ORIGINAL PAPER

Investigation of hydrogeochemical processes and groundwaterquality in Upper Vellar sub-basin Tamilnadu, India

K. Saravanan1& K. Srinivasamoorthy1 & S. Gopinath1

& R. Prakash1& C. S Suma1

Received: 28 September 2015 /Accepted: 8 February 2016# Saudi Society for Geosciences 2016

Abstract An attempt has been made in the Upper Vellar sub-basin to assess the hydrogeochemical processes influencingthe water chemistry along with suitability of water for domes-tic and agricultural utilities. A total of 35 groundwater sampleswere collected for two different seasons, premonsoon (PRM)and post monsoon (POM), and analyzed for major cations,anions, and trace elements. The obtained results indicate thatthe dominance of silicate weathering, ion exchange process,and anthropogenic and microbial activities alter the chemistryof groundwater. The Piper plot suggests the facies evolutionfrom Ca-HCO3, Ca-Mg-Cl and mixed Ca-Na-HCO3 and Na-Cl fluxes influencing the water chemistry. The ionic ratio plotssuggest the predominance of Na+, Ca2+, HCO3

− and Cl− indi-cating the silicate minerals dissolution and anthropogenic ac-tivities. All the trace elements are within the scale; however,Zn exceeds the WHO standard. The stability plot suggestssamples representing kaolinite field during PRM and evolvestowards montmorillonite and chloride field during POM infersthe dissolution of silicates minerals and ions from host rocks.According to the WHO standard, 23% of PRM and 6% ofPOM water samples exceed the maximum permissible limitsfor drinking purposes.

Keywords Geochemical characteristics .Water qualityparameters . Ionic exchanges . Rock water interaction .

Upper Vellar

Introduction

In hard rock terrain with arid and semi-arid climatic conditions,all the water requirements are met with sub-surface water dueto reducing surface water resources, changing climatic condi-tions, growing population, industrialization, and intensive agri-cultural, and urbanization activities have put high demand forgroundwater especially in growing countries like India(Srinivasamoorthy et al. 2011). Besides, the unawareness ofgroundwater significance and absence of regular legislativemethods have created a huge pressure on groundwater bothquantitatively and qualitatively; hence, appraisal of chemicaland physical parameters of groundwater is essential for effec-tive groundwater planning and management to meet the in-creasing water requirements (Sophocleous 2000). The concen-tration of the chemical species is due to various processes suchas precipitation, rock water interactions, prolonged storage ofwater into the aquifer, effective mineral dissolution and humanactivities (Vasanthavigar et al. 2010). Owing to these processes,the chemical composition of groundwater is altered with re-spect to space and time, and the concentration of the chemicalspecies increases along the groundwater flow path (Sharif et al.2007; Suma et al. 2014 and Rattan et al. 2005). Based on thechemical compositions and hydrogeological process, thegroundwater quality is categorized for drinking, industrialand agricultural purposes (Subramani et al. 2009). All overthe world, research community have paid attention to studythe hydrochemical process and quality of groundwater(Krishna Kumar et al. 2008) in Manimuktha river basin,Salem district of Tamilnadu, India (Nagaraju et al. 2014) inGuntur district of Andhra Pradesh (Subba Rao et al. 2011) inVaraha river basin in Andhra Pradesh (Jinzhu et al. 2008) inShiyang river basin, China, (Odukoya et al. 2013) in Lagosprovince of Nigeria in mid-Western coastal aquifer system ofKorea and by Edmunds et al. (2003) in chalk aquifer

* K. Srinivasamoorthymoorthy_ks@yahoo.com

1 Department of Earth Sciences, School of Physical, Chemical andApplied Sciences Pondicherry University, Puducherry, India

Arab J Geosci (2016) 9:372 DOI 10.1007/s12517-016-2369-y

of Berkshire, UK. The primary activity in the proposed studyarea is agriculture followed by industries like sago factories,transport, textiles, paint industries and food processing units.The net groundwater availability in the study area accounts28,402ham (10,000m2), and gross draft for agricultural irriga-tion activities is 54,492ham and 643ham for domestic andindustrial utilities. Overall, the net deficiency of groundwaterin the study area is 26,733ham (CGWB 2008). Due to thedeficiency of surface water sources, non-perennial river con-ditions and growing water requirements have created hugepressures on groundwater in terms of quality and quantity.Hence, an attempt has been made to assess the hydrochemicalprocesses influencing water chemistry along with assessingsuitability of groundwater quality for domestic and irrigationpurposes.

Description of study area

The Upper Vellar sub-basin is located in Salem and partsof Perambalur districts of Tamilnadu (Fig. 1), lying be-tween 78° 14′ and 78° 58′ E longitude and 11° 24′ and11° 53′ N latitudes covering a total area of 1804km2. Theriver Vellar originates in Siddhery and the Kalrayan hillsof Eastern ghats, runs 74km towards East, and configuresriver Swedha at Thiruvalandurai in the Perambalur dis-trict. The study area experiences tropical climate withannual temperatures ranges between 20 and 42°C. The

annual rainfall over the area varies from 640 to1100mm , and the major part received during NorthEast monsoon from September to October followingSouth West monsoon from June to August.

