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ScienceDirect Aquatic Procedia 4 (2015) 685 – 692

INTERNATIONAL CONFERENCE ON WATER RESOURCES, COASTAL AND OCEAN ENGINEERING (ICWRCOE 2015)

Assessment of Groundwater Quality for Drinking Purpose in Rural Areas Surrounding a Defunct Copper Mine H. Annapoorna*a, M.R. Janardhanab a

DOS in Earth Science, University of Mysore, Manasagangotri, Mysore, 570006.India. b Dept. of Geology, Yuvaraja’s College,University of Mysore, Mysore, 570005. India.

Abstract The suitability of groundwater quality of 22 wells located in the rural areas surrounding Ingaldhal defunct copper mine in Chithradurga district of Karnataka state was assessed for drinking purpose based on the various water quality parameters. Standard methods for physicochemical analysis of groundwater samples were employed. The results of analysis carried out showed the following concentration ranges: pH (7.61-8.34), EC (950-3120μS/cm), TH (410-1400mg/l), TDS (594-1913mg/l), F(0.15-1.43mg/l), NO3- (14-162mg/l), HCO3- (417-574mg/l), SO42- (68-286mg/l) and Ca2+ (59-150mg/l), Mg2+ (49-250mg/l), Na+ (38-290mg/l), K+ (6-58mg/l). The ionic dominance for the major cations and the anions respectively were in the order of Mg2+ > Na+ > Ca2+ > K+ and HCO3- > Cl- > SO42- > NO3- > Fe- > F- > CO3-. Most of the samples analyzed were above the Guidelines set by both national (BIS) and international (WHO, 2011) bodies for drinking water. Geographical Information System (GIS) capabilities are used to classify zones with acceptable groundwater quality for drinking purpose. The Gibbs diagrams show that the groundwater samples fall both in the rock and evaporation dominance fields as well as about 18% samples fall outside the defined fields indicating integrated mechanisms for hydrochemistry such as high weathering and low rates of evaporation in addition to input from the anthropogenic activities. According to plots on the piper diagram the groundwater of the Ingaldhal and surrounding regions consists of 4 hydrochemical types, viz., Ca-Mg-HCO3 type (n=9), Ca-Mg-SO4 (n=6), mixed Ca-Na-HCO3 (n=6) and Na-Cl type (n=1). Assessment of groundwater samples from various parameters indicates that groundwater in most part of the study area is chemically unsuitable for drinking purpose. © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license © 2015 The Authors. Published by Elsevier B.V. (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-reviewunder under responsibility of organizing committee of ICWRCOE Peer-review responsibility of organizing committee of ICWRCOE 2015 2015. Keywords: Groundwater quality; Drinking water; Major ions; Copper mine

* Corresponding author. Tel.: +0-944-977-9260, +0-934-211-6241 E-mail address: [email protected], [email protected]

2214-241X © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of organizing committee of ICWRCOE 2015 doi:10.1016/j.aqpro.2015.02.088

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H. Annapoorna and M.R. Janardhana / Aquatic Procedia 4 (2015) 685 – 692

1. Introduction Distribution of fresh water resources is uneven throughout the world and the fresh water availability is becoming scarce day by day owing to population growth and diverse human activities. In the absence of fresh surface water resources, groundwater is exploited to meet the demand exerted by various sectors. Spatial variation in the quality of groundwater in response to local geologic set-up and anthropogenic factors warrants the evaluation of the quality of groundwater for any purposes including that for human consumption. Assessment of the water quality for drinking purpose involves the determination of the chemical composition of groundwater and the remedial measures for the restoration of the quality of water in case of its deterioration demand the identification of possible sources for the contamination of groundwater. This paper presents findings on the chemical composition of the groundwater and investigates the possible geogenic and anthropogenic sources for chemical solutes. Many researchers across the globe (Babiker et al., 2007; Vennila et al., 2008; Shomar et al., 2010 and Magesh et al., 2013) have carried out studies with spatial technologies and interpreted the quality of groundwater. Mapping the spatial distributions of major elements and their interpolation with the geology and land use/land cover maps in GIS environment (Bruce et al., 2003; Zhang et al., 2013) have contributed for the better understanding of the chemical processes of water and the methods of their acquisition. The present study pertains to the evaluation of the physico-chemical characteristics of the groundwater in and around a defunct copper mine located in a semi-arid region wherein the people of the terrain are entirely dependent on the groundwater for their needs. The paper also provides an assessment on the suitability of the groundwater for drinking purposes. 2. Study Area Ingaldhal is a small village in the outskirts of Chitradurga town of Karnataka state. The study area lies between 654130.590 - 658706.818 E longitudes and 1570329.645 – 1565527.110 N latitudes (Fig. 1a) and covers an area of 168. 44 sq. km. The area had hosted a copper mine and defunct now due to low recovery of copper and other base metals. Geomorphologically, the area represents an undulating plain with linear structural hills and valleys exposing volcano-sedimentary sequence. The average annual precipitation is around 600 mm and its climate is essentially semi-arid. The aquifer is recharged by direct infiltration of precipitation, the main source of groundwater recharge. Groundwater in the study area occurs under water table conditions ranging in depths from about 24 m to 55 m (Fig. 1b). The average annual temperature varies from 40°C to 20°C. Drainage of the study area is of ephermal type and there are no surface water bodies in the study region. (a)

