient samples and which would be expected to exhibit. si!(nificant loss in ext.ended Tedlar bag storage. In ad~

dition to t.hese compounds, oxygenat.ed and ot.her compoundsformed by the at.mospheric reactions of t.he directly emitt.ednatural hydrocarbons would also be expected not. to st.ore wellin Tedlar bags. Relat.ed t.o t.his is the quest.ion as to whethert.he GLC system used by t.he authors was calibrated t.o detectt.he higher molecular weight. oxygenat.ed compounds such asare shown in Table I. Since only C" and C" oxygenates areincluded in the analytical listings shown in t.he Lonnemanpaper, it. is assumed t.hat the analysis of these higher molecularweight. compounds was not attempt.ed.

In summary, our calculat.ions and t.he work of ot.hers showthat. t.he results presented by Lonneman are consistent wit.huse of a sampling and storage syst.em in which large losses ofnat.ural emissions and t.heir at.mospheric reaction productswould be expected~ To det.ermine t.he ext.ent of t.hese emissionsrequires a sampling/st.orage/analytical system which willhandle not only t.he react.ive hydrocarbons and oxygenat.eswhich are directly emitted from nat.ural sources, but also thevolatile atmospheric reaction products of these compoundsas well. This is a complex and difficult problem which requiresmore sophisticat.ed and advanced techniques than have yetbeen developed and applied by t.he aut.hors. Until such techniques are developed and applied, t.he result.s presented byLonneman et. al. cannot be int.erpreted to indicate t.hat nat.uralemission sources are not significant.

In t.he meant.ime, the static/dynamic enclosure techniquedeveloped by Zimmerman (9) minimizes the sampling/storageloss prohlems associated wit.h ambient. sampling methods andappears to provide t.he most reliable emission data for trees,shrubs, and other nat.uralsources.

Carvone·

Nfl,thyl J-hydro!l.y-hcxililOillt··

~ /1'( Jrtanol "IP-l~opn)p(,llyll(1I11t'nt' b

Linalool h

Ethyl J-hydroxy-hexanoah'·Terpincn-4-ol"~ Ethyl octalloalt'''Ia.-lt'rpincol h

DCl"dna] h

(klyl acetate"Citronellol ..

F-' h'x('n~l-olII-Hl'xanol"o-Xy!t'lit'

~ Myrct'l1t' b

I Ethyl Ill'xalloate'Limoll!:ll(,"

Citral"P~rillald(:hyd~•

Biph~nyl f

Ethyl hUI,ulOa(e h

Ethyl h('IIZ('IlC'

p-Xylcllt' and/or IIl·Xyll'm··

3-Hexcn-J-ol"

42

29Jl

30

35

JR

401'

444751

52

,354,R59

601'606R

27l8Jl2'1

19A

I'tak

Hl'Il.l('!le·

Ethyl SlT·hutyl t'th('r·l'ydolh'xane •\ I,l-Dil.'thuxy ..:thallt'·14. Ml·thyl-l-pl'ntanont' •J.ll.tdhyl·l-hulanol"Toluene·II·llt·'(allal"

,..llc:.""'I1<: •Ethyl acetate"2· Mdhyl-J-butt'n-l-o)-

~'fl'lh<ln(' •

)"ldhyl dlluril!e':\n.t;lldl'hydr h

\ Ethanol h

IACt'lonc"

l>i('(h)'1 dh('T'

Ethyl furmate 4

7/\ tl·Bllt)'raldl·hyde·

p·j\h·thy l l't.'lltanc·

I Mdhyl (,lhyl ketone'

"/1' l-f'rop'Hlu\4

I!

IJ141\

9

10II

24!520

!J

I'uk

-----------• ~nurct' unknown. J)'t'rhal)S {rom solvmt uKd. to apply rnin to tht' fruit... f', tviously n:vortt'd as an orangt' volatile with identification hy

das!>iC"al or s~(tral mt'thods., Sol cllt used in prt"sent work.• l·rt· iuu~ly ~u ..a:est('d as an oranR~ ...olatile or tentati ...ely identified.• Nl,:wly found orange volatile., FUl\tti~lal frolll packaginR m._._te_r_;._I. _

Jat~d that a product from the reaction hetween a-pinene and"zon~ was r~reacting with a-pinene, as one of the steps whichleath, t" aerosol formation~ These investigators report that theratio "f "~pin~ne/O,,reacting varies from 2 to 5~,5 depend;ngUp"ll illil ial reactant concentrations. Since under the condi~

lions "f the field sample storage, the ozone concentration isprobably greater than that of the a~pinene,an enhanced lossof ,,-pinene over that calculated would be expected. Furthermore, other trace atmospheric constituents such as NO"SO,.. H"O, particulate matter, etc., may react with the ,,~

pinene (and other terpenes) and adversely affect storagestability~ Experiments to assess these possibilities are necessary before concluding that ,,~pineneand other terpenes arestable when stored in Tedlar bags for long periods.

A further Concern with the storage system is the expectedloss of oxygenated compounds arising from natural sourees,to the walls of the Tedlar hags during storage. While LonnellIan et al. show that Tedlar hags are strong sources for someof these compounds, viz. acetaldehyde and acetone, the hagswould be expected to be strong sinks for others. Polasek andHullin (6) have shown that carbon monoxide, stored in Tedlarbags, exhibits an average 42% loss in a 100-h period. This period of time is comparable to the 4 to 5 days that Lonnemanet al. stored their samples in Tedlar bags prior to analysis.More reactive oxygenated compounds would he expected toshow even greater storage loss. To further complicate matters,Denyszyn and co-workers (7) have indicated that Tedlar bagsare sources of significant concentrations (1-2 ppmC) of FlOresponsive species in the Cr, to C IO range. These authors havealso shown that ,,-pinene and (:I-pinene, at the 10-pphC level,stored in stainless steel containers, exhibit a 40% loss in 2 daysand a 100% loss in 1 week. They considered stainless steelcontainers superior to Tedlar bags for storage of most C" to

236 Environmental Science & Technology This arlicle not subject to U.S. Copyright. Published 1979 American Chemical Society

concludes that ambient concentrations of natural hydrocarbons are low and probably not the cause of high smog levels.We presume that when Sculley says "smog" he means ozone.The technique used by Sculley combined a simple diffusionmodel with natural hydrocarbon emission rate estimates (2)to predict ambient concentration of natural hydrocarbons. Wehave used similar techniques for a loblolly pine forest in NorthCarolina and have also concluded low downwind concentrations of ,,-pinene (3).

There were specific comments in Sculley's correspondencethat suggest a misunderstanding of our results and requireadditional comments. These comments include the long-termstorage of bag samples that contain mixtures of C IO terpenesand ozone, the reactivity of terpene hydrocarbons, i.e., theability of C IO terpenes to produce ozone, and the importanceof the oxygenated products of terpene ozonolysis in thedownwind formation of ozone.

The bag storage of terpene hydrocarbons in the presenceof 0" was discussed in detail in our paper (1). Loss of terpeneby ozonolysis was compensated for by the application of apseudo-first-order rate equation. It was also pointed out thatbag surface deposition of ozone competes with terpene ozonolysis in these stored samples. Complete loss of stored ozonein these small 10-15 L Tedlar bags was estimated to occur inthe order of 4-6 h. After this time, the terpene loss due toozonolysis drops to zero. Later studies designed to simulatethe collection of ambient air containing 50 ppb of 0'1 indicatedthat a 4-6 h storage period was a gross overestimation. A morereasonable storage period for ozone would be about 1 h forthese bags. Although not presented in the paper, past storagestudies of air-hydrocarbon mixtures (including several of theCIO terpenes) in Tedlar bags suggest excellent storage of thesecompounds for up to 30 days. Therefore, if the concentrationof the CIO terpene compounds in these Florida samples werejust a few parts per billion of carbon (ppbC) we should havebeen able to observe them on our gas chromatographic system.Also, in concluding that the CIQ hydrocarbons should not beexpected in the bags because of their reaction with ozone,Sculley has neglected the fact that the cis-2-0Iefins, the pentenes, and propylene were found in the samples. These olefinswould also be expected to react if Sculley's argument is correct.

The issue of natural hydrocarbon reactivity suggested bySculley as an important consideration in the formation of ruralozone requires further comment. True, the C IO terpenes areamong the most reactive hydrocarbons tested in smogchamber studies (4, 5); however, it is not correct to relate hydrocarbon reactivity to ozone production. Tn recent studiesperformed in our laboratory (6), maximum ozone formationper hydrocarbon compound reacted was investigated forseveral natural hydrocarbons. Propylene was also investigated.Some of the results from these studies are given in Table I. Tnthe table it is shown that at lower HCINOx ratios the amountsof ozone produced per carbon reacted are quite similar for allthe hydrocarbon compounds tested. However, at high HC/NOx ratios, typical to those found in rural areas, the naturalolefinic hydrocarbons become less efficient producers of ozone.This is primarily due to ozonolysis reactions and aerosol formation. If butane or any other paraffin were studied, the results would show that these compounds are the most efficientproducers of ozone on a carbon parts per million basis.