Geology

The geology of the study area is predominantly underlain bycrystalline rocks of Achaean age with a major share ofgneisses encompassing 69% of the study area and charnokitecovering 31% of the study area followed by 0.14, 1, and 0.8%of pyroxene, amphibole granulite, and mylonite, respectively.The study area experienced dominant tectonic activities androcks holding evidences of shearing activities such as weath-ered, joints, fractures, foliations, and lineation. The well-known Attur-Salem shear zone runs in an E–W trend(Biswal et al. 2010). The river course is covered by recentvalley fills and alluvium soil covers (Fig. 1). The geomorphol-ogy of the study area represents mixed morphological featuressuch as structural hills, pediplain, denudation hill, pediments,and flood plains. The structural hill ranges are located in thenorthwestern and northeastern parts of the study area, whereasthe southwestern and eastern parts are occupied by gentlyundulating and dotted relic isolated hillocks; the pedimentsare occupied in foot hills, and the flood plains are noted alongriver courses.

Fig. 1 Location, geology, and sampling points of the study area

372 Page 2 of 14 Arab J Geosci (2016) 9:372

Hydrology

Groundwater in the study area occurs in weathered portions ofrocks along joints and fractures. The occurrence and move-ment of groundwater in a hard rock terrain are restricted tofissures and joints in unweathered portion and porous zones ofweathered formations. The recent sediment deposits such asalluvium and colluviums comprised of boulders, cobbles,gravels, sands, and silts are noted in the foot hills and alongthe river courses with the thickness from a few meters to 25m.The ground water occurs under phreatic conditions in weath-ered mantle and under semi-confined conditions in the frac-tured zones. The thickness of the weathered and fracturedzones for charnokite ranges between 17 and 72mbgl withgroundwater discharge of 1.5 to 4Ls−1, and in gneisses, thethickness ranges from 5 to 94mbgl with discharging capacityof 0.21 to 1.5Ls−1. The discharge noted in the recent sedimentdeposits accounts as 0.44–0.73Ls−1. Due to excess withdraw-al, the groundwater level goes up to 27.4mbgl along the NWparts and about 10.72mbgl in SE parts of the study areaencompassing deeper water level along NW and shallow wa-ter level along the SE parts of the study area. The flow ofgroundwater mainly controlled by topography of the areaand flow in the regional direction of NE and SE directions

beside some of the local flows identified which infers minorscale topography features (Fig. 2). Groundwater extracts bydeep tube wells, and water level has already reached analarming excessive withdrawal condition.

Materials and methods

In order to assess the hydrogeochemical evaluation processand quality, groundwater samples were collected from 35 borewells for two different seasons namely pre monsoon (PRM)and post monsoon (POM) during the months of March andSeptember, respectively. The groundwater samples were col-lected in 1l polyethylene bottles soaked with 1:1 HNO3 acid,washed with double distilled water, and again rinsed with fieldsample water. Groundwater samples collected were analyzedfor major cations and anions using standard methods (APHA1995). The charge balances for the analysis were within±10%. The pH and electrical conductivity (EC) was measuredusing a digital conductivity meter at the time of sampling.Sodium (Na+) and potassium (K+) were measured by a flamephotometer, and the calcium (Ca2+), magnesium (Mg2+), bi-carbonate (HCO3

−), and chloride (Cl−) were analyzed by vol-umetric methods. SO4

− and PO4− were analyzed in

Fig. 2 Groundwater flow direction

Arab J Geosci (2016) 9:372 Page 3 of 14 372

spectrophotometer and F− using UV spectrometer. For thetrace elements, groundwater samples were filtered usingthe 0.45-μm membrane filter and acidified with ultrapurenitric acid to pH <2 and then stored at approximately 4°C.The trace elements analyzed were Sc, Ti, V, Ni, Cu, As,Se, Rb, Zr, Mo, Sn, Ba, Pb, and U using inductivelycoupled plasma–spec t rometer ( ICP MS) . Whi leperforming the analysis, two sets of internal standardswere run, one at the beginning and other in between theanalyses, to have a check on the accuracy and precision ofthe results.

Results and discussion

Groundwater chemistry

The pH of the groundwater samples varies from acidic toalkaline with ranges between 6.0 and 8.9 and 6.2 and 9.2 withmean values of 7.4 and 7.3 during PRM and POM seasons,respectively (Table 1). Acidic pH was noted along the re-charge area, and alkaline was noted along the discharge areas,during both the seasons. The range of pH was within themaximum permissible limit of WHO (WHO 2011). The totaldissolved solids (TDS) ranges between 216.00 and2490.00mgL−1and 190.00 and 2070.00mgL−1 with meanvalues of 1097.00 and 933.00mgL−1 during PRM and POM,respectively. When compared with the permissible limit of(WHO 2011) (1200mgL−1), a total of 77 and 94% of thesamples fall in maximum permissible limit during PRM andPOM seasons. The EC during PRM ranges between 410.00and 4710.00μScm−1 with a mean value of 2065.00μScm−1

a nd du r i ng POM be tween r ange s 344 . 00 and3760.00μScm−1with a mean of 1687.30μScm−1. Higher ECrecorded during PRMmight be due to the prolonged rockwaterinteraction. The higher EC and Cl− infer the influence of het-erogeneous processes such as natural and anthropogenic activ-ities (Srinivasamoorthy et al. 2012). The dominance of cationsand anions during PRM and POM follows the trend such asNa+>Ca2+>K+>Mg2+=HCO3

−>Cl−>NO3−>SO4

−>F−>PO4−.

