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Effects of heavy metal contamination on river water quality due to the release of
industrial effluents

Marzieh Mokarram, Ali Saber, Vahideh Sheykh

PII: S0959-6526(20)33425-9
DOI: https://doi.org/10.1016/j.jclepro.2020.123380
Reference: JCLP 123380

To appear in: Journal of Cleaner Production

Received Date: 4 January 2020

Revised Date: 4 July 2020
Accepted Date: 20 July 2020

Please cite this article as: Mokarram M, Saber A, Sheykh V, Effects of heavy metal contamination
on river water quality due to the release of industrial effluents, Journal of Cleaner Production, https://
doi.org/10.1016/j.jclepro.2020.123380.

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Effects of heavy metal contamination on river water quality due to the release of industrial

effluents

Marzieh Mokarram1, Ali Saber2*, Vahideh Sheykh3

1
Department of Range and Watershed Management, College of Agriculture and Natural

Resources of Darab, Shiraz University, Iran

2
Department of Civil and Environmental Engineering and Construction, University of Nevada

Las Vegas, Las Vegas, NV, USA

3
Department of Geology, Shiraz University, Iran

* Corresponding author:

Ali Saber, Department of Civil and Environmental Engineering and Construction, University of

Nevada, Las Vegas, 4505 S. Maryland Pkwy. Las Vegas, NV 89154, USA

Office: SEB 3248, Tel: 702-285-2836, Fax: 702-895-4436, Email: sabersic@unlv.nevada.edu

ORCID ID: https://orcid.org/0000-0002-4618-5042

Authors’ email addresses:

Marzieh Mokarram: m.mokarram@shirazu.ac.ir; https://orcid.org/0000-0003-4282-1950

Vahideh Sheykh: vahidehsheykhi@gmail.com

1 Effects of heavy metal contamination on river water quality due to the release of industrial

2 effluents

3 Abstract

4 This study seeks to evaluate the quality of Kor River water located in southern Iran, and presents

5 techniques for identifying the main sources of contaminations discharged to the river by

6 neighboring factories. Water quality constituents, including water temperature, pH, total hardness,

7 chloride, phosphate, nitrate, arsenic, cadmium, trivalent chromium, hexavalent chromium,

8 copper, molybdenum, nickel, and zinc in twenty-nine stations along the river were evaluated

9 during two years. The Dunnett statistical test and principal component analysis were employed to

10 determine the most influential constituents on river water pollution. The Kriging method was

11 also applied to analyze the spatial distribution of contaminants in the vicinity of polluting

12 industries. Results of the Dunnett test indicated that the stations located in the vicinity of an

13 industrial area, including petrochemical, pulp mill, home appliances, meat, sugar, tanning, flour,

14 and licorice extraction factories were among the most polluted stations. Water quality index and

15 heavy metal evaluation index were used to determine the contamination level at each station.

16 Stations with water quality indices of 0.9 ± 5.0 and 87.3 ± 2.0 had the lowest and the highest

17 contamination levels, respectively, corresponding to very poor (undrinkable) and very good

18 water qualities. Stations with poor water qualities were also found to be highly polluted

19 according to the heavy metal evaluation index, showing high concentrations for arsenic and

20 cadmium.

21 Keywords: Heavy metals; Heavy metal evaluation index (HEI); Industrial contamination; River

22 water quality; Water quality index (WQI)

1
23 1. Introduction

24 Environmental pollutions caused by municipal, industrial, and agricultural wastewaters as well

25 as the landfill leachate and runoff flown from the urban areas and the farmlands, are considered

26 as the main sources of water contamination (Samadi et al., 2009). Water contamination by heavy

27 metals is one of the serious threats to the health of mankind (Saha and Paul, 2019). Heavy metals

28 enter into the ecosystem as highly stable and somewhat non-degradable contaminants (Burgess,

29 2015), polluting both surface and groundwater resources. Increasing demand for water and

30 decreasing water supplies combined with environmental polluting activities indicate the

31 importance of water quality monitoring, particularly for the drinking water supplies (House and

32 Ellis, 1987). The concern is more serious in arid and semi-arid regions where there is a scarcity

33 of water. The water quality index (WQI) is a lumped index based on concentrations of different

34 water quality constituents (Sánchez et al., 2007), which could be used by managers to assess the

35 overall quality of various water resources (Rao, 2006).

36 Ramakrishnaiah et al. (2009) utilized the WQI index to assess water quality in India. They

37 incorporated 12 parameters of pH, total hardness (TH), calcium (Ca2+), magnesium (Mg2+),

38 bicarbonate, chloride (Cl-), nitrate (NO3-), sulfate, total dissolved solids (TDS), iron (Fe2+),

39 manganese (Mn2+), and fluoride (F-).

40 Multivariate statistical analysis is among the most frequently used methods in recent years for

41 water quality assessment and environmental pollution analysis. Shrestha and Kazama (2007) in

42 Fuji river basin, Japan, and Zhang et al., (2009) in Daliao river basin, China, used principal

43 component analysis (PCA) to reduce the number of parameters to assess water quality.

2
44 Singh et al. (2005) used 24 parameters to classify Gomti River water pollution into three

45 categories of low, moderate, and high pollution levels. Their results showed that PCA, by

46 reducing the number of parameters involved in water quality assessment, could enhance the

47 robustness of statistical analyses. Shrestha et al. (2007) used a multivariate statistical analysis to

48 evaluate the water quality of the Fuji River, Japan. They also categorized the river pollution level

49 into three classes of low, moderate, and high pollution, and reported that BOD, pH, EC, NO3-,

50 and ammonium (NH4+), as parameters with the higher impacts on water quality. Findings of a

51 study by Boyacioglu et al. (2008) on assessing sources of water contamination of the Tahtali

52 River, Turkey, indicated the robustness of multivariate statistical analysis for reducing the

53 number of relevant parameters and stations required for water quality monitoring. They

54 incorporated BOD, DO, COD, Cl-, TDS, Na+, NO3-, SO42- to classify river water contamination

55 into two categories of low and high pollution levels. They identified TDS, Cl-, and Na+

56 concentrations as the most effective river water contamination factors. Huang et al. (2010) used

57 geostatistical methods to assess the sources of water contamination in the Qiantang River, China.

58 Their findings indicated that the majority of contamination occurred in tributaries, while the

59 mainstream suffered from relatively lower contamination rates.

60 Monitoring the river water quality is an indispensable part of water management where the river

61 water might serve as the sole water resource for different purposes (Viville, 1997). For instance,

62 Vaigha et al. (2017) investigated the impacts of climate and land-use change on streamflow,

63 water quality, and suspended sediment in the Kor River Basin. The results of their study showed

64 that land-use change was a significant factor affecting the nutrient concentrations in the river.