The issue that natural hydrocarbons produce gaseous aldehydes that serve as downwind sources of free radicals is notsubstantiated by past laboratory studies (7). Tn these studiesit was found that less than 15% of the C IO terpenes formedgas-phase oxygenates; the remainder is apparently convertedto aerosols. Since natural hydrocarbons react quickly withozone and hydroxyl radicals to produce oxygenates that

Table I. Ozone Production Efficiency Relative toCarbon Consumption as a Function of HCINOx Ratio

ppb03 produced/ppbC consumedHeINO. propylene Isoprene a-pinene

4 0.50 0.50 0.30

5 0.42 0.40 0.21

10 0.27 0.22 0.10

15 0.21 0.15 0.07

20 0.18 0.12 0.05

50 0.10 0.05 0.02

100 0.06 0.03 0.01

quickly form aerosols, it seems reasonable that the best attempt to determine the ambient burden of natural hydrocarbon would be to measure both gas-phase concentration ofthe C IO hydrocarbon and the organic fraction of the collectedaerosols. In past studies (8), however, the organic portions ofcollected aerosols were typically low, no more than 10% of thetotal mass, i.e., 10% of 100 /ig/m:J (TSP) or approximately 10/ig/m:l. If we assume that this entire fraction is comprised ofoxygenate terpenes, we still observe that ambient levels ofnatural hydrocarbon are just a few parts per billion. Of course,we would have to take deposition velocities of the aerosols intoconsideration if we are to arrive at a better estimate of naturalhydrocarbon emissions rates; however, particulates beingphotochemically produced would be in the small size range(fraction of a micron) and therefore have a low depositionvelocity.

Zimmerman has reported (2) that natural hydrocarbonsaccount for 68% of the total hydrocarbon emissions in theTampa Bay area of Florida. If this indeed is correct, we wouldexpect similar composition in the ambient air, i.e., 68% of theTNMHC to be of natural origin, particularly in the rural areaswhere our samples were collected. These samples, however,show a predomination of anthropogenic emissions. Efforts toaccount for natural hydrocarbon loss due to ozonolysis andhydroxyl radical reactions (3) do not significantly change thisdominance of anthropogenic emissions. Tn order to explainthe discrepancy between Zimmerman's estimate of naturalhydrocarbon abundance and observed ambient air samplecomposition, we propose two possibilities: Zimmerman'snatural hydrocarbon emission rates are too high or anthropogenic emission source strengths in the Tampa Bay area areunderestimated. We believe that a combination of both is themore likely explanation.

Lastly, it is important to comment on the role of smogchamber results to predict ambient air photochemistry. It iscorrect to state that smog chamber results cannot be directlyrelated to the real world conditions; however, the importanceof smog chamber studies is in the determination of the photochemical mechanism taking place in the ambient atmosphere. This is done by investigating the reactants andproducts of simple hydrocarbon-nitrogen oxide systems. Fromthese results, a photochemical reaction mechanism or modelis developed and validated. More complicated parameterssuch as intermittent hydrocarbon and NOx injection, atmospheric dilution, sunlight, and temperature variations canlater be added to the model to more simulate the rea) world.At present, no model is perfect and updating of the photochemical mechanism is a seemingly constant operation.However, without the use of smog chambers and their contribution to the development of ambient air models, ourknowledge of the photochemistry of hydrocarbon-nitrogenoxide mixtures would be minimal.


Table II. Storage Studies of Selected C10 OlefinicHydrocarbon-Air Mixtures in 2 Mil Tedlar Bags

conen, PpbCcompel Ink final (30 days) % decrease

n-pinene 98.9 95.4 3

IJ-pinene 92.3 84.1 9myrcene 65.1 63.8 2A-{;Mene 82.8 79.8 4d-limonene 64.8 64.7 1

Many of the comments made in reference to Sculley's noteare also applicable to the correspondence of Ludlum andBailey (L&B). There are, however, some additional specificcomments that we would like to direct to the note of L&B.

In response to the first point, we will agree that this is indeed a possibility, i.e., that the rate constants for 0 3 withmyrcene and 0 3 with d-limonene are much greater than therate constant used in our calculations for isoprene, and,therefore, much more natural hydrocarbon had reacted.However, the calculations made by us and also employed byL&B are no longer applicable when the rate constant betweenthe natural hydrocarbon and 0 3 is very large. Our calculationsshow that all of the 0 3 will be consumed by the natural hydrocarbons. Therefore, if30 ppb of 0 3were present this couldobviously react with 30 ppb of reactive hydrocarbon assuming1:1 stoichiometry. Since myrcene and d-limonene are CIQhydrocarbons, the amount of d-Iimonene or myrcene reactedwill be 300 ppbC. When both are present at the same time, i.e.,in the same container, then 197 ppbC of myrcene and 103ppbC of d-limonene are expected to react with 30 ppb of 0 3,This assumes that there is no degradation of 0 3 to thewalls.

We indicated in our paper that the Tedlar bag surfacescompete with the terpene hydrocarbons for ozone reaction.We had calculated the Oalifetime of 5 h in our original work(1). This calculation was based on ozone stability studies inlarge 03-treated Tedlar bags (approximately 150 L). We havereinvestigated the collection of ambient air samples thatcontain ozone into the smaller 10-15 L untreated Tedlarsample bags. We found that most (about 80%) of the ambientozone is destroyed during the filling process, probably due tothe turbulent mixing of the sample air and the more frequentcontact of ozone with the bag surface. After the filling process,the remaining ozone is essentially gone after a 30-60-minperiod. The short lifetime of the remaining ozone in thesmaller bags is probably due to the large surface to volumeratio. Therefore, the calculations made in our paper (I)overestimated the amount of CIQ olefin loss expected in thesample bags. This will also affect the calculations given earlier.We would expect less hydrocarbon to have reacted since the0 3 will also degrade to the walls.

The nonstoichiometry of terpene/03 reactions is anotherinteresting issue. Ripperton et al. (4) did indeed find that the,,-pinene/Oa ratio varied between 1.9 and 3.4. However, theduplication of the experiments was poor. Also, not all naturalhydrocarbons react in the same manner. Arnts and Gay (6)have recently shown that the isoprene-ozone reaction isstoichiometric when excess isoprene is present; however, whenexcess ozone is present the reaction is less stoichiometric withmore ozone than isoprene consumed. The apparent explanation for this lack of stoichiometry is that the diolefin willcontinue to consume ozone as long as th~re is a double bondavailable for reaction. Therefore, two ozone molecules will beconsumed for every isoprene. We expect the same results forthe terpenes with more than one double bond, such as myrcene, d-limonene, cr-terpinene, ocimene, and Il-phellandrene.


When stoichiometry is considered in calculations givenearlier, 197 ppbC of myrcene and 103 ppbC of d-limoneneneed to be corrected for the number of double bonds present.Since myrcene is a triolefin and Iimonene a diolefin, oneshould expect 65 ppbC of myrcene and 51.5 ppbC of limoneneto react with the :10 ppb of 0:,.

The limit of sensitivity of 1 ppbC for the hydrocarbons wasgiven as a gro~s approximation in our original work. This waslargely done since it simplified the calculations. However, ascan be seen in the data presented, our limit of detection forthe hydrocarbons is in fact closer to 0.2 ppbC for the he;lviercompounds and 0.1 ppbC for the lighter molecular weighthydrocarbons. Since the total amount olefin (ignoring ethylene) observed in samples is 5.3 ppbC for G-2 and 5.2 ppbC forG-3, then the reactivity factor, i.e., the rate constant X concentration, will he approximately 10-:' ppm-I S-I (5.2 X 10-3ppm) or 5.2 X 10-6 S-I. If the limit of sensitivity of 0.2 ppbCis used for d-Iimonene, then a reactivity factor of (1.6 X10-2)(0.2 X lO-a) or 3.2 X 10-6 S-I is obtained for the d-limonene. Since d-Iimonene was not observed in any of oursamples, and we did observe other olefins, we must concludethat lillie if any d -limonene was present in the original samples. A similar argument could be made with myrcene. However, as L&B suggest, this hydrocarbon constitutes only 1-3%of orange oil and therefore cannot be considered as a veryimportant natural hydrocarbon in the atmosphere.

There is no experimental evidence to suggest that SOx andNOx will react at significant rates with natural hydrocarbonsto make these reactions important. Also, since both NOx andSOx compounds are in the low pph level it is highly unlikelythat their reactions with the natural hydrocarbons would bevery significant at all. No reaction is expected with H20. Toour knowledge, particulate matter does not react at a significant rate with olefins. When one considers even a moderatelyloaded atmosphere of 150 Ilg/Ma, the gaseous equivalent ofthis particulate loading is in the low ppb level. Unless the reaction of natural hydrocarbons with particulate is extremelyfast, the reaction cannot possibly be important.

On the issue of stability of the natural hydrocarbons inTedlar bags, we stated in our paper (1) that storage studiesshowed excellent stability of the CIO terpenes down to 5-25ppbC. These studies were done for 5-10 days only. In TableII are shown some longer term storage studies done in Tedlarbags for 30 days. Obviously, our results do not agree with thosereferenced by L&B (9). In our studies the natural hydrocarbons showed excellent stability.

In retrospect, hydrocarbon emissions near citrus typevegetation may be unimportant. In our original work (1) weconsidered citrus vegetation the most important source ofnatural hydrocarbons in the Tampa Bay area; consequently,grab samples were collected within inches of orange trees.However, in ensuing studies by Zimmerman (10), emissionsfrom citrus type vegetation contributed only 3% of the totalnatural hydrocarbon emission burden. Zimmerman (10) reported that deciduous or broad leaf type vegetation consti·tuted the largest percentage of natural hydrocarbon sourceburden, with isoprene being the single most important hydrocarbon. In our samples, isoprene was the only natural hydrocarbon observed. This compound, however, contributedonly 1-4% of the totalnonmethane hydrocarbon concentration.