The Na+ and Ca2+ were the dominant cations, with Na+

ranging between 151.00 and 1198.00mgL−1 and 48.00 and1258.00mgL−1 and with mean value of 443.40 and623.40mgL−1 for PRM and POM periods, suggesting influ-ence of silicate minerals leaching especially from Na+ andCa2+-associated minerals like plagioclases (2(Na+,Ca2+)AlSiO3O8), pyroxenes (Ca-Mg (Si2O6), and amphibole(Ca2Mg5Si8O22 (OH) 2). The maximum allowable limit forNa+ and Ca2+ is 200.00mgL−1, respectively (WHO 2011). Atotal of 3% of samples during PRM and 9% of samples duringPOM fall within the most desirable limit, and the remainingexceeds the maximum allowable limit. Calcium ranges be-tween 8.00 and 136.00mgL−1 and 20.00 and 524.00mgL−1

with mean values of 53.14 and 215.30mgL−1, respectively,during PRM and POM seasons. All the samples duringPRM were within the maximum allowable limit, and duringPOM, 46% of samples exceed the maximum permissible limitof WHO (2011). The other cations Mg2+ ranges between 3.60and 78.00mgL−1 and 9.00 and 187.00mgL−1 and with meansof 32.70 and 79.70mgL−1 and K+ ranges between 2.00 and290.00mgL−1 and 0.50 to 394.00mgL−1 with mean values of40.28 and 43.30mgL−1 during PRM and POM, respectively.When compared with both seasons, 9% of the POM samplesexceed the range of WHO (2011) of 150mgL−1. The magne-sium and K+ during both the seasons were within the permis-sible limits. The sources of Mg2+and K+ might be from disso-lution of pyroxene minerals and non-point sources like addingof K− fertilizer and Mg2+ nutrients in agricultural fields(Härdter et al. 2004).

In anions, the HCO3− ranges were noted between 127.00

and 564.00mgL−1 and 116.00 and 586.00mgL−1 with meanvalues of 340.57 and 385.40mgL−1 during PRM and POMseasons, respectively. The sources of HCO3

− might be fromdissolution of silicate and calcic minerals and from car-bonic acid of organic materials (Drever and Stillings1996; NosratAghazadeh and Mogaddam 2010) as wellas atmosphere sources (Srinivasamoorthy et al .2008).The chloride during PRM ranges between 89.00and 413.00mgL−1 and between 0.46 and 921.00mgL−1

with mean values of 243.48 and 368.60mgL−1 duringPOM. The increase in Cl might be due to the contributionfrom anthropogenic supplies such as domestic and indus-trial activities moreover from mineral dissolution of bio-tite, apatite, and hastingsite (Arina Khan et.al. 2014) iden-tified from the litho units of the study area containing Cl−

ions (Boomeri et al. 2006). The other anions NO3− and

SO4− were within the permissible limit except F− exceed-

ing the permissible limit. The NO3− in groundwater

ranges between 1.50 and 86.00mgL−1 and 1.00 and87.00mgL−1 with mean values of 14.72 and 19.70mgL−1

and SO4− from 2.00 to 62.00mgL−1 and 0.33 to

4.50mgL−1 with mean values of 9.80 and 0.86mgL−1 dur-ing PRM and POM seasons, respectively. Higher nitratein groundwater might be due to the process of nitrogenfixation of microbial process and usage of nitrogen fertil-izers in agricultural fields (Spalding and Exner 1993).Sulfate was within the most desirable limit of 200mgL−1

(WHO 2012) during both the seasons, and the POM sam-ples have lower ranges, indicating its higher dissolutioncapacity by water (Xu Dao2014). Fluoride in the ground-water ranges between 0.30 and 1.80mgL−1 and 0.08 and4.80mgL−1 with mean values of 0.780 and 2.29mgL−1

during both the seasons. Higher range of F (4.8mgL−1)was noted during POM in 3% of the samples, and 11%of the samples during PRM exceed the maximum allow-able limits of 1.5mgL−1 (WHO 2011).The sources of

372 Page 4 of 14 Arab J Geosci (2016) 9:372

fluoride might be from dissolution of fluoride associatedminerals like halogens and apatite (CaF) from the gneissesand charnocki te (Joshua Amarnath et al . 2015;Jagadeshan et al. 2014). Anthropogenic sources of fluo-ride are also from agricultural practices (Motalane andStrydom 2004). In terms of average wise except Ca2+

and Cl−, all other elements were within the scale(Fig. 3); however, the Mg2+ was within the scale duringPRM but exceeds in POM. All the elements show in-creased ionic concentrations in PRM than POM, inferringthe effective contribution of ions from the host silicaterocks and anthropogenic sources through precipitation.