65 Explored by Sheykhi and Moore (2013) in Kor River, the calculated geo-accumulation index

66 indicated that half of the 12 stations in the study area were moderately to extremely polluted.

3
67 Rasouli et al. (2012) reported Mg/Ca ratios of one-third of the Kor river water samples and two-

68 thirds of well waters leading to the reduction of the yields of barley, wheat, maize, and sugar

69 beets in local farmlands. Moreover, the saturation indices of their study showed that 94 % of the

70 analyzed water samples were supersaturated with calcite, aragonite, and dolomite in Kor River.

71 Asrari (2008) also showed that agricultural runoff and industrial effluents were the most

72 important sources of Kor River pollution.

73 Liu et al. (2017) investigated the status of heavy metal contamination and source apportionment

74 in sediments of Songhua River Harbin region, northeast China. Their analysis of chemical

75 speciation indicated that Cr and As in surface sediments were relatively stable while Pb and Cd

76 were readily bioavailable. Mondal et al. (2017) examined the spatial distribution and ecological

77 risk assessment of total and mild acid-leachable trace elements in surface sediments along the

78 Hooghly (Ganges) River Estuary and Sundarban Mangrove Wetland, India. Using mean

79 probable effect level quotient, the results of their study suggested that surface sediments in the

80 vicinity of the region could probably (21 %) toxicate biota. Furthermore, the results of

81 multivariate analyses confirmed the lithogenic sources (e.g., weathering parent rocks, dry

82 deposition) for As, Pb, Cr, Cu, and Ni, whereas Cd and Hg originated from anthropogenic

83 activities such as urban and industrial activities.

84 There are different methods for determining the water quality including the Bayesian

85 autoregressive (BAR) model for water quality variation prediction, Isolation Forest (IF)

86 algorithm applied in Potomac River of West Virginia, USA (Liu et al., 2020), Analysis of

87 variance (ANOVA) used in the Three Gorges Reservoir Area, China (Zhang et al., 2019), and

88 optimization-simulation method (Wang et al., 2019), fuzzy logic (Gaafar et al., 2019).

4
 89 Ishikawa et al. (2019) used a Standardized Hydrology-based Assessment (AIST-SHANEL) tool

90 to simulate water quality and evaluate the effects of the company's consumer products on three

91 Japanese rivers. The results showed that the AIST-SHANEL model is useful to determine water

92 quality in rivers.

93 Howladar et al. (2018), Kükrer and Mutlu (2019), Gao et al. (2020), and Yu et al. (2020)

94 evaluated water quality in Dinajpur basin, Bangladesh, Saraydüzü Dam Lake, Turkey, Xi’an

95 area, China, and Maddhapara Granite Mining area, Dinajpur, Bangladesh respectively, using

96 water quality index (WQI). The findings of the Howladar et al. (2018) study indicated the WQI

97 of the samples to vary from 10.23 to 63.64 for drinking purposes (96.77 % were excellent and

98 3.23 % were good). Kükrer and Mutlu (2019) found the WQI values in Saraydüzü Dam Lake

99 between 17.62 and 29.88. Water quality parameters in Saraydüzü Dam Lake did not exceed the

100 recommended limit values in all months and at all stations. The results of the WQI in Gao et al.

101 (2020) study showed that 28.82 % of the samples were inappropriate for drinking. China and Yu

102 et al. (2020) compared the WQIs of the water samples collected in 2011 and 2017 from a region

103 near the Maddhapara Granite Mining area, Dinajpur, Bangladesh, reporting that WQI values in

104 2017 (WQI = 59.2) were lower than those of 2011 (WQI = 72.8).

105 Considering the scarcity of water resources in arid and semi-arid regions, water quality of many

106 freshwater resources, particularly those located in the vicinity of agricultural and urban areas,

107 suffer from contaminations produced by anthropogenic activities. The ever-increasing population

108 growth combined with water scarcity, particularly in arid and semi-arid regions warrant the need

109 for the protection of limited freshwater resources including the rivers. However, agricultural

110 areas and industrial units are typically located in the vicinity of rivers, leading to the

111 contamination of downstream waters. Therefore, to protect the downstream populations, it is

5
112 crucially important to identify the primary sources of contamination along a river (Komariah and

113 Matsumoto, 2019).

114 Although the contaminants produced by industrial activities could also affect lotic ecosystems,

115 the current study focused on drinking water quality and heavy metal contaminations. More

116 information regarding the detrimental effects of industrial activities on lotic environments could

117 be found in Vidal et al. (2019) and Holloway et al. (2018).

118 Aris et al. (2015) and Zulkifli et al. (2010) argued that different factories caused the increased

119 levels of Zn, Cu, Ni, Fe, Al, Pb, Mn, Cr and Sn nearby Langat River. NWSC (National Water

120 Services Commission) showed that the discharges of industrial effluent (Krishnan, 2009) led to

121 increased water pollution in rivers (Bernama, 2014). The Selangor Water Management Authority

122 (SWMA) also reported that the concentration of ammonia (> 0.7 mg/L) in water increased from

123 2012 to 2015 due to industrial activities (Alkimia, 2014).

124 Previous studies have mostly focused on the release of contaminant(s) from limited polluting

125 sources. However, the current study attempts to offer some methods for identifying the main

126 sources of contamination among a variety of polluting point-sources along a river, using

127 advanced spatial distribution maps to specify the major point-sources of different contaminants

128 along a river. The results of the study could be usefully applied in management practices to

129 identify the main sources of pollution as well as the polluted areas along a river, helping

130 managers set appropriate policies for protecting public health.

131 Kor River is the mainstream of Marvdasht county in Fars Province, southern Iran, collecting

132 runoff from all tributaries within the county. Kor River is one of the major drinking water

133 sources in the region and is the prime water supply for agricultural activities in the province.

134 Hence, contamination in this water body imposes major consequences on the prosperity of the

6
135 region. However, effluents released from several industrial units, including meat, leather,

136 petrochemical, pulp mill and sugar, home appliances, flour, and licorice factories as well as

137 wastewater discharge, significantly reduce the water quality of the river.

138 The current study employs statistical methods to identify the main contamination sources among

139 different industrial units polluting Kor River. The study also uses spatial distribution maps to

140 determine the occurring heavy metals in the river the factories that they originated from.

141 As mentioned before, different heavy metals such as Cl-, PO43-, NO3-, As, Cd, Cr(III), Cr(VI),

142 Cu, Mo, Ni, Zn exist in Kor river water. On the other hand, there are many pollutant sources

143 around the river that have added to the amount of heavy metals in its water. This study, therefore,

144 seeks to identify the pollutant sources of each of the heavy metals, which could be regarded as

145 one of the innovations of this research.