In summary, our calculations and our past work done in thisarea show that the conclusions put forth in our paper arecorrect. The results showed that natural hydrocarbon emissions are not as important as anthropogenic sources of hydrocarbons in the formation of ambient ozone.

Literature Cited

(I) Lonneman, W. A., Seila, R. L., Buralini, J. J., Environ. Sci.

Terhnol., 12,459-63 (1978).(2) Zimmerman, P., "Procedure for Conducting Hydrocarbon

Emission Inventories of Biogenic Sources and Some Results ofRecent Investigation", presented at EPA Emissions Inventory/Factor Workshop, Raleigh, N.C., Sept 1977.

(3) Bufalini, J. J., Lonneman, W. A., "Ozone Formation from RuralHydrocarbons", presented at the 1978 Coordinating ResearchCouncil Air Pollution Research Symposium, New Orleans, La., May1978.

(4) Ripperton, L. A., Jeffries, H. E., White, 0., Adv. Chern. Ser., No.113,219-31 (1972).

(5) Pitts, J. N., Winer, A. M., Darnall, K. R., Lloyd, A. C., Doyle, G.J., in "[nternational Conference on Photochemical Oxidant Pollution and Its Control, Proceedings", B. Dimitriades, Ed., Vol. II,pp 687-704, EPA 600/:J-77-00Ib, 1977.

(6) Arnts, R. R., Gay, B. W., "Photochemistry of Naturally EmittedHydrocarbons Isoprene, p-Cymene, and Selected Monoterpenes",to be published as an EPA report, 1978.

(7) Gay, B. W., Arnts, R. R., "International Conference on Photo-

chemical Oxidant Pollution and Its Control, Proceedings", B.Dimitriades, Ed., Vol. II, pp 745-51.

(8) Grosjean, D., Van Cauwenberghe, K., Schmid, J. P., Kelley, P.E., Pitts, J. N., Environ. Sri. Technol., 12,313-16 (1978).

(9) Denyszyn, R. B., Hardison, D. L., Harden, J. M., McGaughey, J.F., Sykes, A. L., "Evaluation of Various Hydrocarbon SamplingDevices," presented at NBS Symposium on Trace Organic Analysis,Gaithersburg, Md., April 10-13,1978.

(10) Zimmerman, P. R., "Bimonthly Progress Report, No. VIII,Determination of Emission Rates of Hydrocarbons from IndigenousSpecies of Vegetation in the Tampa/St. Petersburg, Florida, Area",EPA Contract No. 68-01-4432, Aug 26,1977.

William A, LonnemanJoseph J, Bufalini

U.S. Environmental Protection AgencyEnvironmental Sciences Research LaboratoryResearch Triangle Park, N.C. 27711

Correction

In the article, "Chemical Modeling of Trace Metals in FreshWaters; Rule of Complexation and Adsorption" IEnviron.Sci. Technol., [2, 1302-9 (1978)], by Jasenka Vuceta* andJames J. Morgan, the following corrections should be made.Figure 3 on page 1:103 should be interchanged with Figure 5on page 1304. The existing captions for both figures shouldremain where originally printed. Figure 4 on page 1304 shouldbe interchanged with Figure 6 on page 1304. The existingcaptions for both figures should remain where originallyprinted. On page 1305, the second line of the title to Table IIIshould read :1 X 10-" haiL Fe(OH);,(s), instead of (OH);,(s) asprinted.


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BOOKS

Solar Energy Uirectory I9711-79. 115pages. Centerline Co., Department149.401 South 36th Street. Phoenix.AZ S5034. 1975. $12.50.

Th is directory has over 1400 nationa� and international listings. Theselistings cover architects. associations,education, wind. rcsearch. markeling.and other related topics. Thc idea is totry to bring suppliers and potentialusers of solar energy together.

Sulfur in the [1lI'ironment. P:trt II:[cological Impacts. .Ierol11c O. Nriagu. Ed. xii + 4lQ pages . .Iohn Wiley& Sons, Inc., 605 Third Ave., NewYork. NY 10016. 1975. $14.25, hardcover.

This volume consists of a number 01"contributed papers covering topicssuch as material damages done by atmospheric sulfur compounds. SOc effects on plants, chemistry pollulantsulfur in natural waters. the aquaticeeosystel11 and sulfur, soil, and acidmine drainage problems arc alsoamong the nUl11erous subjects discussed.

The Use of High-Purity Oxygen in theActivated Sludg(' Process, Vols. I andII. J. R. McWhirter. Ed. Vol. I. 276pages: Vol. 11,274 pages. CRC Press.Inc .. 2255 Pall11 Beach Lakes Rd ..West Pall11 Beach. 1-1. 33409. 197'1'..Each volul11e, $53.95. hard cover.

Oxygen-activated sludge is onewastewater I rca tmen! tech niqueevoking strong interest. These volumesdiscuss the field. and cover systemsdesign, clarifiers. oxygenation itselLsludge production, digestion. and nitrification. Also dealt with arc UNOXsyslel11s, ozone applications. safety,supply. and cryogenics.

The Complete Greenhouse Book. PeterClegg and Derry Watkins. 2'1'.0 pages.Garden Way Publishing, Charlotte,VT 05445. 1975. $S.95, paper.

Greenhouses can range anywhcrebetween coldframes and sophisticatcdstructurcs heated wholly or partly bysolar energy. This book covers many ofIhese structures. and eX[Jlains theprocess of actually growing plants inthel11.

Oecupationaillealth and Safety Rl'gulation. Marshall Lee Miller, Ed. v +154 pages. Government Institutes.Inc., 4733 Bethesda Ave.. Washington.DC 20014. 197X. $1'1'., paper.

This work constitutes the Pl'lJcccdings of the First Annual OccupationalHealth and Safety Symposiul11, held atWashington, DC, last April. It isaimed at businessmen and industrialofficials. both familiar with. and n<:wto l11allers concerning occupationalheaIt11/safety. Also. government pcopic and others coneerncd should findit useful. It COWl'S OSHA hal.ardcitations: record keeping reljuir<:m<:nts:civil/criminal liabiliti<:s: what an inspector looks for; and many oth<:rpertinent topics.

EIlI'ironmental Chemistry and CyclingProcesses: Proceedings of a Symposium. D. C. Adriano. I. L<:hr Brisbin.Eds. xxxii + 911 pages. NationalTechnical Information S<:rvic<:. U.S.Dep\. of COl11merce. Springfield. VA12161. 1975. $15. paper.

There arc 61 papers covering design.sal11pling, and l11odeling: analyti,'altechniques: soils and sediments: plantand animal uptake: and terrestrial andaquatic ecosystcms. Designing c.\periments. analysis 01' dala. and results llI'spceific studies arc among topics COI'ered. Order CON 1'-760429.

Advances in Pestiddl' Scil'nec. IIGeissbiihler et aI., Eds..\ vols., '1'.44pages. Pergamon Press. Fairview Park.Elmsford. NY 1051:1. 1')7') $150 f"rthe scI.

The sci consisls of 110 invited C'"1

tribulions. and ~rows out I)f lhe h,unhInternational <'-olwrcss of PesticidcChemistry. It cov~rs pcsti<:idc '"1thesis. chemical strudurc. biologicaladivily, pest biochemistry. pesti,'idemodes of action. and formulaliollchemistry. Pesticidc residucs anddegradation arc also consid<:red.

I'rocecdings- W'lter Tfl'ahll<'ntWaste Disposal. A nl<:rica n Wa l<:rWorks Association. 6666 West ()uill'cy. Denver, CO ~()2J5. 197'1'.. $'1'..50.

These proceedings conlain eightseparate pap<:rs on the subje<:t.

MUlagc/lc,i,. W. (jary I· loll 1111 I. MyrullA. M<:hlilian. I:ds . .\ii + ·W I I'ag<:s.Halsted Pres,. 6051 hiI'd Ave .. NewYork. NY 10016. I'.I/l'>. ~2·UlJ. hard~ovt.:r

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Esse/llials of Im.icology. Jrd cd. I cd,\. Loolnis. hi. i.\ + 2·b p.lg<:'. l.e,1 &:I-cbig<:r. bOO Washingl')11 ::>LJuarc.Philadelphia. 1'/\ I') lOb. I '.I 'IX. ::, 12.50.Iwrd cover.

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Fehruary 19-20 Wa,hillgtoll. O.c.Toxic Sub,tances: Decisions andV,lIues. Tc<:hllical IllfL>r1l1atiollproject

Tupi(,; uf disCUS.'lIUIl will be th':l'isiulImaking. "Vrile: Thomas Cunry, PrujcdManager, Tt:chnicallnrunll~ltioilPrujl.xl,1346 Conneetinll live .. N.W .. Suite 207.Washington. D.C. 20036

Fehruary 27-211 Atlanta. (j:\

Symposium on ('ontrol Tcdlllology inthe Plastics and Resins Industrv. NalionallllstilUte or Occupational Sakt)and llealth (N IOSH)

Writ£': S. T hllu. 1-:11\ iro CUlltrol. Inc ..1130() Rockville Pike. Rudvilk. Md.20X52

Fl'hruary 27-March 2 San Diego.Calif.Second National ('onferl'nct' on lIa/.ardous Malt'rials Managl'menl. U.S.EPA. California Slate Ikpartnlentol'Health Service,. Cahl'ornia ChenlicalWaste Proces,;L>rs A,;,;ociation

~flril(': O. James Paruau. L.\ccutivc Directur, P.U. Bux 214X7X, S<lCr~IlI1CIl:U.