Table 1 Statistics of water chemistry during PRM and POM seasons (WHO-World Health Organisation)

Parameters Units Min Max Mean Stdev Min Max Mean Stdev Desirable limits Allowable limits

PRM POM (WHO 2011)

pH – 6.00 8.90 7.40 0.61 6.20 9.40 7.33 0.59 7–8.5 9.2

EC μScm−1 410.00 4710.00 2065.00 1100.27 344.00 3760.00 1687.30 865.20 – –

TDS mgL−1 216.00 2490.00 1097.00 584.45 190.00 2070.00 933.10 471.60 500 1500

Na mgL−1 151.00 1198.00 443.40 245.70 48.00 1258.00 623.40 307.90 – 200

K mgL−1 2.00 290.00 40.28 70.30 0.50 394.00 43.30 76.20 – –

Ca mgL−1 8.00 136.00 53.14 32.18 20.00 524.00 215.30 120.20 75 200

Mg mgL−1 3.60 78.00 32.70 17.34 9.00 187.60 79.70 44.50 50 150

Cl mgL−1 89.00 413.00 243.48 95.96 0.46 921.00 368.60 215.50 200 600

HCO3 mgL−1 127.00 564.00 340.57 114.12 116 586.00 385.40 110.00 – –

SO4 mgL−1 2.00 62.00 9.80 18.00 0.33 4.50 0.86 0.75 200 400

PO4 mgL−1 0.18 0.51 0.34 0.08 0.12 4.00 0.58 0.72 – –

NO3 mgL−1 1.50 68.00 14.72 17.11 1.00 87.00 19.70 20.20 – –

F mgL−1 0.30 1.80 0.780 0.40 0.08 4.80 2.29 7.90 – 1.5

H4SiO4 mgL−1 13.00 97.00 62.25 27.60 33.00 700.00 110.80 105.90 – –

Sc μgL−1 2.30 12.30 7.90 2.30 1.50 11.50 7.49 2.50 – –

Ti μgL−1 3.60 70.20 9.60 11.30 4.50 40.00 9.72 8.10 – –

V μgL−1 5.90 173.10 39.20 37.50 6.04 100.20 36.07 27.00 5000 –

Ni μgL−1 1.50 12.00 3.70 2.30 1.34 9.90 3.77 2.00 20 –

Cu μgL−1 4.80 115.30 19.80 20.20 4.80 67.80 16.80 10.70 1500 –

Zn μgL−1 17.70 18,090.00 1896.00 3912.90 53.70 13,830.00 2037.20 2671.70 50 –

As μgL−1 0.00 6.20 1.20 1.20 0.09 6.16 1.27 1.20 10 –

Se μgL−1 −0.30 16.10 2.70 3.50 −0.40 12.70 2.18 2.50 – –

Rb μgL−1 0.10 40.60 6.00 10.20 0.164 39.80 6.45 10.50 – –

Zr μgL−1 0.70 8.00 2.30 1.40 0.60 7.30 3.05 1.60 – –

Mo μgL−1 0.60 17.30 3.70 3.80 0.90 11.05 3.59 2.50 70 –

Sn μgL−1 0.40 5.50 1.00 0.90 1.03 3.20 1.03 0.50 – –

Ba μgL−1 14.20 803.00 152.40 158.50 18.20 1251.00 151.80 207.60 1000 –

Pb μgL−1 1.20 65.80 7.80 11.40 1.04 17.61 5.28 3.70 10 –

U μgL−1 0.10 15.90 2.90 3.30 0.12 17.12 2.72 3.60 – –

TH mgL−1 67.40 561.50 267.17 113.70 17.20 107.50 53.80 23.70 – 500

SAR - 2.70 59.11 14.18 14.09 0.69 37.60 10.40 8.30 – –

Na% % 58.40 97.06 82.51 8.70 36.40 90.40 67.30 13.80 – –

RSC mgL−1 35.00 516.00 254.60 120.90 −207.00 362.00 90.30 134.30 – –

PI % 89.40 136.86 115.12 10.80 56.26 115.50 87.90 14.00 – –

Mz 6.25 70.37 40.35 17.80 2.79 71.60 30.10 16.60 – –

Kelly ratio 1.38 29.55 7.092 7.04 0.17 9.40 2.62 2.09 – –

CAI-1 mgL−1 −2.23 0.11 −0.98 0.57 −959.87 0.02 −28.30 162.09 – –

CAI-2 mgL−1 −1.38 0.24 −0.60 0.36 −1.19 1.03 0.40 0.46 – –

EC electrical conductivity, SAR sodium adsorption ratio, CAI chloro alkaline index, TDS total dissolved solids, RSC residual sodium carbonate, SIsaturation index, TH total hardness, PI permeability index

Arab J Geosci (2016) 9:372 Page 5 of 14 372

Ionic ratio plots

The groundwater quality is mainly due to the interaction be-tween groundwater and aquifer minerals which have signifi-cant information to understand the genesis of groundwater(Wu et al. 2012; Yadava et al. 2012). Results obtained fromthe chemical analysis were used to know the process control-ling the hydrochemical behavior of aquifer system.