146 2. Materials and methods

147 The measurement of water quality follows four steps including the identification of the

148 characteristics of the study area (subsection 2.1), the sources of contamination and the sampling

149 stations (subsection 2.2), and statistical analysis to determine the status of water quality in whole

150 the study area (subsection 2.3), all of which would be elaborated in the following.

151 2.1. Study site

152 Kor Watershed is located in Marvdasht Province, Iran, between 29 °18 ΄ N – 30 °48 ΄ N and 51 °

153 42 ΄ E – 53 ° 24 ΄ E (Fig. 1), with an area of about 6,035.8 km2. The highest and lowest altitudes

154 in the region are at 3,709 m and 1,542 m, respectively, from the sea level. (Fig. S1) The most

7
155 recognized river in this watershed is the Kor River, originating from the Zagros mountain range

156 along the northwestern regions of the province towards the southeastern sectors.

157 The average annual rainfall in the southeastern parts was 300 mm during the study period (2010

158 to 2016), but could reach over 800 mm in mountainous areas (Fars Regional Water Company,

159 2017). The average annual air temperatures of the region were 19.9 ± 7.2 °C and 22.1 ± 9.9 °C in

160 2010 and 2016 respectively (Table S1), with average annual evaporations being 178.5 ± 129.0

161 mm/year and 199.0 ± 146.1 in 2010 and 2016, in turn (Table S2). Tables S1 and S2 could be

162 found in the appendix.

163 From a geological standpoint, the study area consists of two types of carbonate and non-

164 carbonate constituents, with the carbonated category contributing to 40 % of the entire rocks of

165 the region, comprising formations such as Asmari, Sarvak, Ilam, Tarboor, Daryan, Fahlilan, with

166 karstic systems or fractions. The middle part of the non-carbonate formations consists of

167 quaternary alloys. As seen in Fig. S2 in the supplementary material, about 57 % of the region is

168 covered by rangelands.

169 2.2. Contaminant sources and sampling stations

170 The main contamination sources in Kor River water include effluents from petrochemical plant

171 and leather product manufacturers towards the western sectors of the study region. The main

172 products of the petrochemical plant include ammonium and granular urea, with capacities of

173 680,000 and 1,073,000 ton/year, respectively. These chemicals are primarily used as fertilizers

174 for agricultural activities. In urban or rural areas within the vicinity of the river, municipal

175 wastewater, and runoff are discharged into the river. Furthermore, fertilizer-rich agricultural

8
176 runoff generated due to the irrigation of agricultural lands in northern parts is also discharged

177 into the main river runway and result in contamination of downstream regions.

178 Fig. 1 depicts the locations of 29 sampling stations used for river water quality monitoring.

179 Water temperature and pH were measured onsite. For other water quality constituents, 0.5 L

180 water samples were collected and transferred (at 4 °C) to a laboratory in less than 2 h. A total of

181 three samples were collected from each sampling station at each sampling time, and the average

182 concentrations of water quality constituents obtained from three water samples were reported.

183 The water samples were collected during April, September, December of the years 2010 and

184 2016. Twelve water quality constituents of total hardness (TH), Cu, Cr(III), Cr(VI), Cl-, Cd, As,

185 Ni, Mo, Zn, PO43-, and NO3-, were measured in each water sample. Chlorine was measured

186 through standard AgNO3 titration (Mohr method). The pH measurements of water samples were

187 carried out in-situ, using a portable pH meter (model PCD650). Total hardness and calcium were

188 measured titrimetrically, using standard EDTA. Nitrate and phosphate were measured through a

189 spectrophotometer (model, DR/2,500). Concentrations of other heavy metals were measured by

190 ICP-MS. The accuracy and precision of the measurements were checked by the use of reference

191 materials and appropriate replicates.

9
192

193 Fig. 1. Study site, locations of sampling stations, and discharge points of urban wastewater and

194 different industrial effluents along Kor River.

195 2.3. Statistical analysis

196 Prior to statistical analysis, the Kolmogorov-Smirnov test was used to assess the normality of

197 datasets. Upon establishing normality of data, PCA was employed to determine the significance

198 of each water quality constituent in the overall river water contamination at monitoring stations

199 and to reduce the number of water quality constituents in statistical analyses. The WQI and HEI

200 were also used to assess the contamination level at each station. All statistical and mathematical

201 operations were conducted using SPSS STATISTICS 22.0 and Minitab 14. Geostatistical models

202 in ArcGIS. V5.10 were also used to obtain a spatial distribution of contaminants in the study

203 area.

204 2.3.1. Water Quality Index (WQI)

10
205 WQI was calculated as (Brown et al., 1970):

∑q ×w i i
WQI = i =1
n

∑w
i =1
i
206 (1)

207 where, wi is the weight of constituent i, determined based on the significance of the constituent in

208 terms of health and hygiene. qi is the quality index determined as:

v -v
209 qi = a i (2)
si - vi

210 where, va is the concentration of the ith constituent during sampling, vi is the ideal concentration

211 for constituent i, k is proportionality constant and can also be calculated using Eq. 4, and si is the

212 standard value for constituent i. wi and k were calculated based on Eqs. 3 and 4 (Asadi, 2007):

k
213 wi = (3)
si

214 k = 1 / Σ (1 / si ) (4)

215 Table S4 summarizes the required parameters and critical values for each element of the WQI

216 index.

217 According to Table S4, water quality was categorized into 5 classes of good, acceptable, fair,

218 poor, and unacceptable, respectively, for WQI ranges of 91 - 100, 61 - 91, 31 - 61, 16 - 31, and

219 lower than 16, respectively (Brown et al., 1970).

220 2.3.2. Heavy Metal Evaluation Index (HEI)

221 The HEI index was employed as an indicator of water contamination by heavy metals. HEI

222 indicates the ratio of heavy metal contamination in the region to the maximum allowed heavy

11
223 metal contamination in drinking water (Prasanna et al., 2012). HEI was calculated as (Nayek et

224 al., 2013):

n
H ci
225 HEI = ∑ (5)
i =1 H max

226 where, HC,i is the measured concentration for constituent i and Hmax,i is the maximum allowed

227 concentration of constituent i.

228 In order to calculate HEI, As, Cu, Cd, Cr, Mo, Ni, and Zn concentrations measured at each

229 station during December, April, and September, were averaged over the course of two years

230 (2010 and 2016) and then divided by the corresponding critical values (Table S5). HEI was then

231 used to categorize the contamination level at each station. HEI < 10 indicates a low

232 contamination level, 10 < HEI < 20 indicates moderate contamination, and HEI > 20 indicates a

233 high contamination level (Prasanna et al., 2012).