Ctlif. ~5X21

March 5-6 Wa.shington. D.C.('ogent'ration: For Luge USl'lS. TheEnergy Bureau

Wrir.:: Rouert W. Nash. heelltive Directllr. The !:nerg)' BlIleau Inc, IOi P;\fki\ve .. NewYmk.NY!OOI7

"larch 9-11I New York, N.Y.New York Einstein {'enlt'nnial {'ell'hration. The New York Acadell!y Ill'Sciences

ItVrile: Lin;-,lcin COlllllliltt.:l:. Till: 1\'1.:\\'

Ylll-k ACIOctn\ or SCit:[h':C~, 2 LL'l1 <13r<..lSI.. :'-lew York~ NY IlJ021

March 11-13 \/V'lShington, D.C.71h Annual Med;ng of the NaliullalOCl'an Industril" A"ociation. Natio",,1Occan Indu,trie, A,sociation(NOlA)

Thl: llll:l:ting willl!is\:u:-.~ \)1.':\,.'0111 rL"~Our\,,'l

devc!opnlell[. Write. NOlA. Suite 410.t IlJO 17th SI. ~.\V .. Wa,lti"~I"". IH_2UlJ.16 •

March 11··14 i\tlantd. G:IFuel ('vele '79. Atomic I"uu,tri:dForum.·lnc.

~Vrill': COIlk'rl:IICC Ullil'L'. I\tolllit: Industrial h)ru~l1.lnt:., 7101 \Vi~l"l.)1\~itl Ave"N.W .. Washington. D.C. 20014

244 Environmental Science & T~chnoloyy

MEETINGS

March 11-16 La,ton, Md.Hydropower: A National Ent'rgy Re'uurce. The Engineering Foundation

~.yrile: TIll: Fngilll:cring Foundation,34:\ E. 47th SI., New York, N. Y. IlJlJ 17

March 12-13 Washington, D.C.Managing Solid Wastes: Nt'w Rt'gulalions, New Challenges. The Energyl3ureau, Inc.

Write: Rouer! W. Nash, I:xeelltive Director, The Energy Bureau. IIIc.. IlJl ParkIIl'c .. New York. N.Y. 10017

March 14-15 Washington, D.C.Thl' National Council on RadiationPrott'ction and Measurements (NCRP)1979 Annual Meeling. NationalCouncil on Radialion Protection andMea,uremenls

Write: W. R. Ney. heeulive Dircetor.NCRI', 7~10 Woodmonl Avc .. Suite 1016.Wa,hington. D.C. 20014

March Ill-24 Washington,O.c.1979 American Sucil'ly of Phologrammelry / Amt'rican Congress unSurveying and Mapping AnnualMeding and Exhihit. Amcrican Socicty or Photogrammclry and theAmerican Congress un Surveying andMapping

Write: RIl"Ilie Breckenridge. Chairman,Registration COlllllliltcc. 2047 Golf CourseDrive. Reston. Va ..220~ I

M.lrch 19-21 Mi,ttni Beach, ria.Xtl! National Conft'rt'nct' and Exhibiti'/II on Municipal Sludge Management-Impact of Industrial Sonrct's ofTmics on POTW Sludgt'. Inrormation'1 ranskr InL, and the Ila/ardousM::tcrials Control Research Insti·tutc

Write: Beverly Waleoll Sludge Man;:g.I':J11cl1! Conkrcllec, t:/o InformationI r"".,kr Ille .. Suite 202. II (,() RockvillePike. RoL'kville. Md. 20X:\2

March 19-22 Los Angeles, CaliI'.Thl' 6th ('onferl'lll'e on the Prt'\'l'Ilfion,Belial iur, ('ontrol, and Clt'anull of OilPollntion. The American Petr<J!cumInstitute, U.S. EPA, and the U.S.Clla,t (,uaru

Write: Conl'erence headquarters, t (,2~1\ St., N. W.. Washington, D.C. 20006

March 21-22 Washington, D.C.7th Annual APCA Government AffairsSeminar. Air Pollution Control Association (APCA)

Write: Public Relations Department,II PCII, P.O. Box 2861, Pittsburgh, Pa.15230

March 26-28 Orlando, Fla.Sih Annual Research SymposiumMunicipal Solid Wasle: Land Disposaland Resource Recovery. U.S. EPA,Florida Technological University

Write: Division of Continuing Educa·tion. Florida Technological University,P.O. Box 25000, Orlando, Fla. 32816

March 29-30 New Orleans, La.IUlh Annual Symposium of the NewOrleans Chromalography-AnalyticalDiscussion Group of the LouisianaSeclion of the American ChemicalSociety. New Orleans Chromatography Discussion Group

Write. Tom W. Pewill, Shell Oil Co..1'.0. Box 10, Norco, La. 70079

Courses

Fehruary 19-23 Madison, Wis.Adminislering EPA ConstructionGrants Contracts, Course No. 468. TheU11 ivcrsi ty or Wisconsi n- Extension

Fcc: $400. Write: The University ofWisconsin Extension. Dept. or Engineering & IIpplied Science. 432 N. LakeStreel, Madison. Wis. 53706

Fehruary 19-March 2 Cincinnati,OhioAnalysis of Organic Compounds inWalt'r. The Finnigan Institute

Fcc: $1500. Write: The Finnigan Insti·tute. Atkinson Square Building 5, 11750Chesterdale Road, Cincinnati, Ohio4524(,

Fehruary 20 Minneapolis, Minn.Permits Under Ihe Clean Air Act.Trinity Consultants

Fcc: $150. Write: Trinity Consultants.1'.0. nox 314XI. Dallas, Tex. 75231

Feburary 11 Chestnut Hill. Mass.Practical Lake Managemenl. WestonOb,ervatory-Boston College

Fcc: $40. Write: Lake Symposium III.c/o Carl' Research Laboratory, Inc., 3X4Washington St.. Wellesley, Mass. 02181

(('I;//fil/llt'd UII !Jr/gt' 147)

CLASSIFIED SECTION • POSITIONS OPEN

All tqudl Oppurtullity Employer MIF

AIR QUALITY SCIENTIST

Or. Oemelrios Moschandreas-Oirector of Environmental Sciences

GEOMET. Inc_15 Firstfield Road. Gaithersburg, Maryland 20760EOf. Mil-

SENIORENVIRONMENTAL

ADVISOR

PENNZOILCOMPANY

8. R. HigleyP.O. Box 2967Houston, Texas 77001

P",nnzoil Company is seeking an individual with technical as well as good interpersonal skills to work in itscorporate Environmental Safety and Health Department.

The individual will advise operating and executive levelmanagement on the control of air, water and solid wastepollution. Job will include 50% travel to company'sdomestic facilities.

Candidate must have a BS in basic Engineering, andpreferably, an MS in Environmental Control, with 5 yearsconsulting experience in air, water, and solid wastepollution control. Familiarity with EPA regulations aswell as prior experience in dealing with governmentalagencies is necessary for this job.

Pennzoil Company offers a wide range ofbenefits, a good salary and a stimulating professional working environment. If you are interested in this position, please sendyour resume in confidence to:

GEC?MET.lnc.. a~ Environ'!lental s.';le~ces consul ling firm in Gaithersburg. Maryland. has positionavalla~le for Ind.~ldual WIth academrc or professional experience in meteorology, dispersionmodeling. aIr quahly atmospheric chemistry, and/or related sciences.This is a newly-created position established. due to reorganization. to expand corporate capabilitiesfor research and analysis.

Masters degree required PhD preferred-·in relevant physical science.

GEOMET, h.le. offers a high degree 01 individual freedom. responsibility, and competitive salary andlotal beneftts package.

PrincipCJls only. please send resume, including compensation history, to:

,..

FACUlTV POSITIONSENVIRONMENTAL MICROBIOLOGYANO AIR QUALITY ENGINEERING

The School of Civil Engineering at GeorgiaInstitute of Technology is seeking tenuretrack faculty members in environmentalmicrobiology and in air quality and pollutioncontrol within the Environmental Engineeringprogram. These two positions involveteaching at the undergraduate and graduaterevels and leading the research thrust in therespective areas. A doctorate in environmental science or engineering with a microbiology specialty is required tor the microbiology position; a doctorate in engineering is required for the air quality pasi.tion. Rank and salary are commensuratewith qualifications. A detailed resume andnames of three references should be submitted to Dr. J. E. Fitzgerald, Director,School of Civil Engineering, Georgia Institute of Te<:hnoJogy, Atlanta, Georgia 30332.An equal opportunity/affirmative actionemployer.

EXECUTIVE DIRECTOR-STATE OF FLORIDAFLORIDA INSTITUTE OF PHOSPHATE RESEARCH

Bartow. Florida (Temporary Address: 903 W.Tennessee St.. Tallahassee. Florida)

The Board of Directors invites applicationsfor the position of Execulive Director 01 theInstitute. Qualilicalions are PhD/SeD orequivalent experience (phosphate p.efcHe<J)in sciences related 10 mining. mineral processing. geology or environment: al leaslliveyears proven competence in research andadministration: demonstrated skillin effecllvecommunication: ability to plan. allocate resources and provide for evaluation of pr<>gams.Salary is negotiable.