Effect of silicate weathering

The ionic ratio for Na+K vs. Tz during PRM and POM were0.9577 and 0.7737, respectively (Fig. 3a, b). This suggests

effective involvement of silicate weathering in hydrochemicalprocess, which mainly contributes sodium, potassium, andcalcium ions to the groundwater. The weathering of plagio-clase feldspars (albite, anorthite) and orthoclase (K− feldspar)identified in the study area are greatly responsible for thecontribution of Na+, K+, and Ca2+ due to higher susceptibleof feldspar to weathering (Ullman and Welch 1998; Dehnaviet al. 2011). The average range of pH observed during PRMand POM is 7.4 and 7.33, inferring dissolution of atmosphericCO2 and organic material decomposing process. The mixingof CO2 with water reacts with albite and anorthite mineralsand releases Na+, K

+, Ca2+, SiO2, and HCO3 which in turn isexhibited in the groundwater by the following reaction

2Albiteð Þ

Naþ;Kþð ÞAlSiO3O8 þ 2CO2 þ 3H2O ¼ Al2SiO5Kaoliniteð Þ

OHð Þ4 þ 2 Naþ;Kþð Þ þ 2HCO3 þ 4SiO2

CaAlSi2Anorthiteð Þ

O8 þ CO2þ 2H2O ¼ CaCO3Calciteð Þ

þAl2Si2OKaoliniteð Þ

5 OHð Þ4

The plotting of Mg2+/Mg2++ Ca2+ ratio is another wayto infer the silicate weathering processes. If the ratio is>0.5, it indicates effective silicate dissolution in crystallinecondition (Drever and Stillings 1996). The ratios notedduring PRM and POM were 0.5096 and 0.4436, respec-tively (Fig. 3c, d). The Ca2+ and Mg2+ might be derivedfrom pyroxene and amphibole group of minerals (augite,enstatite, and hornblende) noted in the litho units of the

study area and, during effective groundwater interaction,might have contributed Mg2+ and Ca2+. Higher Mg2+ dur-ing POM signifies ion exchange between Ca2+ and Mg2+

and higher electro negativity of Mg2+ than Ca2+ and disso-lution of Mg2+ affinity minerals (Hirokawa et al. 2001).The interaction between CO2 and water reduces the pHof the water and effectively releases Ca2+ and Mg2+ fromparent rocks by the following reactions.

Ca Mg Si2O6ð Þ þ 4CO2 þ 6H2O↔CaþMgþ 4HCO3 þ 2 Si OHð Þ4Pyroxeneð ÞCa2Mg5Si8O22 OHð Þ2 þ 14CO2 þ 22H2O↔2Caþ 5Mgþ 14HCO3 þ 8Si OHð Þ4Amphiboleð Þ

The Na vs. Cl ratio less than 1 infers ionic exchange pro-cess between Ca2+ and Na+ (Fig. 3g, h) and results in soften-ing of water (Naidu e t a l . 2012; Gopina th andSrinivasamoorthy 2015). Ca2+ and Mg2+ can exchange for

Na+ on exchangeable sites of clay minerals resulting in thereducing of Ca2+ and Mg2+ and increasing of Na+ in thegroundwater (NosratAghazadeh and Mogaddam 2010). TheNa vs. Cl ratios observed in the study area are 0.4496 and

0

100

200

300

400

500

600

pH Na K Ca Mg Cl HCO3 SO4 PO4 NO3 F H4SiO4

mgL

-1

PRM POM WHO - Scale

Fig. 3 Mean value of majorelements

372 Page 6 of 14 Arab J Geosci (2016) 9:372

0.7665 during PRM the POM seasons. The higher range dur-ing POM infers Na+ derivation from dissolution of Na+-bear-ing minerals and ionic exchange between Ca2+ and Mg2+.Some of the samples also signify Cl dominance and mightbe due to domestic, industrial effluents, human and animalwastes (Panno et al. 2006). Litho sources of Cl might alsobe from minerals like sodalite (Na4 (Si3Al3) O12 Cl) andhauyen (Na, Ca) 4–8 (AlSiO4)6 (SO4, Cl) 1–2 affiliated inalkaline igneous rock like feldspathoid and phosphatic miner-al of apatite Ca5 (PO4)3 (Cl, F, OH) (Jayabalan et al. 2012;Kincaid and Findlay 2009) isolated from the litho units of thestudy area. The ionic ratio plot Ca+Mg vs. HCO3+SO4

(Fig. 3e, f) suggests the contribution from chemicalweathering process (Subba Rao and John Devadas 2003) withranges of 0.0066 and 0.1885 for PRM and POM seasons,respectively. During POM, higher range infers greater Ca2+

and Mg2+ ions by chemical weathering process.

Trace element chemistry

The trace elemental concentration (Table 1) shows increasingo r d e r o f d om i n a n c e : Z n >B a > V>C u >T i > Pb>Sc>Pb>Rb>Ni>U>Zr>Se>As > Sn irrespective of boththe seasons. Higher concentrations were noted during POMindicating additional sources from rock leaching and anthro-pogenic sources. All the trace elements were within the limitsof WHO (2011), but the transition metal elements of Zn, Ba,Va, and Cu recorded with higher concentrations (18,090.00,803.10, 115.30, and 173.10 expressed in μgL−1) during PRMwhen compared with POM values of 13,830.00, 1251.00,100.20, and 67.82, respectively. The natural occurrence ofthese transition elements were mainly confined to silicaterocks (White 2013) in traceable level, and its usage in variousindustrial activities such as paint, auto mobiles, textiles, andfood processing industries (Kung 1989) are the probablesources into the groundwater environment. The concentrationof Vand Cu were within the standard limit, but for Ba, 3% ofsamples during POM exceeds the most desirable limits of1000μgL−1 (WHO 2011). During both the seasons, Zn record-ed the maximum ranges but within the scale. The sourcesmight be from silicate minerals like willenite (ZnSiO4),4CaZnSiO6) petedunnite, zincite (ZnO), gahnite (ZnAlO4),and spalerite (2ZnS) and also from industrial activities likeautomobile and paint industries and from agricultural seedprocessing industrials (Ghadimi et al. 2013; Osemwegieet al. 2013).