234 2.3.3. Spatial distribution of water quality data

235 The Kriging method was used to evaluate the spatial distribution of each contaminant. The

236 Kriging geostatistical method estimates the spatial distribution of the target based on a variogram

237 fitted to the data. A variogram is a mathematical model used to explain the spatial continuity of a

238 variable as (Li and Heap, 2008):

1 n(h)
239 γ (h) = ∑ [ z ( xi ) − z ( xi + h)]2 (6)
2 n ( h ) i =1

240 where γ(h) is the semi-variance for contaminant z, h is the distance between the measured

241 samples, n is the number of measured samples, and z(xi) and z(xi + h) are the measured

242 contaminant concentrations at locations xi and xi + h.

12
243 Several semi-variogram models such as spherical, exponential, and circular models were

244 evaluated to obtain the best fit for the data. Spatial dependence for the water parameters were

245 evaluated by the nugget/sill ratio. A water quality constituent would have a strong spatial

246 dependence if the nugget/sill ratio is less than 25 %, a moderate spatial dependence if the ratio is

247 as ratios between 25 % and 75 %, and a weak spatial dependence if the ratio is greater than 75 %

248 (Shi et al., 2007).

249 3. Results and discussion

250 In this section, first the variation range of water quality constituents is measured (subsection 3.1).

251 Then, water quality variations at different stations would be determined (in subsection 3.2).

252 Subsection 3.3 investigate pollution status at all stations using the Dunnett test. The most

253 important heavy metals which contribute to the pollution of the Kor River would be identified

254 through PCA analysis, the results of which are reported in subsection 3.4. Finally, the

255 investigation of spatial properties via the Kriging method would be elaborated in subsection 3.5.

256 3.1. Variation ranges of water quality constituents

257 This study considered the status of Cl-, PO43-, NO3-, As, Cd, Cr(III), Cr(VI), Cu, Mo, Ni, and Zn

258 at different years (2010 and 2016) to measure pollution levels. Table 1 shows average

259 concentrations obtained from different stations in the years mentioned. As the table shows, all

260 variations of water quality indicate that the concentration of other contaminants increased

261 throughout the years from 2010 to 2016.

262 Table 1 summarizes the average concentrations of contaminants (Cl-, PO43-, NO3-, As, Cd,

263 Cr(III), Cr(VI), Cu, Mo, Ni, and Zn) at different stations in 2010 and 2016 respectively. As the

13
264 results of T-test analysis show (Table 1), except for Ni and Zn, the concentration of other

265 contaminants significantly increased from 2010 to 2016 (p-value < 0.05).

266 Table 1. Variation of water quality constituents at different years.

Year 2010 Year 2016 T-test1

Parameter
Mean ± Std dev Range Mean ± Std dev Range p-value

pH 6.5 ± 0.6 6.0 - 7.9 8 ± 0.6 7.1 - 8.9 < 0.01

TH (mg L-1) 185 ± 111 20 - 313 700 ± 407.8 24 - 1200 < 0.01
Cl- (mg L-1) 405 ± 165 0.7- 662 845 ± 302 8 - 1145 < 0.01
PO43- (mg L-1) 0.8 ± 0.4 0.00 – 1.35 8.2 ± 5.1 0.01 – 13.4 < 0.01

NO3- (mg L-1) 35.01 ± 75.52 0.55 - 290 81.43 ± 93.17 2.54 - 312.92 0.005

As (mg L )-1
2.03 ± 2.48 0.32 - 10.80 11.12 ± 11.51 0.17 - 44.73 < 0.01

Cd (mg L )-1
0.04 ± 0.04 0.02 - 0.19 6.12 ± 6.37 0.13 - 17.36 < 0.01
-1
Cr III (µg L ) 1.36 ± 0.16 0.77 - 1.57 6.50 ± 6.37 0.59 - 17.53 < 0.01

Cr VI (µg L-1) 10.12 ± 15.49 0.19 - 48.50 14.13 ± 13.55 0.15 - 38.44 0.027

Cr total (µg L-1) 11.48 ± 15.53 0.97 - 50.00 20.63 ± 19.77 0.74 - 55.50 < 0.01

Cu (mg L-1) 2.94 ± 2.14 0.08 - 8.53 8.95 ± 7.05 0.12 - 22.71 < 0.01

Mo (mg L-1) 20.37 ± 22.91 0.70 - 83.30 29.15 ± 24.74 2.50 - 87.19 0.027

Ni (mg L-1) 7.42 ± 6.19 1.23 - 23 7.63 ± 5.39 1.10 - 25.28 0.43

Zn (mg L-1) 43.91 ± 54.03 5.90 - 167.30 37.93 ± 22.24 21.92 - 225.17 0.26
1
T-test evaluates if concentrations in 2016 are significantly (95 % confidence level) greater than concentrations in
2010.
267

268 3.2. Water quality variations at different stations

269 Fig. 2 shows the WQI values obtained at different stations at different sampling times. The

270 lowest average value for two years was observed at station 17 (WQI = 11.2 ± 5.0) in September

271 (average of 2010 and 2016), corresponding to poor water quality conditions, and the highest

272 occurred at station 6, with a value of WQI = 88.3 ± 2.0 in December, indicating acceptable water

273 quality conditions.

14
274

275 Fig. 2. WQI values at different stations for different months in 2010 and 2016. The magenta

276 lines show a WQI of 30 corresponding to the upper threshold for poor water quality conditions.

277 The lowest WQI values for three consecutive months in both 2010 and 2016 were observed at

278 stations 16 through 25. As Fig. 2 shows, WQI values were lower in September of 2010 and 2016

279 compared with the December and April of such years. Similar observations were reported by

280 Singh and Reza (2010) who carried out their study in Orissa, India. They reported the WQI

281 values between 14 and 57, and 19 and 67 for summer and the seasons following monsoon rains,

282 respectively. Keshavarzi and Nabavi (2007) reported a flow rate of 552.75 m3/s, with an average

283 recurrence interval (1.11 year) in upper parts of Kor River in 2007.

15
284 Fig. 3 shows the obtained heavy metal evaluation index (HEI) for different stations. As seen,

285 stations 16 and 17 had the highest HEI values. It can also be concluded that As and Cd were

286 substantially higher than the maximum allowable concentrations for drinking water particularly

287 at stations within the vicinity of factories (stations 16 - 25) (Table S6). Analysis of WQI and

288 HEL at different stations showed a correlation coefficient of 0.83 between the two indices with a

289 negative slope, indicating the negative impact of HEI in WQI (Fig. S3).