The application wilt reqUire a vita and names01 three references. Please forward all applications to Personnel Officer. Flo(ld~ B(J<)rd ofRegents. Room 226. Collins Building. Tallahassee. Florida. 32304. ApplicatIOn deadlineis March 15. 1979. For further Infonnationcontact C. W. Hendry, Jr.. Chairman. Board ofDireClors, Florida Instilute of Phosphate Research. 903 W. Tennessee SI., Tallahassee,Florida 32304.

An Alllrrrl<l!lve AC!lC)n/EqI.l31 Opportunlly EnlJllOyt#

DENVER RESEARCH INSTITUTE requires Ph.D.or M.S. in Physics. Electrical. or MechanicalEngineering in expanding R&D programssponsCH'ed by several government <tgencies andindustrial organizations. Activities includetheoretical studies of electrostatic fields andHigh Voltage Supply control: charging. collection. and adhesion phenomena: design.fabrication. and installation of bench·scalethrough pilot·scale precipitators: ESP consultation and analysis. Two years experience inone or more of these topics and IwO more yearsin related R&D engineering are desirable. Fourto six years experience in closely-related activities at a high technical level will be considered. Send resume and salary history to:

Mrs. Phyllis Riggs

DRl/ElectronicsUniversity of Denver

P.O. Box 10127, Denver, Colorado 80210

"The University or OeoYel ICokxado Sefm",:vYIIS anAlhrrTk1live Aclion Eql.l31 ()ppof1uMy Employer"'

ELECTROSTATIC PRECIPITATORSCIENTISTS. ENGINEERS


CLASSIFIED SECTION • POSITIONS OPEN

ENVIRONMENTAL SCIENTISr:L-'S AND BIOLOGISTSThe Research Institute of the University of Petroleum & Minerals, Dhahran. Saudi Arabia. has immediate openings for the following positions:

f. WA TER QUALITY SCIENTIST:Responsibilities include experience in new analytical technique and thorough background in water chemistry studies. statistical data interpretationand report preparation. Should be able to apply and employ a wide variety of instrumentations used in water pollution. Qualifications shouldinclude an M.S. or equivalent in Environmental Chemistry or related field. AI least four years of related experience is necessary.

2. AIR QUALITY SCIENTISTApplicants should have a minimum of a Master Degree in Environmental Science or related field with experience in air quality investigationincluding the application of a wide variety of instrumentations used in air pollution. Must have the ability to interpret data, prepare and reportfindings in good writing skills. At least four years of related experience is necessary.

3. RESEARCH BIOLOGIST:Responsibilities include experience in marine biology and fisheries. Applicant must hold a university degree in this specialty with a thoroughbackground in the chemistry of water and air in addition to his field. Duties will include field sampling, bioassay capabilities, laboratory analyses,data handling and report writing. Experience in this field is a great factor in selecting applicant. M.S. degree or equivalent is preferred.

Minimum regular contract for two years, renewable. Competitive salaries and allowances, all earned income without Saudi taxes. Free air conditionedand furnished housing, free transportation to and from Ohahran annually. Attractive educational assistance grants for school-age children. Localtransportation allowance in cash each month. Ten and a half month duty each year with 45 days vacation paid.

Apply with complete resume on academic and professional background, list of references and with copies of degrees/testimonials, including personaldata such as home and office address, telephone numbers, family status (spouse's name, names at children, ages and sex) to:

The Research Institute, University of Petroleum & Mineralsc/o Saudi Arabian Educational Mission

2223 West Loop South, Suite 400, Houston, Texas 77027

MARKETINGSPECIALISTS

A large water and wastewater treatmentequipment manufacturer requires twoProduct Engineers to prepare andpresent proposals, review cost and pricedata, and support a national direct fieldsales organization on equipment appli·cations. An Engineering degree andexcellent written and oral communication skills are required. Both competitiveand user experience will be considered.Competitive salaries and benefits.

For further information contact:

M. Pendergrass

Dunhillof maine, inc.

449 Forest AvenueForest Avenue PlazaPortland, Me. 04101

207-774-0366Cliem Is An Equal Opportunity Employer MlF

POLLUTION CONTROL PROFESSIONALSSpecialists In placing envrronmental personnel exClUSively since 1968. All diSCiplines. aU levels National/international affilialions. No lees.

PROFESSIONNEL al RossmoorRossmoor Bank Building

J''PIOH~ER~'I~pJOl~~~I~~CONTRO(~~A~lMEWO


ENVIRONMENTAL ENGINEERS AND SCIENTISTSPacific Environmental Services. Inc. is now expanding. PES provides services to industry and government to solve problems related to energy and the environment. Our nationwide consulting firmis seeking innovative and aggressive engineers and scientists who are interested in technical andmanagement challenges. Positions are available at our Los Angeles, Chicago, and Durham. NorthCarolina offices.PES has immediate openings for applicants with experience in industrial process engineering, controltechnology evaluation, control strategy analysis, and air pollutant emission measurements. Thesetechnical and management positions require familiarity with industrial and energy facilities. andknowledge of recent EPA regulations. In addition. PES is seeking scientists and engineers with analytical skills in computer simulation modeling, water quality, atmospheric science, toxicology,and solid waste.PES offers an excellent salary, competitive benefits (including dental). and outstanding professionalopportunities. Apply today.

Send resume. salary history, and location preference to:

PESAttention: Dorothy Tanabe1930 14th Street, Santa Monica, California 90404ArlEDI: M/FfH

PROGRAM MANAGERExpansion of energy and environmental consulting program has created immediate need for anexperienced pollution control engineer to manage source emissions measurement and related~C1i~ities. ~uccessful candid~te. must h~ve demonstrated technical and managerial competence10 Wide variety of source emiSSions projects for electric utilities, mining. and process industries.Responsibilities include directing a program staff of professional and technical personnel. marketing

and proposal development. overseeing field operations: and preparationof reports. Excellent starting salary with significant growth potential. Sendresume in confidence to:

York Research Consultants7100 Broadway, Bldg. 3-D, Denver, Colorado 80221Telephone (303) 426-1582

CLASSI~IED SECTION • POSITIONS OPENMICETINGS (mlltilllled)

METEOROLOGIST

February 21-22 Minneapolis, Minn.Fundamentals of Dispersion Modeling.Trinity Consultants

Fec: $320. Write: Trinity Cunsultants,P.O. Box 314~ I. Dallas. Tex. 75231

Consumers Power Company one of the largest investor owned utilities in theU.S., currently has an opening for an experienced Meteorologist. The individual will analyse and evaluate meteorological data, as well as perform theatmospheric diffusion modeling and dose calculation analysis that are requiredby NRC regulation for Nuclear Power Plant.

The individual should have a degree in meteorology with at least 2 yearsexperience and interest in computer programming and data processing;thorough knowledge of NRC regulations; strong verbal and written commL:nications skills; and ability to work independently.

Please send a complete resume and salary requirements to:

@Professional Employment Supervisor

Consumers Power Co.~ 1945 W. Parnall Rd., Jackson, Michigan 49201An Equal Opportunity Employer MI F

A leading contract research organization needs junior or mid-level professionals forthe following positions:

February 22-23 Atlanta, Ga.Plant Energy Conservation. The Association of Energy Engineers

Fcc: $305 (members): $360 (nunlllcmbers). Write: The Association of EnergyEnginecrs. Attention: AEE Encrgy Seminars. 464 Armour Circle. N.E.. Atlanta.Ga 30324

February 26-28 East Brunswick,N.J.Cooling Water. The Center for Professional Advancement

Fcc: $450. Write.' Mary Sobin, Dept.N R. The Ccntcr for Profcssional Advanecmcnt. P.O. Box H, East Brunswick,N.J.08816

February 26-March Cincinnati,OhioSampling and Evaluatinl( AirborneAsbestos Dust, Course No. 582. National Institute for OccupationalSafety and Health

Fec: $200. Write: Donna Wclage,Training Rcgiwar. NIOSH, Div. ufTraining and Manpower Devclopmcnt,4676 Columbia Parkway, Cincinnati. Ohio45226

Environmental Health Information AnalystRequires background in environmental health. public health, information or computersciences. A combined background in biological and information sciences is highly desirable. Initial assignment will involve development of an interagency data system.

Environmental BiologistRequires a background in environmental biology and chemistry, with experience in qualityassurance activities. Initial assignment will be to assist an interagency group on standardization of environmental monitoring and bioassay programs.Both positions require bachelor's degree with some graduate work and a minimum oftwo years experience. preferably in a consulting environment.Please submit resume, including compensation history, to:

March 6-8 Pittsburgh, Pa.Industrial IIYl(iene Traininl( Courseand Workshops. Industrial HealthFoundation, I nl:.