Hydro chemical phase’s evolution

The graphical tri-linear (piper 1944) diagram (Fig. 4) is usedto isolate the groundwater phase changes and genesis ofchemical parameters by plotting the concentration of majorcations and anions. The major cations and anions are clustered

according to their similar chemical characters. During PRM,most of the samples fall in mixed region of Ca-Na-HCO3

(17%) and Na-Cl (83%) indicating matured groundwater typedue to prolonged rock water interaction with higher Na+ re-leased from feldspar minerals and Cl− from anthropogenicsources. During POM, a shift in phases towards Ca-HCO3

(14%), Ca-Na-HCO3 (23%), Ca-Mg-Cl (14%), and Na-Cl(49%) is noted. The excess Ca2+, Mg2+, and HCO3

− duringPOM than PRMmight be due to additional supply of Ca2+ andMg2+ from Ca2+and Mg 2+affiliated minerals in aquifer hostrock mineral matrix such as plagioclase and pyroxenes min-erals as well as base ionic exchange of Ca2+, Mg2+ with Na+.The excess HCO3

−might be from silicate mineral weathering,atmospheric sources, and decomposition of organic materials.From the plot, it is inferred that excess alkalis (Na+K) over thealkaline earth (Ca+Mg) in PRM and shift towards alkalineearth in POM and strong acids (Cl−, SO4

−) exceeds the weakacid (HCO3) in both seasons. In general, the chemistry ofgroundwater is influenced by leaching of silicate minerals,anthropogenic activities, and ionic exchange process.

Chloroalkaine indexes

Chloroalkaine index (CAI-I, II) coined by Schoeller (1977)indicates the ion exchange between host rock and groundwa-ter, which is vital to know the base exchanges taking placeduring the groundwater flow (Sujatha and Rajeswara Reddy2003).The CAI is calculated using the formula:

CAI–I Cl−– Naþ þ Kþð Þ½ �=Cl−CAI–II Cl−– Naþ þ Kþð Þ½ �= SO4

− þ HCO3− þ CO3

− þ NO3−ð Þ

If there is an exchange between Ca2+ or Mg 2+ in thegroundwater with Na+ and K+ in the aquifer material, theabove said index is negative, and if there is a reverse ionexchange, then the index will be positive. In the study area,the range of CAI-I during PRM and POM seasons are−0.98343 and −28.331, respectively, and CAI-II ranges are−0.60965 and −0.7137, respectively. Comparing PRM, thePOM samples record with higher negative values signifyingeffective exchanges between Ca2+ andMg2+ in the groundwa-ter with Na+ and K+ in the aquifer matrix (Subramaniet al.2009).

Stability diagram

The stages of structural breakdown of minerals can beestablished by the stability field of the silicate minerals atlow temperature conditions (Garrels and Christ 1965). Waterinteracting with rocks alters thermodynamically upon unstableprimary minerals like silicon oxide, pyroxene, and feldsparsand produce new stable mineral clays that have a differentmineralogy when compared with parent rock. The changing

Arab J Geosci (2016) 9:372 Page 7 of 14 372

mineralogy is the key to decipher the geochemical processesin the groundwater samples due to higher mobility of Mg2+,Ca2+, and sometimes Si4+ that gets released from host rocksenters into groundwater, but lower ionic mobility elementslike Al, Fe (II), and Ti are conserved consequently, and asweathering proceeds, the bulk chemistry of residual rocksbecome more Al rich derived from silicate rocks (Ehlmannet al. 2011). The clay mineral kaolinite (Al4SiO10 (OH) 8)is formed by weathering of alumina silicate and feldsparsthat alter as kaolinite by release of ions such as Na+, Ca2+,

Mg2+ and K+ into groundwater. Further addition of cationsand excess H4SiO2 with kaolinite will result in a new claymineral smectite/montmorillonite (1/2 (Ca, Na) (Al, Mg,Fe) 4 (Si, Al) 8O20 (OH) 4 nH2O). The stability of ground-water in the study area has been attempted by plotting(Na+/H+), (K+/H+), (Ca2+/H+), and (Mg2+/H+) for thegroundwater in two different seasons of PRM and POMas a function of (H4SiO4) were plotted because of its pre-dominant presence in groundwater; moreover, these plotsinfer the possible sources.