(b)

44

44 24

44

40

36

32

Fig.1. (a) Location map of the study area; (b) Map showing the location of the sample stations and depth to the water table in the study area.


3. Materials and Methods Groundwater samples from 22 bore wells (Fig. 1b) of the unconfined aquifer were collected in duplicate in new pre-cleaned polypropylene bottles (1L capacity) in the month of October 2013 (post-monsoon season). Before collecting the water samples, the water was pumped out from bore wells for about 10 min to remove stagnant groundwater. Prior to sampling, water was filtered through 0.45 Millipore membranes. The physical parameters measured and recorded in the field are colour, taste, odour, temperature, EC (using conductivity meter) and pH (using pH meter). Groundwater samples collected were colourless, odourless but were very unpleasant to taste. As far as temperature is concerned there was not much difference between the groundwater and that of atmosphere excepting in a few samples wherein the temperature varied between 2 and 4 oC. Water samples meant for cation estimation were acidified with 1% HNO3 to decrease the pH value to 2. Water samples meant for NO 3- estimation was acidified with H2SO4 to decrease the pH value to 2. All samples were stored at 4 0C. Calcium (Ca2+), magnesium (Mg2+), carbonate (CO32-), bicarbonate (HCO3-) and chloride (Cl−) were analyzed by volumetric titration methods, sodium (Na+) and potassium (K+) were measured using the flame photometer, sulphate (SO 42−), nitrate (NO3−) and fluoride (F-) were determined by spectrophotometric technique as per the methods described by the American Public Health Association (APHA 1995). The analyses were completed within a week from the date of collection of the water samples at the chemical laboratory of Mines and Geology Department, Government of Karnataka. Charge balance errors (CBC) were calculated using the following formula (Freeze and Cherry 1979) and are found within the permissible limit of ±10 %. CBC ¼ h_XZmc _XZma_=_XZmc þXZma_i_100. Where Z is the ionic valance, mc is the molarity of cation species and ma is the molarity of anion species. Table 1 provides physico-chemical data of 22 groundwater samples of the present study. The analytical data were taken in to GIS environment. In GIS, spatial distribution maps were prepared for the selected parameters, which show significant variation. 4. Results and Discussion 4.1. Physico-chemical characteristics Groundwater of the study area in terms of me/l, is characterized by Mg + > Na+ > Ca2+ > K+ and HCO3- > Cl- > SO42- > NO3- > F- > CO3-. Average contribution of individual cations to total cations is 22.09 % Ca2+, 49.86 % Mg+, 28.81 % Na+ and 0.24 % K+. On an average, anions are made up of 51.62 % HCO3-, 14.55 % SO42-, 27.18 % Cl-, and 6.64 % NO3-. Averages me/l content of (Ca2+ + Mg+) is higher than that of (Na+ + K+) and averages me/l content of (HCO3-+SO42-) is higher than that of (Cl-+NO3-). 4.2. Natural mechanisms controlling the hydrochemistry Plots of Gibbs ratios of groundwater samples on Gibbs diagrams (Gibbs 1970) can provide information on the relative importance of three major natural mechanisms controlling water chemistry: (1) atmospheric precipitation (2) mineral weathering, and (3) evaporation and fractional crystallization. On the bivariate TDS versus Gibbs ratio 1 [weight ratio of (Na++K+)/(Na+ + K+ + Ca2+)] diagram (Gibbs diagram), groundwater samples (n = 15) plot either in rock dominance or very close to the boundary line between rock dominance and evaporation dominance fields (Fig. 2a). Four samples plot in evaporation dominance field and two samples plot outside the three defined fields. Gibbs diagrams together indicate rock weathering and evapo-concentration of solutes. In addition, samples which fall on outside the designated fields may indicate the role of anthropogenic activities in altering the chemistry of the groundwater.