Fce: $IX5 (members): $245 (nonmembers). Write: Geurge Reilly, IndustrialHealth Foundation. 523 I Centre Ave ..Pittsburgh. Pa. 152.1 2

March 5-8 St. l.ouis, Mo.Sanitary Chemistry and Microbiologyfor Practicing Enl(iueers. The University of Missouri- Rolla

Fee: $325. Write: Ju-Chang Iluang.p",ressor of Civil Engineering. Univer,ityuf Missouri Rulla, Rolla, Mo. 65401

February 26-March 2 Chicago, 111.Applied Combustion Technolol(Y. TheCenter for Professional Advancement

Fcc: $6~5. Write: Mary Sobin. Dept.N R. The Ccnter for Prufessional Advancement. P.O. Bux H. East Brunswick.N.J. 0~816

March 1-2 Madison, Wis.Solid Waste Collection Systems. University of Wisconsin ·Exlcnsion

Fee: $130. Write: University of Wisconsin Exlcnsion. 432 N. i.ake St .. Madisun. Wis. 53706

ENVIRONMENTAL CHEMISTTenure-track Assistanl or Associate ProfessorshipBeginning September. 1979 in an A.C.S. accreditedDepartment with 10 Chemists. Dulies includeteaching undergraduate environmental chemistry.quantitative analysis and participating in lower division environmental science and chemistrycourses. Ph.D. required. A strong background inchemistry at the graduate level required. Postdoctoral experience desired. Strong commitmentto teaching and ability to develop a research program expected. Send application. 3 letters of recommendation and transcripts to: Faculty SearchSecretary. College of Arts, Sciences and Letters,The Universily of Michigan-Dearborn, Dearborn,MI 48128, A non-discriminatory, affirmative action.Tille IX employer.

GEOMET, Inc.15 Firstfield Road. Gaithersburg, Maryland 20760

Dr. Niren L. Nagda-Manager, Exposure and Health Efl.ects Assessment

~OE MfF

CLASSIFIED ADVERTISING RATESHall' hasl,d "n 1II11lllwr "f ins"rlj.'n,.: 11l-I·d willlll1I:! l11"ll\h~ fr"lll lIal., "f fir,,( in""rli"ll ilnd rhol "nllll' Illllllht'f "f inell!''' USN!. ~P:I"(' ill ,'b".~iril'd

adn·rti"ing ,'<11111,,1 lit' ,'''llIbilll,d r'or fn'q\ll·l\t·.\"wilh H(ll' ;llln·rli,..ll1g. ('la,.;,..ifi.·,1 ad\·Nli,..illl.: :U··('I·ptt·d in indllllllhipll'stllll.\".

Unit l-T 3-T 6-T 12-T 24-Tlinch S63 S60 SSB $56 $54j('lu·,·k C!a,..,..ifil'd ,\dq·rli,.;illJ.: I)"parrlll"111 f,.rral"."ifadq·rriM'IllPII\ i,.. !art!"r Ihal1 111"'.1

SHIPPING INSTRUCTIONS:S.·ndallmaINial II>

Environmental Science & TechnologyClassilled AdverUslng D-epanmenl

25 Svl .. n Rd South. We~tl>ort, CT 06660


MEETlN\.;S (colllillll"d)

March 7-9 Atlanta, GaSolar Energy. New York University

Fcc: $610. Wrile: Registrar. 14th Floor,!'I.Y.U. (onkrc'nee Center. 360 LexingtonAve .. New York, N.Y. 10()J7

Marl'll 7-9 Washin~ton. D.C.Air Pullution Contr~ EquipmentUpcraliun and Maintenance. GeorgeWa,hington University

he: ),415. Wrile: Director. ContinuingEngillt.:l:ring Educalion. GeorgI.: Wash~

ington University. Washington, D.C.2U1J:i2

I~eedlove Asso<:iates Inc.~ £nvironmental Consultants

• Dredge .and fill Perlnits

• HcCIJrnatitHl Programs• Aquatic Sy~tCltl Restoration

• tnVirOll111cntJl MOllilorill9• Analytical Laboratory

• l::Jio<..lssay• f.IlVIHlll1l1cnlal LiC(,tlSlll~

• Lilllllological StU(JICS• LnvlrOrllllcntal 1l1lp'1{.:t $t<ltcl\lcnb

1904}·376·2320618 Northwest 13th AvenueGainesville, Florida 32601

CAMP DRESSER & McKEE INC.

1'lt'("Il!."i'I,,:oI

B·' I HI',',,1 '111",'lhO?10H

CDMcnVIIOlJmentaJ CflYlnCCf::, SCientIsts

p1d1HlCI<; & nldf"Jagcment conSultan/,,;

W WALK,HAYDEL&ASSDCIATES.INC.~Complete Environmental Servites

Refinefles. Chemical PlafltsFerti/iLer Facilities. Pipelines. Docks.Oil & Gas Offshore Facilities. Terminc1/s

600 Carondelet St ,New Orleans,La 70130

5045868111

An Employ.. Owned Com~ny

GREELEY AND HANSEN

1501 N Bro..d ....,)"

W.lny\ C,eek,CA 94596

(415) 9)7·9010

BROWNAND CALDWELLCONSUL fING ENGINEERS

ENVIRONMENTAL ENGINEERINGSource Control. Waste Treatment _ Solids Handling

Reclamation _ Energy and Resource RecoveryOperatlo", Consultation laboratory Analysesand Training SInce 1947 and SurveysATLANTA 'ASADENA SEATTLE WALNUT CREEl(

EUGENE SACRAMENTO TUCSON

I~,6u,~ .I.E.SIRRtNE COMPANY

Engln••rs Since 1902

March 12-13 Washington. D.C.Ernironlllenial Regulation and legislation. New York University

Fee: $5<>U. Wrile: Registrar. 14th Floor.N.Y.U. (,)Ilkrenee Center, 360 LexingtonAve .. New York. N.Y. 10017

March X-9 Philadelphia. Pa.Industrial Safely. Drexel University

j'ee: $350. Wrile: orriee or ContinuingPrurt.:~~jollal EduG.llion. Drexel University.32nd and <- he,lnut Streds, Philadelphia,Pa.191U4

ILITES PEl{ Issei·:

USE THE CONSULTANTS' DIRECTORY

Sl. Louis, MO

HAVENS ANDEMERSON, INC.Environmental Engineers

C1t'vPlilnd,OH Sdddle Grouk, NJ

't',

$~lF,,-LABORATORIES INC.

545 Comm~ru St Fro"ldl" lok~s. N J 07417201·337.4774 201·891·8787

• Alomlc Abloration • Optical Eml"lon• Ch••1eaI • X-ta, $pedro",*,

Compl~t~ Anolytlcal Services forEnvlronm(ntol St..dI(S a Pollution Control

E

Six 'I\\'t'ln' Yuur t'ardUNtT l",;slIPs lsslIP"';Illav al'l,,'ar 111

('Vl'ry Issue [u'r (lIH' vpar.I" I col. $ :1:.) ::; :t:\ I'VI'!'y ISStlt~ [or SIX 1l1')lllhsI" :!Ctll. f)~J li;-,

( l't)IlSt 1I'utiV(I iSSlILlS l. orI" :lcol. 111~ !J] utlli'r fort en!. Ii!) I):, t'v,'r~' ISSUl' unl-'

:! I'ld 1:11\ I tH \"';\1' I,lit\'mal\' iss UPS ),

t el,l. 1:111 IIH S\'lld ~:()llr I'opy to:

BY ElHTRON MI(RO\COPY

CHARLES R VElZYASSOCIATES, INC.

CONSULTING ENGtNEERSWATER POLLUTION COIHROL • SOLID

WASTE DISPOSAL. AIR POLLUTIONCONTROL. INDUSTRIAL WASTES.

DRAINAGE. WAHR SUPPLY355 Main StreetArmonk, N.Y. 10504

Mineola New York Ba byron, New York

ERNEST F FULLAM. INCPO 80X 444 • SCHlNtCTADY N y 11301IlllPHONl ')111 185 ')')3J

WRITE. FOR CAIALOG

SMALL PARTICLE ANALYSIS

Complete Design otEnvironmental Facilities

USA GreenVille. SC 29606 HouSlon rEx 77027Ralelgtl. NC 27t3C7 0 Riyadh. Saudi Arabia

March 19-20 San Antonio. Tex.Sular Energy Storage Options, U.S.Department or Energy

j'ee: MU. Wrile: Trinity UniversityContinuing f:dueation. Storage Workshop.715 Stadium Drive. 130x 79, San Antonio."' ex. 7~~X4

March 14-15 Cleveland, OhioThe National Conference on EnergyAuditing and Cunsl'nation. Associationror Media-based Continuing Education ror Engineers. Association or Encrgy Engineers. Case Institute orI'echnology

Fee: $225. Write: Yae,)v Y. Haimes.Cl}lIl'l:rClh':l: Chairman. Case Institute of

Technc,log}. Cleveland. Ohio 44106

i\brch 2(1-21 San Francisco.Calif.Energy Management in Buildings. NewYork University's School orContinuinl! Educatiun

J'ee: $56U. Wrile: Heidi F. Kaplan.Uept. 20 NR. New York University Sehouluf CUlllillUil1g h.iucation. 360 Lexington.\vc.. ,,,"ew \\Jrk. N.Y. 10017

:Vlarl'h 21-22 Minneapolis. Minn.R"Il'r'l' OSJlwsisjlJllrafillration forWaslc Water Treatment or ResourceHecoH'ry. O"l1\)flies. Inc.

J'ee: ~300. Write: Patricia A. Lelson.ChIlHlIIIC,. Inc 15404 Industrial Road.Ilop'i'b. Minn. 55343

ENVIRONMENTAL SCIENCE & TECHNOLOGY


professional consulting services directoryenvlroovneenGineers

COf=lPORATION

222 Wesl Adams 51 • Ch,c.go. IIl1nOI' 60606

(312)263-011.