PRM POM

Fig. 4 Ionic ratio plots

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During PRM for (Na+/H+) and (Ca2+/H+) systems, all thesamples that lie in kaolinite category infers the incongruentdissolution of feldspar minerals (Fig. 5) and kaolinite produc-tion and in POM due to the mixing of meteoric water withsilicate rocks increases the dissolution of H4SiO4 and Na+

from aquifer host rocks hence the shift from kaolinite fieldto Na – montimorillonite type is noted. The same trend also

obeys in the Ca – system. During PRM, samples lie in kaolin-ite field, and in POM, it moves towards Ca –montimorillonitedue to the effective dissolution of plagioclase minerals such asalbite and anorthite during POM. The Na+ and Ca2+ that getsprecipitated with alumina silicate as clay products and theexcess amount of Na+ and HCO3

− mix with groundwaterand leads to increasing of these ions in the groundwater.

2:33NaAlSi2O8 þ 8:64H2Oþ 2O2↔ Na0:33Al2:33Si3:6O10 OHð Þ2 þ 2Naþþ 2HCO3 þ 3:32 H4SiO4

Albiteð Þ Na−montmorilloniteð Þ7Al2Si2O5 OHð Þ4 þ Ca2 þþ 8H4SiO4a

2 þ 8H4SiO4 ↔ CaAl2SiO10 OHð Þ2 þ 2Hþþ 23H2OKaoliniteð Þ Ca−smectiteð Þ

During PRM, in the K+/H+ system, most of samples fall inkaolinite and muscovite field, and in POM, evolution towards

K− feldspar field is noted, inferring addition of H4SiO4 and K+

from K− feldspar by dissolution of rain water by following thereaction.

2 Naþ; Kþð Þ AlSiO3O8 þ 2CO2 þ 3H2O ¼ Al2SiO5 OHð Þ4 þ 2 Naþ; Kþð Þ þ 2HCO3 þ 4SiO2

Albiteð Þ Kaoliniteð Þ

InMg2+/H+ system, majority of samples (82%) during PRMfalls in kaolinite field, and 18% samples are also noted in chlo-ride type; during POM, the reverse is noted where 73% ofsamples is noted in kaolinite field and 27% of samples evolvetowards chloride due to the adding ofMg+2 andH4SiO4 derivedfrom biotite and muscovite bearing biotite gneissic rocks iso-lated in the study area by the following reaction.

Biotiteþ 14CO2 þ 7H2O↔Kaoliniteþ 2K þþ 3 Mg2þ

þ 3Fe2þ þ 14HCO3− þ 4SiO2

Drinking and domestic purpose

Total hardness

The quality of water is important for a healthy societybecause it is directly linked with human life. The

chemical characteristics of groundwater play an impor-tant role in classifying and assessing water quality forvarious purposes particularly with regard to drinkingand domestic. The moderate and soft water serve Ca2+

and Mg2+ for the metabolism of the human being; how-ever, the range exceeds which results in adverse healtheffects such as cardiovascular disease (Sengupta 2013),eczema (inflammation of the skin), and kidney stone for-mation (Keshavarzi et al. 2014). The total hardness (TH)of the groundwater is calculated according to SawyerMcCartly (1967) as

TH CaCO3ð Þ ¼nCa2þ þMg2

þo*50 meq=l ð1Þ

When compared with classification, a total of 88% ofthe samples during PRM are categorized as hard and very

0

1000

2000

3000

4000

5000

Sc Ti V Ni Cu Zn As Se Rb Zr Mo Sn Ba Pb U TH

µgL

-1

PRM POM WHO - SCALE

Fig. 5 Mean value of traceelements

Arab J Geosci (2016) 9:372 Page 9 of 14 372

hard and the remaining 12% as soft and moderately softwater type, inferring the long-time residence of water withhost rocks and dissolution of Ca and Mg associated min-erals from host rocks (Matter and Takashi 2007; FrancescoFrondini et al. 2014) During POM, 83% samples fall in softtype and 17% samples in moderately hard category. Thewater changes from hard to soft water type from PRM toPOM due to the dilution of chemical solutes throughadding of infiltration water into the aquifers and ionic ex-changes (Lakshmanan et al. 2003).

Suitability of water for irrigation activities

The development and maintenance of successful irrigationprojects not only depend on supply of irrigation water tothe land but also aim in controlling the solutes and alkali ofthe soil (Oster 1994).The factors influencing the aboveparameters can be judged using parameters like sodiumadsorption ratio (SAR), sodium percentage (Na %), resid-ual sodium carbonate (RSC), permeability index (PI), andmagnesium hazards (Mz).

Sodium adsorption ratio

Sodium concentration in water is important because of itspeculiar character to reduce the soil permeability and soiltexture (Mahanta and Sahoo 2012; Krishna Kumar et al.2008 Bronick and Lal 2004 and Bazzof et al. 1998). Anincrease in Na+ results in immobilization of other nutrientssuch as Ca, Mg, and K that causes deficiency of theseelements and overall reduction in crop productivity(Koyro et al. 2013). The sodium adsorption ratio(SAR) indicates the relative proportion of Na+, Ca2+,and Mg2+ and calculated using the formula (Richards,1954):

SAR ¼ Na= CaþMgð Þ=2f g � 1=2 ð2Þ

The classification of water on the basis of SAR asexcellent, good, and doubtful as attempted by Richards(1954) is given in Table 2. A total of 71 and 91% ofwater samples fall in excellent and good category and the