290

291 Fig. 3. HEI values at different stations for 2010 and 2016.

292 3.3. Results of the Dunnett test

293 Analysis of variance and Dunnett's test indicated significantly greater concentration of

294 contaminants in the vicinity of the polluting industries. As Table 2 shows, except for stations 1 to

295 8, other stations experienced increased concentration of contaminants.

296 Significance levels of the Dunnett test at different stations are shown in Table 2. As no

297 significant differences were observed in stations 1 to 9, in conjunction with the fact that these

298 stations were not in the vicinity of factories, the significance level of the Dunnett test was only

16
299 obtained for stations 9 to 29. As evident from the Table 2, stations 9 to 12, located in the vicinity

300 of the tanning, leather, meat, and petrochemical factories showed significant levels (p < 0.05) of

301 Ni, Cr(VI), Cr(III), Mo, Cl-, Cd concentrations, indicating the impact of these contaminants on

302 water quality. Stations 18 to 28 were of the most contamination stations, located in close

303 proximity to the home appliances, pulp mill, and sugar factories, wherein PO4 was identified as

304 the most significant contaminant (p < 0.05), demonstrating the effects of these two factories on

305 the level of contamination of Kor River. Stations 18 to 24 within proximity of the flour factory

306 also showed significant levels of Cd, Mo, Cr(III), NO3-, Cl-, PO43-, and TH, all due to the

307 contamination from this factory. Increasing Cr(III) in nearby the flour factory due to large

308 amounts of chromium leaching from upstream.

309 Finally, stations 25 to 29, nearby the licorice extraction factory, showed significance amounts for

310 all contaminants, except Cl-, Cd, Cr(VI), and Cu, indicating the influence of the licorice extract

311 factory on water contamination of Kor River.

312

313

314

315

316

17
317 Table 2. Statistical significance for different constituents at different monitoring stations based

318 on the Dunnett test. Shaded cells indicate the occurrence of statistically (p < 0.05) higher

319 concentrations.

Station As Cd Cl Mo Cr(III) Ni Zn Cr(VI) Cu PO43- TH NO3 Factories near stations

1 1 1 1 1 1 1 1 1 1 1 0.97 1 Non
2 1 1 1 1 1 1 1 1 1 1 1 1 Non
3 0.97 1 1 1 1 1 1 1 1 1 0.98 1 Non
4 1 0.97 1 1 0.95 1 1 1 1 0.97 1 0.96 Non
5 1 1 1 1 1 1 0.87 1 0.96 1 1 0.95 Non
6 0.95 1 0.95 1 1 1 0.86 1 0.98 1 1 1 Non
7 1 1 1 1 1 1 0.97 1 1 1 1 1 Non
8 0.98 1 0.97 1 1 1 1 1 1 1 1 0.97 Non
9 1 0.032 0.016 0.012 0.01 0.034 1 1 0.87 1 1 1 Meat factory
10 1 0.021 0.032 0.021 0.02 0.85 0.54 0.67 0.69 1 1 0.98 Leather and Tanning
11 0.043 0.021 0.76 0.65 0.01 0.023 0.02 0.031 1 1 0.01 1 Petrochemical plant
12 1 0.024 0.043 0.32 0.01 0.21 1 0.04 0.02 1 1 1 Wastewater
13 1 0.87 1 1 0.02 0.04 1 0.049 0.043 1 1 1 Wastewater
14 0.03 0.013 1 0.84 0.32 1 1 0.038 0.048 1 0.022 0.98 Pulp mill and sugar
15 0.03 0.01 0.58 0.93 0.021 1 1 0.047 0.032 1 0.016 0.78 Pulp mill and sugar
16 0.62 0.75 0.32 0.047 0.32 1 0.43 1 0.69 1 1 1 Home appliances
17 0.68 0.84 0.42 0.46 0.032 1 1 0.97 1 1 1 1 Home appliances
18 1 0.021 0.41 0.43 0.037 0.89 0.65 1 1 0.019 0.014 0.047 Flour
19 1 0.016 0.027 0.67 0.031 1 1 1 1 0.032 0.012 0.49 Flour
20 1 0.016 0.043 0.1 0.017 1 0.87 1 1 0.043 0.02 0.045 Flour
21 0.65 0.018 0.07 0.21 0.015 1 1 0.98 1 0.032 0.021 0.047 Flour
22 0.98 0.032 0.024 0.54 0.078 0.42 1 1 0.87 0.049 0.016 0.05 Flour
23 1 0.043 0.054 0.046 0.76 1 1 1 0.89 0.038 0.025 0.05 Flour
24 1 0.94 0.032 0.046 0.34 1 1 1 1 0.029 0.018 0.046 Flour
25 1 1 0.059 0.014 0.58 0.01 0.032 1 1 0.048 0.012 0.048 Licorice extraction
26 0.01 1 0.78 0.017 0.43 0.034 0.035 1 0.67 0.048 0.035 0.05 Licorice extraction
27 0.02 1 1 0.016 0.34 0.03 0.039 0.67 0.89 0.032 0.029 0.016 Licorice extraction
28 0.01 0.87 1 0.019 0.265 0.02 0.048 1 1 0.05 0.032 0.012 Licorice extraction
29 0.01 1 1 0.021 0.019 0.034 0.045 0.89 1 1 0.045 0.048 Licorice extraction
320

321 Although the Dunnett test could effectively identify the stations with statically greater

322 contamination loads in comparison with other stations (including the upstream ones), the

323 contamination loads at upstream stations could have also resulted in statistically non-significant

324 increases in contaminants released into the river’s water.

18
325 3.4. Results of PCA analysis

326 Fig. 4 shows the results of PCA analysis considering the concentrations of water quality

327 constituents at different monitoring stations. As observed, the first and the second principal

328 components could explain about 75.7 % of the variance at different stations. The first and second

329 components could explain 61.0 % and 14.6 % of the variance, respectively.

330

331 Fig. 4. Percentage of variance expressed by the first 14 principal components for water quality at

332 all stations in 2010 and 2016

333 Fig. 5 also shows the average distribution of different weights allocated to the first and the

334 second components for all stations in both 2010 and 2016.

19
335

336 Fig. 5. Distribution of weights for different elements in the first and second principal

337 components.

338 According to Fig. 5, parameters Cl-, PO43-, Cr(III), Cu, NO3-, Cd, and Cr(VI), with the greatest

339 weights that had the most distance from the determined line, were the most influential

340 parameters for the measurement of water pollution. On the other hand, pH, As, Cu, Ni, Mo, and

341 TH, with the least amount of weights, were useful for predicting the water quality (Table S7).

342 To evaluate the suitability of principal componential analysis, Kaiser–Meyer–Olkin (KMO) and

343 Bartlett’s Sphericity tests were administered. KMO is a measure of sampling adequacy that

344 indicates the proportion of variance due to the underlying factors. Desired KMO values are

345 typically greater than 0.5 (Kaiser, 1974). In this study, a KMO value was reported to be 0.66,

346 indicating that PCA could result in a significant dimensionality reduction. The Bartlett’s test

347 compares the correlation matrix with an identity matrix, evaluating the redundancy among the

20
348 variables (Kaiser, 1974). In the study, the significance level was found to be < 0.01, indicating

349 significant relationships among variables.