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Table 1. Physico-chemical characteristics of the groundwater of the Ingaldhal region Sl. No

pH

EC

TDS

TH

Ca2+

Mg2+

Na+

K+

HCO3-

CO3-

Cl-

NO3-

F-

SO4 2-

W1

7.43

3489

1937

1440

56

325

120

6

877

0

372

170

0.19

350

W2

7.71

3253

1882

1320

75

283

123

6

724

0

412

154

0.18

364

W3

7.55

2002

1154

860

96

155

56

2

586

0

171

51

0.18

280

W4

7.43

1686

946

720

86

126

51

0

481

0

143

50

0.2

200

W5

7.55

1059

597

356

42

63

47

1

431

0

42

106

0.16

51

W6

7.48

1235

697

480

61

84

55

1

386

0

98

80

0.24

95

W7

7.58

1613

844

688

93

112

52

1

623

0

134

36

0.24

75

W8

7.42

2316

1317

1000

112

80

64

0

623

0

255

80

0.13

215

W9

7.68

2316

1336

916

91

172

102

2

536

0

316

95

0.18

190

W10

7.24

1928

1032

828

117

134

56

0

715

0

148

30

0.14

140

W11

7.48

1325

720

468

66

76

86

0

563

0

76

60

0.09

45

W12

7.71

1170

638

440

56

75

63

0

451

0

78

41

0.12

75

W13

7.55

1219

693

368

50

61

108

0

544

0

87

45

0.17

40

W14

7.43

2025

1196

600

59

113

183

2

485

0

288

33

0.2

176

W15

7.58

1553

857

472

72

73

135

2

578

0

118

28

0.18

110

W16

7.28

2440

1407

548

67

95

299

9

833

0

308

13

0.18

90

W17

7.58

1307

743

444

46

82

92

1

367

0

137

80

0.11

92

W18

7.62

2126

1263

588

54

13

212

2

573

0

224

20

0.13

252

W19

7.68

1408

815

460

83

63

108

2

461

0

109

110

0.06

80

W20

7.24

2246

1355

560

83

100

231

2

500

0

364

150

0.08

75

W21

6.84

2265

1279

884

126

142

108

0

707

0

294

96

0.07

60

W22

7.35

1467

815

508

58

91

97

3

510

0

129

105

0.2

47

EC: μS/cm at 25°C. All values, except pH are in mg/l Table 2. Statistics of Physico-Chemical parameters Parameter pH EC (μs/cm) TDS (mg/l) TH (mg/l)

Min 6.84 1059 597 356

Max 7.71 3489 1937 1440

Mean 7.47 1884.00 1069.23 679.45

Standard Deviation 0.20 648.26 378.33 293.69

Ca2+ (mg/l)

42

Mg2+ (mg/l)

13

126

74.95

23.52

325

114.45

Na+ (mg/l) K+ (mg/l)

71.21

47 0

299 9

111.27 1.91

66.22 2.33

HCO3- (mg/l)

367

877

570.64

134.31

CO3- (mg/l)

0

0

0

0

Cl- (mg/l) NO3- (mg/l) F- (mg/l) SO42- (mg/l)

42 13 0.06 40

412 170 0.24 364

195.59 74.23 0.16 141

111.24 45.12 0.05 98.9


4.3. Hydrochemical facies Hydrochemical facies of groundwater can be evaluated by plotting the major cations and anions such as Ca 2+, Mg2+, Na+, K+, CO32−, HCO3−, SO42− and Cl− (in me/l) on Piper’s trilinear diagram (Piper 1944, 1953). On the diamond-shaped Piper diagram, the plot (Fig. 2b) shows the total dominance of alkaline earth metals (Ca2+, Mg2+) over the alkalies (Na+, K+); and dominance of strong acids (SO42−, Cl−) over weak acid (CO32−, HCO3−). In all samples (n = 22) of the groundwater, alkaline earths exceed alkalis (n = 21) and strong acids (SO 42- and Cl-) exceed weak acid (HCO3-) (n = 13). In 9 samples, carbonate hardness (secondary salinity) exceeds 50%. In 12 samples, none of the cation-anion pairs exceeds 50%. In 1 sample non-carbonate alkali (primary salinity) exceeds 50% (Fig. 2b). The plot displays that the chemistry of the groundwater belongs essentially to CaMgHCO 3 (n = 9), CaMgSO4 (n = 6), NaCl (n = 1) but groundwater from five bore wells reveals the signature of mixed type hydrochemical facies.

Fig.2. (a) Bivariate TDS versus Gibbs ratio 1: Gibbs diagram; (b) Piper (1944) tri-linear diagram showing chemical character of the groundwater of Ingaldhal region.