• Cadre engineered CUSTOM Structural Bagl'1ouses for Hot Gas& Abrasive "'ppllc.Ulons

• C"dre Special-Design Fume & Fly "'sl'1 Collection UnltsSl'1op Assembled

Transportation. Enyironmental

Food Engineeringe Energy. Civil/Sanitary

Systems Studies and Design

• Retrofit SPECIALIST or larg~ ~ltlSling Bilghousr Systrms

• EJlp~ru In correction of air flow or dlrrlcult duct design for reductionIn pressure drop tl'1rougl'1 laboratory & scale modellng

• F~aslbllity & cou trade-off studJes with use ofCadre", Computing Center

PLEAsr CONT"'CT JERRY B....RTLETT • THE ("'ORE CORPORATiON

PO BOX 47837 • ATLANTA. GEORGI .... 30362 • 14041 4~8-'1SZ1

Engineering & Testing ConsuJtanfsCherry Hill, N.J. (609) 424-4440Charlotte. N.C. (704) 333·8411

Atlanta, GA. (404) 377-4248South Euclid. OH. (216) 382-1719

METAIRIE. LA. 700022932 LIME STREET

WATER AND AIR POLLUTION CONSULTANTSEnvironmental Services - Water and Air Quality

Testing - Emission & Ambient Air TestingMicrobiological and Chemical Analyses

ANALYSIS LABORATORIES, INC.

TURNKEY AIR POLLUTION CONTROL SYSTEMS

(504) 889-071 0

~COMPLETE ENVIRONMENTAL SERVICES:.... ' "" ~

Stear':;~:i'~ ,.' .. ' Environmental Impact assessments. _ . Pollutant emis·Slon, air quality & water quality monitoring ... Dis-persion estimates ... Ecological consulting .

Meteorological field studies & consulting services. Contact

ENVIRONMENTAL SCIENCES DIVISION P. O. Box 5888(303) 758-1122 Oenver. Colorado 80217

Ambient Air Quality StudiesDiffusion Model ing ASTRO

Source Sampling ENVIRONMENTAL INC.Industrial Hygiene Services

Water and Wastewater Surveyslaboratory Services Complete Environmental Services

Engineering Services Water Pollution Control

[fIg,9.t~~Waste Disposal

Industrial Wastes

87 Main Street, Hempstead, NY 11550

6601 KIrkVille Road. East Syracuse. N.Y. 13057 516-586-8935(315)437-7181

,.. -.., r Woodward·Clyde ., ""IIIlL1OOr,.lOrV ,.nd Procps<; Devf'loprnenl

In(\US111,,1 W,I<;I{' W"I(-". Control Consultants1l!lUlO ,inti S01l0 In(lnerilllon

Air PulluTlon Conlrol • Site Selection StudiesIn pl."" Curl!rOI ,1f1<1 PrOCe"'" ModdlCcll,OflS

• Impact AssessmentDe..,.II,n,ttIOn

CATALYTIC,Evaluation

• Decision and Risk Analyses

INC.• Environmental Field and

Laboratory Studies

('nn'll!i ,Ill... I n.:IIlN-'f'). COII')lll.lCIOr') Envlronmenfal Systems OlvlSlon

l nvlronnl('fll,ll S'I'<;lem, D'VISion Headquarters San FranCiSco. CAr"'ll',- l;qll,"" 1f"',>1 1')00 M.H~el Sfr!"!"!

•Other olllCcs III Clltton. NJ • Washmgton. 0 CPtlll,Ith'lph." p" !<j\O,J !\~-86J18000.... Charlotte, N.C. 28210 704-542-4220.....lIIl

\.. Ancflorage AK • San Diego CA ~

~ GI 0 LABWATER INFORMATION CENTER, INC.

CHEMICAL ANDPubl.shers ollClerence books te~ts

ENVIRONMENTAL.lnd nc,,"slcttcrs on lhe subject 01 waler TECH NOLOGY

S".mJ lor ~ar,}'og

," JAIl.· .. ' ',I ""1(''' '-, .... ~O", ". OJ . ~" '!>I' 'J'~FAIRHAVEN, MASS. U.S. A.

8515 Elin Ordlald Rd.Sui~210

~.Co.80111

13031 719-4940

• AIR. WATER. SOLIOS • NOISE. ODOR• .....,.... • WIit i...1..fIICt~ Syst_

• eH." • ~iIIt

ENVIRONMENTAL PLANNING'

PROBLEM SOLVING for

INDUSTRY.GOVERNMENT

125sa. DeaneH~vw.thtfcfie4d., Ct. 0810012031583-1.31

TRC

sg!~lY~Environmental services.air and water pollutioncontrol engineeringand consulting

4 Research PlaceRockville. Md 20850301/948-7010TWX: 710-828-0540

ECOLOGY AUDITS. INC. ~11061 Shady Trail Dallas TX 75229

(214)350·7893

AmblentAIrStu<hs·StKll5amplln;·W.lIfTtstlng·~dParty

PwClltuloNl Rtpt'HoM.llon· NPOfS MonItoring' 0lsper'5I0n IlIodtlIngEnYll'onmIntMlrnpactSt.ltmffIIs

!lJif,Ch (l!I(~ hI.!~ LA· illSl .~ mi.~ '1iY· t))1l 166 IN

Subsidiary of Core Laboratories Inc

AIR & WATERSTACK & EXHAUST TESTS

CONSULTING. LABORATORYParticulates. Aerosols. Odor. Smoke

Or~~ci.Cth:~~:rA~~li:sSe~jo~s~~.~he.s."TEST IT FIRST SO YOU REALLYKNOW WHAT THE PROBLFM IS"

ROSSNAGEL & ASSOC.

I·,

I·I rIe


INDEX TO THE ADVERTISERS IN THIS ISSUE MEETlN(;S (col/til/I/i'd)

22 ..... The CarborundumCompany .......•.•... IBC

Ellis Singer & WebbLtd. Adv.

CIRCLEINOUIRY NO. PAGE NO.

CLASSIFIED SECTION

PROFESSIONAL CONSULTINGSERVICES DIRECTORY .

PAGE NO.245-247

248-249

March 22-23 Madison. Wis.Powcr Plant Ash-S02 ManagementIII. University of Wisconsin-Extension

Fcc: $130. Write. University of Wisconsin-Extension. 432 N. Lake St .. Madison. Wis. 53706

20 ..... Environmental ResearchCompany ..•........•. 178

Omni Advertising

4 ERT 131Impact Advertising.Inc.

6-9 .... Foxboro Analytical. . 141, 149Shepherd. Tibball, 151,153Galog Associates

....•. Grillin Environmental 178The Ad Shop

19 ..... Huyck Corporation . . . • . . 165Gray & Rogers, Inc.

21 ..... InstrumentationLaboratory 165

Aries Advertising,Inc.

2 ...... KontesGlass Co. ....... 165Aitkin-Kynett Co.,Inc.

3 •..... Lear Siegler, Inc. ••..... IFCR.A.S.P. Advertising

12 ..... Martek Instruments,Inc. .•.•••.•.......... 139

Tekmar MarketingServices

14-17 .. Mine SafetyAppliance • . . . . . . . . . . . . 136

Ketchum, Macleod &Grove. Inc.

11 .....Orion Research Inc. .... OBCaBC Advertising

18 .....Perkin-ElmerCorporation 148

Marquardt & Roche,Inc. Adv.

5 Research ApplianceCompany ....•........ 134

W F Minnick &Associates, Inc.

10 ..... Whatman Inc. . . . . . . . . . . 154J. S. Lanza & Associates


Advertising Management for theAmerican Chemical Society Publications

CENTCOM, LTO.

Thomas N. J. Koerwer, President; ,James A.Byrne. Vice President; Clay S. Holden, VicePresident; Benjamin W. Jones, Vice Prf'sident; Robert L. Voepel, Vice President; 25Sylvan Rd. South, Westport, Connecticut06880 (Area Code 20~) 226-71:11

ADVERTISING SALES MANAGER

Alfred L. GregC'ry

SALES REPRESENTATIVESAllanta, Ga.... Robert E. Kelchner, CENTCOM.

LTD.. Phone (Area Coce 203) 226-7131Boston. Ma.... Anthony J. Eagan, CENTCOM. LTO.,

(Area Coce 212)972-9660Chicago, II.... John McGuire, CENTCOM, LTO.. 540

Frontage Rd., Northfield, III. 60093 (Area Coce312) 441-6383

Cleveland, Oh.... Bruce Poorman. CENTCOM,LTD., 17 Church St, Berea, OH 44017 (AreaCode 216) 234-1333

Denver, Co.... Clay S. Holden, CENTCOM, LTO.,(Area Coce 213) 325-1903

Houston, Tx.... Robert E. LaPointe, CENTCOM,LTO., (Area Code 415) 781-3430

los Angeles, Ca.... Clay S. Holden. CENTCOM3142 Pacific Coast Highway, Suite 200, Torrance, CA 90505, (Area Code 213) 3251903

New York, N.Y.... Anthony J. Eagan, CENTCOM,LTD .. 60 E. 42nd Street. New York 10017,(Area Coce 212) 972-9660

Philadelphia, Pa.... Anthony J. Eagan, CENTCOM,LTO., GSB Building. Suite 510,1 Belmont Ave..Bala Cynwyd, Pa. 19004, (Area Code 215)667-9666

San Francisco, Ca ... Robert E. LaPointe. CENTCOM, Ltd., Suite 303, 211 Sutter Street, SanFrancisco, CA. 94108. Telephone: 415-7813430.