350 3.5. Investigating Spatial Properties by Kriging Method

351 Table 3 shows the evaluated model on the variogram alongside its constituent factors for the

352 years 2010 and 2016. A low residual sum of squares (RSS) and robust spatial structure are the

353 prime indicators of the best fit of the model on an empirical variogram. The partial-to-threshold

354 ratio can be used to assess the spatial structure of data, wherein a ratio of less than 0.25, indicates

355 a robust structure, a value between 0.25 and 0.75, would show a moderate structure, and values

356 above 0.75 would indicate a weak spatial structure (Shi et al., 2007).

357 Table 3. The best-fit model for the variogram and its constituent factors for 2010 and 2016.

2010 2016
2
Parameter Model Co Co+C Co/Co+C R RSS Model Co Co+C Co/Co+C R2 RSS
pH Spherical <0.01 1.28 <0.01 0.83 0.18 Spherical 0.38 0.61 0.62 0.71 0.01
-
NO3 Spherical 0.01 1.08 <0.01 0.80 0.19 Spherical 0.00 0.41 <0.01 0.53 0.13
PO43- Spherical 0.19 0.46 0.41 0.53 0.19 Spherical 0.23 0.81 0.28 0.81 0.17
Ni Circular 0.99 0.42 2.35 0.89 0.02 Circular 0.35 1.04 0.34 0.82 0.13
Cl- Exponential 0.07 1.00 0.07 0.66 0.19 Exponential 0.31 1.27 0.24 0.71 0.19
Mo Spherical 0.26 0.51 0.51 0.89 0.18 Circular 0.12 0.83 0.15 0.83 0.17
TH Spherical 0.17 0.82 0.20 0.88 0.08 Circular 0.27 1.27 0.21 0.78 0.13
Cd Exponential 0.06 0.71 0.08 0.65 0.18 Circular 0.01 0.78 0.01 0.79 0.18
Cu Spherical 0.15 0.61 0.24 0.80 0.15 Circular 0.07 1.13 0.06 0.98 0.01
Zn Exponential 0.06 0.49 0.12 0.98 0.48 Circular 0.01 0.87 0.01 0.78 0.19
As Exponential 0.10 1.60 0.06 0.96 0.10 Spherical 0.21 0.63 0.33 0.76 0.06
Cr(III) Spherical <0.01 0.60 0.00 0.83 0.28 Spherical 0.34 0.99 0.34 0.93 0.02
Cr(VI) Circular 0.19 0.85 0.22 0.90 0.05 Spherical 0.21 0.74 0.28 0.85 0.20
Cr Total Circular 0.09 1.02 0.10 0.89 0.31 Spherical 0.01 0.67 0.02 0.74 0.26
WQI Circular 0.12 0.89 0.09 0.96 0.10 Circular 0.31 0.68 0.43 0.76 0.09
358

21
359 As lower partial-to-threshold (Co/Co + C) ratios were obtained for parameters Zn, PO43-, pH,

360 NO3-, Ni, Mo, TH, Cu, Cr, and Cl- using circular, exponential, and spherical models, these

361 models were used for generating the final zoning maps for the corresponding parameters (Table

362 3).

363 As Fig. 6 shows, the maximum As concentration increased from 10.7 mg/L in 2010 to 44 mg/L

364 in 2016. As observed, higher arsenic concentrations occurred in the vicinity of the petrochemical

365 plant; hence, it can be considered as the prime source of contamination. The maximum allowed

366 concentration for arsenic in water is 10 µg/L (WHO, 2011). However, in areas nearby the

367 petrochemical plant As concentrations around 44 µg/L in 2016 indicate a significate release of

368 As.

369

370 Fig. 6. Spatial distribution of As to 2010 and 2016 in the study area.

371 Fig. 7 shows the spatial distribution of Cr(III) and Cr(VI) within the study region. As evident, the

372 chromium concentrations increased in 2016 to values higher than the critical limit of 50 µg/L set

373 by WHO (WHO, 2011). As observed effluents from petrochemical, home appliances, pulp mill

374 and sugar, and flour factories alongside sewage resulted in a substantial amount of Cr

22
375 concentration near the factories (stations 16 to 25). Increased Cr concentration in water causes a

376 variety of renal, hepatic, and stomach illnesses (Khairy et al., 2011).

377

378 Fig. 7. Spatial distribution of Cr values within the study area in 2010 and 2016

379 As evident in Fig. 8, the amount of Cu within the central sectors of the study region, within close

380 proximity to the mentioned factories, particularly the petrochemical and pulp mill and sugar

381 factory, in conjunction with sewage was significantly high and beyond the critical value of 1

382 mg/L in drinking water (WHO, 2011). The presence of Cu in water is extremely hazardous, as it

383 could cause toxicity when transferred to the human body (Haidar and Schaffer, 2009).

23
384

385 Fig. 8. Spatial distribution of Cu values within the study area in 2010 and 2016.

386 Fig. 9 shows an increase in the amount of nitrate in water, most likely caused by increased use of

387 chemical fertilizers, to approximately 304 mg/L (Valiallahi and Koochi, 2020). A similar increase

388 was also observed in the amount of Zn to 266 mg/L in 2016, again due to the increased use of

389 chemical composts in the region. The surrounding areas of the study region are primarily

390 agricultural lands, wherein various types of fertilizers, particularly nitrate compounds, are used

391 that can cause water contamination. The presence of nitrogen-containing materials can be taken

392 to show the interference of wastewater and various manures and chemical fertilizers in water.

393 Due to the expanding area of agricultural lands within the study region, extensive use of nitrate

394 fertilizers, and discharge of sewage from wastewater returning from neighboring agricultural

395 lands to Kor River have also resulted in increased NO3- concentration. It should also be noted

396 that area of agricultural lands relying on Kor River as their primary water supply for irrigation is

397 quite high.