4.4. Assessment of Groundwater quality for drinking purposes Groundwater quality may be degraded as a result of natural processes or human activities. Evaluation of groundwater quality for drinking determines its suitability for different purposes depending upon the specific standards set by various agencies including the drinking water standards of WHO (2011). The values of the physical parameters of the groundwater in the Ingaldhal region indicate that pH ranges from 6.84 to 7.71 with a mean value of 7.47 (Table 2), which indicates the alkaline nature of groundwater of the study area. The pH value of the water thus does not lead to the dissolution of heavy metals in the mineralized part of the study area. As per the (WHO, 2011) standards, all the samples fall within the recommended limit (6.5 to 8.5) for human consumption. The EC ranged from 1059 to 3489 μS/cm at 25 o C, with a mean of 1,884 μS/ cm. EC was above the maximum permissible limit (1,400 μS/cm) in 72.72% of groundwater samples as per WHO 2011 standards. Almost all the samples exceed the desirable limit for EC of 500μS/cm. The higher EC may cause a gastrointestinal irritation in human beings. Although the large variation in EC is mainly attributed to geochemical process like ion exchange, reverse exchange, evaporation, silicate weathering, rock water interaction, sulphate reduction and oxidation processes (Ramesh 2008), in the study area the enrichment of salt in groundwater may possibly be due to

689

690


evaporation effect and anthropogenic including agricultural activities. High variation in the SD values of EC (Table 2) probably indicates the variation in the sources. TDS estimated by residue on evaporation method vary in the range of 597–1937 mg/l with a mean value of 1,069 mg/l. As per TDS classification, 50% of the wells are brackish (TDS >1,000) water type and 50% wells are fresh (TDS Na+ >Ca2+ >K+ and HCO3- > Cl- >SO42> NO3- > F- > CO3-. The concentration of Ca2+ in the study area ranges from 42 to 126 mg/l with an average of 75 mg/l. The desirable limit for Ca2+ for drinking water is specified as 75 mg/l (WHO 2011). As per standards the groundwater from this area is safe to use. The major source of Ca 2+ in the groundwater is due to ion exchange of minerals from rocks of this area. Further, this may also be due to the presence of CaCO 3, CaSO4, CaMg(CO3)2 minerals and soils by water. Mg2+ concentration is higher in the groundwater samples of the study area, varying from 13 to 325 mg/l with an average value of 115 mg/l. The spatial patterns of Mg2+ are illustrated in Figure 3d. It can be observed from the tables (Table1 and 2) that magnesium concentration in the groundwater from 21wells is very high and unsuitable for some of the domestic applications (WHO, 2011). Mg2+ may probably have been derived from the same source as that of Ca 2+. Na+ concentration in groundwater ranges from 47 to 299 mg/l with an average of 112 mg/l. According to WHO (2011) guidelines, the maximum admissible limit is 200 mg/l. Groundwater samples of W16, W18 and W20 wells show concentration of Na+ above permissible limit (WHO 2011). The spatial patterns of Na+ are illustrated in Figure 3e. Excess Na+ causes hypertension, congenial diseases, kidney disorders and nervous disorders in human body (Ramesh and Elango, 2011). According to Hem (1985), high values of Na+ in groundwater may either be due to chemical weathering of feldspars or over exploitation of groundwater resources. K+ concentration in groundwater ranges from 0 to 9 mg/l with an average value of 2 mg/l and there is no threat from K+ in groundwater. The CO32- content is 0 where as HCO32- is the dominant anion and the concentration vary from 367 to 877 mg/l with an average of 571 mg/l. Maximum permissible limit for HCO32- concentration is found to be 300mg/l (WHO 2004), hence the groundwater from the study area is unfit for drinking purpose. A concentration of Cl- in groundwater varies from 42 to 412 mg/l with an average of 196 mg/l. The desirable limit of Cl - for drinking water is specified as 250 mg/l as per WHO 2011 and 37% of the samples are above this limit. The spatial patterns of Clare illustrated in Figure 3f. Chlorides are harmless at low levels but at levels higher than 250 mg/l, it causes odour and salty taste apart from aggravating heart problems and contributing to high blood pressure. The concentration of Cl− in groundwater is high may possibly be due to domestic wastages and/or leaching from upper soil layers in dry climates (Srinivasamoorthy et al., 2008). It was found that amount of SO 42− ions range from 40 to 364 mg/l with an average of 141 mg/l, and 19% of samples are above the maximum permissible limit of 250 mg/l (WHO 2011)as shown in the figure 3g.. Samples with higher concentration of SO42- in drinking water are associated with respiratory problems (Subramani et al., 2010). NO3- concentration in the study area ranges from 13 to 170 mg/l with an average of 75 mg/l. Only 41% of the samples are within the permissible limit of 50 mg/l as per WHO 2011. The spatial patterns of NO3- illustrated in Figure 3h. The concentration of NO3- is due to the decaying organic matter, sewage and fertilizer from agricultural runoff (Karnath 1987). Higher concentration of NO 3- can cause methaemoglobinaemia, gastric cancer, goiter, birth malformation and hypertension. Fluoride concentration value in the range of 0.06 to 0.24 mg/l has been obtained from the groundwater samples of the study area and these values are within the permissible limits of WHO 2011. Fluoride may be an essential element for humans (WHO 2004). The source of F- in groundwater is normally attributed to leaching from fluoride rich rocks and easier accessibility of rain water to weathered rock, long-term irrigation processes, semiarid climate and long residence time of groundwater (Datta et al., 1996; Srinivasamoorthy et al., 2008).