Westport, Ct.. . Anthony J. Eagan, CENTCOM,LTO., 25 Sylvan Rd. South, Westport, Ct.06880, (Area Coce 203) 226-7131

United KingdomReading, England . .. Malcolm Thiele, Tech

nomedia ltd .• Wood Cottage, Shurlock Row,Reading RG10 OOE. Telephone: 073-581302

Manchester, England . .. Jill E. Loney, Technomedia ltd., 216 Longhurst Lane, Mellor,Stockport SK6 5PW. Telephone: 061427-5660

Continental Europe ... Andre Jamar, Rue Mallar 1,4800 Verviers, Belgium. Telephone: (087)22-53-85

To~yo, Japan ... Haruo Moribayashi, InternattonalMedia Representatives ltd., 2-29 Toranomonl-chome, Minato-Ku, Tokyo 105 Japan. Telephone: 502-0656

PRODUCTION DIRECTORSJoseph P. Stenza

Diane C. McGrath

March 26-27 Washington. D.C.Hazardous Industrial Materials.George Washinglon Universily

Fcc: $325. Write: Director. ContinuingEngineering Education. George Washington University. Washington. D.C.20052

March 26-28 San Francisco.Calif.Occupational Dermatology Symposium. National Institute of Occupational Safely and Health (NIOSH).and the University of California

Fcc: $200. Wrire: Extended Programs inMedical Education. University of California Hospital. San Francisco. Calif.94143

March 26-30 Boston, Mass.E\'aluation and Control of Occupational Hazards: Basic Skills. HarvardUnivcrsity

Fcc: $500. Write: Short Course Coordinator, Dept. of Environmental HealthSciences. Ilarvard School of Public Health,665 Huntington Ave .. 130ston. Mass.02115

('all for Papers

March I deadline2nd Annual Meeting of the International Society of Petroleum IndustryBiologists. Sociely of Petroleulll Industry Biologists

Conference will be held November12-14. 1979 at Arlington. Va. Wrirc:Geraldine V. Cox. American PetroleumInstitute (API). 2101 LSI .. N.W. Washington, D.C. 20037

March 20 deadlineThe 2nd Symposium on the Transferand Utilization of Particulate ControlTechnology. Industrial EnvironlllentalResearch Laboralory. U.S. EPA

Meeting will be held on July 23-27.1979 at Denver. Colo. Wrire: Fred P.Venditti. Program Chairman. DenverResearch Inslilute. University of Denver.P.O. flox 10127. Denver. Colo. 80208

March J I deadline6th International Conference on liquefied Natural (;as. I nternational GasUnion. and the Institute of Gas Technology.

Conference will be held April 6-11.19XO in Kyolo. Japan. Write: David Roc.SccrL'tary. Progr:111l11ll: COl1lmittee. British(;'\S ('nrp.. 59 I3ryanslon St .. London.WI i\ 2i\/l'ngland

ES&T FEBRUARY 1979 VALID THROUGHJUNE 1979

ADVERTISED PRODUCTS, I 2 3 4 5 67 8 9 10 II 12 13 14 15 16 17

18 19 20 21 22 23 24 25 26 27 2829 30 31 32 33 34 35 36 37 38 3940 41 42 43 44 45 46 47 48 49 5051 52 53 54 55 56 57 58 59 60 6162 63 64 65 66 67 68 69 70 71 7273 74 75 76 77 78 79 80 81 82 8384 85 86 87 88 89 90 91 92 93 94

NEW PRODUCTS, 101 102 103 104 105 106 107108 J09 110 111 112 113 114 115 116 117 118119 120 121 122 123 124 125 126 127 128 129130 131 132 133 134 135 136 137 138 139 140141 142 143 144 145 146 147 148 149 150 151152 153 154 155 156 157 158 159 160 161 162163 164 165 166 167 168 169 170 171 172 173174 175 176 177 178 179 180 181 182 183 184185 186 187 188 189 190 191 192 193 194 195

TO VALIDATE THIS CARD, PLEASE CHECKONE ENTRY FOR EACH CATEGORY BELOW,

NAME,

TITLE,

FIRM,

STREET,

CITY,

STATL

PHONE, __J _

Intensity of product need:o 1. Have salesman callo 2. Need within 6 monthso 3. Future project

Employees atthis location:o LUnder 25o 2. 25 - 99o 3. 100·29904. 300·499o 5. 500·999o 6. 1000· 2999o 7. Over 3000

Areas of yourresponsibility:o A. Air pollution onlyo B. Water pollution onlyo C. Waste treatment onlyo D. Air & Water pollutionU E. Air & Waste treatmentOF. Water & Waste treat.o G. Air/water/Wasteo H. Other Environmental

This copy of ES&T is . .o 1. Personally addressed

to me in my nameo 2. Addressed to other

person or to my firm.

PrinC"iPal product towhich my work relates:o A. Oil/Gas/Petroleumo B. PlasticsfResinso C. Rubbero D. Drugs/Cosmeticso E. food/Beverageso F. Textile/Fibero G. pulp/Paper/Woodo H. Soaps/Cleanerso I. Paint/Coating/lnko J. Agrichemicatso K. Stone/Glass/Cemento L. Metals/Miningo M. Machineryo N. Auto/ Aircrafto O. Instrument/Controlso P. Inorganic Chemicalso Q. Organic Chemicalso R. Other Manufacturingo S. Design/Constructiono T. Utilitieso U. Consulting Serviceso v. Federal Governmento W. State Governmento X. Municipal Governmento Y. Education

Membership status:o 1. J am an ACS membero 2. Not an ACS member

Circle 94 forSUbscriptionform to ES&T

III II I NO POSTAGENECESSARY

IF MAILEDIN THE

UNITED STATES

BUSINESS REPLY CARD

P.O. BOX #7826PHILADELPHIA, PA 19101

EnvironmentalScience & Technology

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POSTAGE WILL BE PAID BY ADDRESSEE

111111 NO POSTAGENECESSARY

IF MAILEDIN THE I

ljNITED STATES J

BUSINESS REPLY CARD

P.O. BOX #7826PHILADELPHIA, PA 19101

EnvironmentalScience & Technology

Philadelphia, Pa.Permit #27346

POSTAGE WILL BE PAID BY ADDRESSEE

FIRST CLASS

I,,•,,•I1iI1----------------------------------------------------------------------,,II,II,,

tlTcle 94 forSUbscriptionform to E5&T

Membership status:o 1. I am an ACS membero 2. Not an ACS member

Princ'ipal product towhich my work relates:o A. Oil/Gas/Petroleumo B. Plastics/Resinso C. Rubbero D. Drugs/Cosmeticso E. Food/ Beverageso F. Textile/Fibero G. Pulp,! Paper/Woodo H. Soaps/CleanersU I. Paint/Coating/Ink[J J. Agrichemicalso K. Stone/Glass/Cemento l. Metals/ Miningo M. Machineryo N. Auto/Aircrafto O. Instrument/Controlso P. Inorganic ChemicalsU Q. Organic Chemicalso R. Other Manufactunngo S. Design/Constructiono T. Utilities[I U. ConSUlting Serviceso V. Federal Governmento W. State Governmento X. Municipal Governmento Y. Education

l'his copy of ES&T is ..["I 1. Personally addressed

to me in my nameo 2. Addressed to other

person or to my firm.

Areas of yourresponsibility:o A. Air pollution onlyo B. Water pollution onlyo C. Waste treatment onlyo D. Air & Water pollutionII E. Air & Waste treatmentEi F. Water & Waste treat.o G. Air/Water/Wasteo H. Other Environmental

TO VALIDATE THIS CARD, PLEASE CHECKONE ENTRY FOR EACH CATEGORY 8ELOW,

Intensity of product need:o 1. Have salesman callo 2. Need within 6 monthso 3. Future project

Employees atthis location:o 1. Under 2502.25·99o 3. 100 - 299o 4. 300 - 499o 5. 500·999o 6. 1000· 2999o 7. Over 3000

617283~

5061728394

107118129140151162173184195

51627384960718293

106117128139150161172183194

41526374859708192

105116127138149160171182193

VALID THROUGHJUNE 1979

31425364758698091

ZIP,

104115126137148159170181192

21324354657687990

103114125136147158169180191

11223344556677889

102113124135146'57168179190

101112123134145156167178189

ADVERTiSED PRODUCTS,7 8 9 10 11

18 19 20 21 2229 30 31 32 3340 41 42 43 4451 52 53 54 5562 63 64 65 6673 74 75 76 7784 85 86 87 88

ES&T FEBRUARY 1979

NEW PRODUCTS,108 109 110 111119 120 121 122130 131 132 133141 142 143 144152 153 154 155163 164 165 166174 175 176 177185 186 187 188

PHONE. ( .) _

STATE, __

STREET,

TITLE, _

FIRM, .

CITY,

,;,,II,I,,I______________________________________________________ _____________ ~_ •. J,1,r,IIIIIIIIIIIrrIrIrrII,rIIIIII

•,,,,,,,,I,,1,II,IIII

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