24
398

399 Fig. 9. Spatial distribution of Zn and NO3 for 2010 and 2016 in the study area.

400 Fig. 10, on the other hand, shows an increase in Cl- content to 1,146 mg/L, owing to the presence

401 of the flour factory and wastewater. The findings also show a substantial increase in the total

402 hardness of water in 2016, because of the presence of calcareous formations and the inlet of

403 sediments thereof, whether solid or diluted, to the river. A comparison among the results

404 obtained from this study indicates an increase in the hardness of the total outlet water of the river

405 compared to inlet water. The highest amount of hardness was obtained at 1,200 mg/L, near

406 wastewater sources and parts of the southern sectors of the river, where the maximum allowed

407 hardness in water is 400 mg/L. Phosphate content, according to Fig. 10, had reached 13.4 mg/L

408 in 2016 at areas within the vicinity of wastewater. Another cause for the increase of phosphate

25
409 concentrations in water is the use of phosphate-containing fertilizers in surrounding agricultural

410 lands.

411

412 Fig. 10. Spatial distribution of the amount of PO43-and TH to 2010 and 2016 in the study area.

26
413 According to Fig. 11, the contamination by Cd in 2010 was comparatively low and restricted to

414 areas in close proximity with the flour, home appliances, and pulp mill and sugar factories,

415 whereas in 2016, a large fraction of areas located downstream of Kor River was contaminated

416 with Cd, which is most likely the result of an increase in the activity of said factories. While the

417 standard concentration for Cd for drinking water is < 0.003 mg/L (WHO, 2011), Cd

418 concentrations in some areas could reach around 16 mg/L (Haidar and Schaffer, 2009).

419

420 Fig. 11. Spatial distribution of Cd concentration (mg/L) in 2010 and 2016.

421 Fig. 12 also shows an increase in the amount of Mo in 2016, primarily caused by wastewater

422 coming from the leather, flour, and tanning factories. Nickel concentrations also increased in

423 2016 due to a rise in wastewater pumped into river waters. In the same regard, Nasrabadi (2015)

424 showed that industrial wastewater discharged to the Caspian Sea increases water pollution by

425 heavy metals such as Ni.

27
426

427 Fig. 12. Spatial distribution of Ni and Mo for 2010 and 2016 in the study area.

428 In general, Cd, Cl-, Cr(VI), Cu, Mo, PO43-, As, and Ni concentration increased in 2016 compared

429 with those of 2010, indicating a rise in the overall amount of contamination in the study region

430 produced by different factories. Moreover, the results of the study show that petrochemical

431 factories alone have so highly contributed to the pollution of Kor River that the areas around

432 them are more polluted with As, TH, Cr, Ni than other areas are.

433 Water quality zoning maps were finally obtained and compared based on WQI indices for the

434 years 2010 and 2016 shown in Fig. 13. As seen, regions nearby factories had lower WQI and

435 higher contamination compared to the upstream regions. Overall, the upstream part of the study

28
436 area showed higher WQI values compared to downstream regions, Moreover, in 2016, the

437 southern sectors of the study area demonstrated lower WQI as opposed to the year 2010,

438 indicating the higher level of contamination in 2016.

439

440 Fig. 13. Spatial distribution of WQI values for 2010 and 2016 in the study area

441 The final water quality zoning maps were eventually generated for each parameter and finally

442 merged to get the overall WQI map of the region. Based on these maps as well as results from

443 PCA, the most significant elements affecting water quality were Cr(III), Cu, NO3-, Cd, Cr(VI),

444 and PO43-. The results also indicated the petrochemical plant as most significant in increasing

445 water contamination by TH, wastewater as contributing to increased contamination by TH as

446 well, the pulp mill and sugar factory to a rise in Cr, Cr(III), Cd, and Cr(VI) contamination, the

447 home appliances factory to an increase in Cd, PO43-, and Cr(III) contamination, and finally the

448 flour factory to a rise in contamination by Cu, NO3-, Cd, PO43-, and Cr(III).

449

450

29
451 4. Conclusions

452 The findings of this study showed that water quality of Kor River is highly affected by

453 surrounding industrial units, to the extent that the central and southern parts of the river were

454 labeled as highly contaminated. The results also indicate greater concentrations of Cd, Cl-,

455 Cr(III), Cu, Mo, PO43-, As, and Ni in regions nearby factories in 2016 compared to 2010. This is

456 likely due to the release of contaminants by industrial units including petrochemical, meat, and

457 leather factories as well as agricultural lands and drainages along the river. Moreover, as Cr(III),

458 Cr (VI), PO43-, Cd, Cl-, and NO3- were identified as the principal components of water

459 contamination, one can make the assumption that the majority of contamination within the region

460 was caused by extensive use of chemical fertilizers in agricultural lands as well as the activities

461 of petrochemical, pulp mill, and sugar factories. Therefore, a reasonable, yet profound solution to

462 decreasing water contamination of Kor River is to define the legal territorial span of the river and

463 prevent illegal cultivation within this span and proper treatment of industrial effluents prior to

464 their discharge to the environment.

465 Acknowledgments

466 The authors would like to thank Shiraz University for providing financial support (grant number:

467 238726-128) for this study.

468 Conflicts of Interest

469 None

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36
 Table 1. Variation of water quality constituents at different years.

Year 2010 Year 2016 T-test1

Parameter
Mean ± Std dev Range Mean ± Std dev Range p-value

pH 6.5 ± 0.6 6.0 - 7.9 8 ± 0.6 7.1 - 8.9 < 0.01

TH (mg L-1) 185 ± 111 20 - 313 700 ± 407.8 24 - 1200 < 0.01
Cl- (mg L-1) 405 ± 165 0.7- 662 845 ± 302 8 - 1145 < 0.01
PO43- (mg L-1) 0.8 ± 0.4 0.00 – 1.35 8.2 ± 5.1 0.01 – 13.4 < 0.01
-
NO3 (mg L ) -1
35.01 ± 75.52 0.55 - 290 81.43 ± 93.17 2.54 - 312.92 0.005

As (mg L-1) 2.03 ± 2.48 0.32 - 10.80 11.12 ± 11.51 0.17 - 44.73 < 0.01

Cd (mg L )-1
0.04 ± 0.04 0.02 - 0.19 6.12 ± 6.37 0.13 - 17.36 < 0.01
-1
Cr III (µg L ) 1.36 ± 0.16 0.77 - 1.57 6.50 ± 6.37 0.59 - 17.53 < 0.01

Cr VI (µg L )-1
10.12 ± 15.49 0.19 - 48.50 14.13 ± 13.55 0.15 - 38.44 0.027

Cr total (µg L-1) 11.48 ± 15.53 0.97 - 50.00 20.63 ± 19.77 0.74 - 55.50 < 0.01

Cu (mg L-1) 2.94 ± 2.14 0.08 - 8.53 8.95 ± 7.05 0.12 - 22.71 < 0.01

Mo (mg L-1) 20.37 ± 22.91 0.70 - 83.30 29.15 ± 24.74 2.50 - 87.19 0.027

Ni (mg L-1) 7.42 ± 6.19 1.23 - 23 7.63 ± 5.39 1.10 - 25.28 0.43

Zn (mg L-1) 43.91 ± 54.03 5.90 - 167.30 37.93 ± 22.24 21.92 - 225.17 0.26
1
T-test evaluates if concentrations in 2016 are significantly (95% confidence level) greater than concentrations in
2010.
 Table 2. Statistical significance for different constituents at different monitoring stations based

on the Dunnett test. Shaded cells indicate the occurrence of statistically (p < 0.05) higher

concentrations.