(a)

(b)

(c)

(d)

(e)

(f)

(g) (h) Fig.3. Spatial Distribution maps of- (a)Electrical Conductivity; (b) Total Dissolved Solids; (c) Total Hardness; (d) Magnesium; (e) Sodium; (f) Chloride; (g) Sulphate; (h) Nitrate.

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5. Conclusions In Ingaldhal region of the Chirthradurga district, Karnataka State there is no public water supply system and the population in these villages depends on groundwater for their needs. In the study area groundwater drawn from 22 bore wells were analyzed for their chemical contents. The analytical results of physical and chemical parameters of groundwater were compared with the standard guideline values recommended by the World Health Organization (WHO, 2011) for drinking purpose. Hydrochemically the ground water contains higher concentrations of TDS, Mg2+ and HCO3-, moderate concentrations of Ca +, Na+ and Cl-, and lower concentrations of K +, SO42- , F and NO3-. Further, hydrochemical data reveal that the groundwater of the study region consists of 3 hydrochemical facies, viz., CaMgHCO3, CaMgSO4 and NaCl. Assessment of the quality of the groundwater from 22 bore wells indicate that the groundwater belong to hard to very hard category and groundwater from majority of the bore wells of the study region is unfit for drinking purposes. The groundwater is laden with objectionable concentration of cations and anions which may possibly have been derived through combined sources viz., mineralization, chemical weathering of rock, mine tailings, sewage contamination and intense agricultural activities. Present authors believe that the chemical weathering of the rocks, open sanitation and agricultural return flow have contributed greatly for the major elements of the groundwater. This preliminary study calls for continuous monitoring of the quality of the groundwater in the region as further exploitation of groundwater may increase the values of the some of the parameters viz., EC, TDS, Mg2+, NO3- and F and deteriorate the water quality in near future which ultimately will prove to be disastrous for the entire living beings in the region. Spatial distribution map of certain parameters prepared from the hydrochemical data in GIS environment is useful in assessing the best groundwater quality zone in the study area. References APHA 1995. Standard Methods for the Examination of Water and Wastewater. ,American Public Health Association,Washington, DC. Babiker, I. S., Mohamed, A. A., Mohamed, T. H., 2007. Assessing groundwater quality using GIS. Water Resour Manage, 6, 699–715. Breton, W., Bruce, Mark, F., Becker, Larry, M., Pope, Jason, J., Gurdak, 2003. Ground-Water Quality beneath Irrigated Agriculture in the Central High Plains Aquifer, 1999–2000. 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Subba Rao, N., 1993. Environmental impact of industrial effluents in groundwater regions of Visakhapatnam Industrial Complex. Ind. Jour of Geology, 65, 35–43. Subramani, T., Rajmohan, N., Elango, L., 2010. Groundwater geochemistry and identification of hydrogeochemical processes in a hard rock region, Southern India. Environmental Monitoring and Assessment, 162,123–137 WHO 2004. Guidelines for drinking-water quality. World Health Organization, Geneva, Switzerland. Vol. 1, 3rd ed., Recommendations. WHO. (2011). Guidelines for drinking water quality, World Health Organization Geneva, 4th ed., Recommendations,1-4. Vennila G., Subramani T and Elango L (2008): GIS Based Groundwater Quality Assessment of Vattamalaikarai Basin, Tamil Nadu, India. Nat.Env.and Poll.Tech.V. 7(4), pp. 585-592 Zhang, W., Kinniburgh, D., and Gabos, S., 2013. 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