Table 2 Summary of waterclassification for differentpurposes

Classification scheme Categories Range Percentage of sample

PRM POM

TH (Sawyer McCartly 1967) Soft <75 3 83

Moderate hard 75–150 9 17

Hard 150–300 63

Very hard >300 25

SAR (Richards 1954) Hyper saline >564.13 37 77

Excellent <10 34 14

Good 10–18 8.5 9

Doubtful 18–26 20

Unsuitable >26

Na % Excellent <20 11

Good 20–40 2 34

Permissible 40–60 69 46

Doubtful 60–80 29 9

Unsuitable >80

RSD (Richards 1954) Good <1.25 70 100

Medium 1.25–2.5 8

Bad >2.5 22

Permeability index (PI) (Dabeen 1948) Suitable <25 17 69

Good 25–75

Maximum 83 31

Permeable >75

Mg—hazards (Szabolcs and Darab 1964) <50 Suitable 43 94

>50 57 6

Kelley’s ratio <1 Suitable 17 43

>1 83 57

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remaining as unsuitable during PRM and POM, andhigher percentage of samples were noted to fall in excel-lent and good category during POM might be due to theexcess supply of meteoric water into aquifer system dur-ing monsoons.

Na%

The Na% is important to assess the suitability of water foragricultural activities since Na+ combines with CO3 to alterthe soil into alkaline soil and reaction with Cl− leads in

Fig. 6 Ground water phasesdiagram

PRM POM Fig. 7 Stability diagram

Arab J Geosci (2016) 9:372 Page 11 of 14 372

forming saline soil. As per the irrigation suitability is con-cerned, both these soils are not suitable for cultivation pur-poses (Munir et al. 2006). The Na% are measured inmilliequivalents per liter and computed according to (Wilcox1955) using the formula:

Na% ¼ Naþ Kf g � 100= CaþMgþ Naþ Kf g ð3Þ

The Na% for the groundwater samples fall in permissibleand doubtful category with a total representation of 71 and80% of the samples during PRM and POM seasons, respec-tively, and the remaining samples fall in unsuitable category.In comparison with SAR, the excess Na% during POM indi-cates sources from rock dissolution.

Permeability index

Permeability index (PI) is essential for water with relationto soil for improvement of agriculture (Joshi et al. 2009).The PI values reflect the groundwater suitability for irri-gation where all the ions are expressed in milliequivalentsper liter.

PI ¼ Naþ HCO3ð Þ � 1=2f g= CaþMgþ Naf g � 100 ð4Þ

A total of 83 and 31% of groundwater samples duringPRM and POM exceeds the maximum permissible limit andremaining 17 and 75% of samples during both the seasons fallin good category.

Magnesium hazard

Generally, Ca2+ and Mg2+ maintain state of equilibriumwith water. Higher Mg2+ in water adversely affects thecrop yield (Bajwa et al. 1992) and changes soil as alkaline(Paliwal 1975). The Mg hazards ratios were formulatedusing the following expression developed by (Szabolcsand Darab 1964).

Mg ratio ¼ Mg= CaþMgð Þf g � 100 ð5Þ

A total of 57% of groundwater samples during PRM and94% of the samples during POM exhibit unsuitable for irriga-tion purposes indicating the effective host rock contribution ofthe alkaline earth (Ca+Mg) derived from magnesium richminerals matrix.

Kelly’s ratio

The Kelly’s ratio describes the ratio between Na+ and Ca2+

+ Mg2+ ions based on the presence of these ions in water.The ratio when greater than 1 signifies water unsuitable for

irrigation and <1 as suitable for irrigation purposes. TheKR is expressed as Kelly (1940) and Paliwal (1967)

KR ¼ Ka= Ca=Mgð Þf g*100 ð6Þ

During PRM, 17% of samples and 43% of the samplesduring POM lie in suitable category, and the remaining fallin unsuitable categories.

Conclusion

The chemical composition of groundwater in the study area isstrongly influenced by silicate and calcite minerals dissolutionand rock water interaction (Fig. 6). The dominant cations areNa, Ca, Mg, and K derived from silicate rocks. Higher HCO3

−

and Cl− indicate influence of organic matter, atmospheric con-tributions, silicate dissolution, and microbial contributions.Compared with PRM, the POM samples record with higherionic ratios. The increased Ca and Mg in POM infer sourcesfrom silicate minerals and ionic exchange process with Na andK. The stability diagram for groundwater samples formationof kaolinite during PRM and shift towards Ca, Na –montimorillonite during POM indicating adding of Ca andNa from litho sources (Fig. 7). The trace elements Ba exceedonly in POM; however, Zn during both seasons exceeds thepermissible limit. The water quality for drinking and irrigationutility showed changing patterns with reference to seasons,where samples from POM recoded good quality when com-pared with PRM indicating the influence of infiltrating mete-oric water into the aquifers. The concentrations of soluteswere found to be increasing from recharge to discharge areaindicating the influence of geology and anthropogenic activi-ties altering the groundwater chemistry.

Acknowledgments The first author acknowledges University GrandCommission (UGC) for providing fund through the BSR fellowship(Ref. No. PU/ES/2013 – 2014) to carry out this research work. Theauthors would also like to thank two anonymous reviewers for theirconstructive comments.

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