Station As Cd Cl Mo Cr(III) Ni Zn Cr(VI) Cu PO43- TH NO3 Factories near stations

1 1 1 1 1 1 1 1 1 1 1 0.97 1 Non
2 1 1 1 1 1 1 1 1 1 1 1 1 Non
3 0.97 1 1 1 1 1 1 1 1 1 0.98 1 Non
4 1 0.97 1 1 0.95 1 1 1 1 0.97 1 0.96 Non
5 1 1 1 1 1 1 0.87 1 0.96 1 1 0.95 Non
6 0.95 1 0.95 1 1 1 0.86 1 0.98 1 1 1 Non
7 1 1 1 1 1 1 0.97 1 1 1 1 1 Non
8 0.98 1 0.97 1 1 1 1 1 1 1 1 0.97 Non
9 1 0.032 0.016 0.012 0.01 0.034 1 1 0.87 1 1 1 Meat factory
10 1 0.021 0.032 0.021 0.02 0.85 0.54 0.67 0.69 1 1 0.98 Leather and Tanning
11 0.043 0.021 0.76 0.65 0.01 0.023 0.02 0.031 1 1 0.01 1 Petrochemical plant
12 1 0.024 0.043 0.32 0.01 0.21 1 0.04 0.02 1 1 1 Wastewater
13 1 0.87 1 1 0.02 0.04 1 0.049 0.043 1 1 1 Wastewater
14 0.03 0.013 1 0.84 0.32 1 1 0.038 0.048 1 0.022 0.98 Pulp mill and sugar
15 0.03 0.01 0.58 0.93 0.021 1 1 0.047 0.032 1 0.016 0.78 Pulp mill and sugar
16 0.62 0.75 0.32 0.047 0.32 1 0.43 1 0.69 1 1 1 Home appliances
17 0.68 0.84 0.42 0.46 0.032 1 1 0.97 1 1 1 1 Home appliances
18 1 0.021 0.41 0.43 0.037 0.89 0.65 1 1 0.019 0.014 0.047 Flour
19 1 0.016 0.027 0.67 0.031 1 1 1 1 0.032 0.012 0.49 Flour
20 1 0.016 0.043 0.1 0.017 1 0.87 1 1 0.043 0.02 0.045 Flour
21 0.65 0.018 0.07 0.21 0.015 1 1 0.98 1 0.032 0.021 0.047 Flour
22 0.98 0.032 0.024 0.54 0.078 0.42 1 1 0.87 0.049 0.016 0.05 Flour
23 1 0.043 0.054 0.046 0.76 1 1 1 0.89 0.038 0.025 0.05 Flour
24 1 0.94 0.032 0.046 0.34 1 1 1 1 0.029 0.018 0.046 Flour
25 1 1 0.059 0.014 0.58 0.01 0.032 1 1 0.048 0.012 0.048 Licorice extraction
26 0.01 1 0.78 0.017 0.43 0.034 0.035 1 0.67 0.048 0.035 0.05 Licorice extraction
27 0.02 1 1 0.016 0.34 0.03 0.039 0.67 0.89 0.032 0.029 0.016 Licorice extraction
28 0.01 0.87 1 0.019 0.265 0.02 0.048 1 1 0.05 0.032 0.012 Licorice extraction
29 0.01 1 1 0.021 0.019 0.034 0.045 0.89 1 1 0.045 0.048 Licorice extraction
 Table 3. The best-fit model for the variogram and its constituent factors for 2010 and 2016.

2010 2016
Parameter Model Co Co+C Co/Co+C R2 RSS Model Co Co+C Co/Co+C R2 RSS
pH Spherical <0.01 1.28 <0.01 0.83 0.18 Spherical 0.38 0.61 0.62 0.71 0.01
NO3- Spherical 0.01 1.08 <0.01 0.80 0.19 Spherical 0.00 0.41 <0.01 0.53 0.13
PO43- Spherical 0.19 0.46 0.41 0.53 0.19 Spherical 0.23 0.81 0.28 0.81 0.17
Ni Circular 0.99 0.42 2.35 0.89 0.02 Circular 0.35 1.04 0.34 0.82 0.13
-
Cl Exponential 0.07 1.00 0.07 0.66 0.19 Exponential 0.31 1.27 0.24 0.71 0.19
Mo Spherical 0.26 0.51 0.51 0.89 0.18 Circular 0.12 0.83 0.15 0.83 0.17
TH Spherical 0.17 0.82 0.20 0.88 0.08 Circular 0.27 1.27 0.21 0.78 0.13
Cd Exponential 0.06 0.71 0.08 0.65 0.18 Circular 0.01 0.78 0.01 0.79 0.18
Cu Spherical 0.15 0.61 0.24 0.80 0.15 Circular 0.07 1.13 0.06 0.98 0.01
Zn Exponential 0.06 0.49 0.12 0.98 0.48 Circular 0.01 0.87 0.01 0.78 0.19
As Exponential 0.10 1.60 0.06 0.96 0.10 Spherical 0.21 0.63 0.33 0.76 0.06
Cr(III) Spherical <0.01 0.60 0.00 0.83 0.28 Spherical 0.34 0.99 0.34 0.93 0.02
Cr(VI) Circular 0.19 0.85 0.22 0.90 0.05 Spherical 0.21 0.74 0.28 0.85 0.20
Cr Total Circular 0.09 1.02 0.10 0.89 0.31 Spherical 0.01 0.67 0.02 0.74 0.26
WQI Circular 0.12 0.89 0.09 0.96 0.10 Circular 0.31 0.68 0.43 0.76 0.09
• Drinking water quality in the vicinity of industrial units was very poor

• Petrochemical plant was identified as one the main contamination sources

• As and Cd were substantially higher than their allowable concentrations in potable water
Contributions

Conceptualization by M.M. and A.S.; Formal analysis by M.M. and A.S.; Methodology and
investigation by M.M. and A.S.; Project administration by M.M.; Grant acquisition M.M.;
Supervision by A.S.; Visualization and software by M.M.; Writing—original draft by and M.M.;
Water sampling V.S.; Water quality analysis V.S.; Writing—review and editing by M.M. and
A.S.
Conflicts of Interest:
The authors declare no conflict of interest.