Journal Pre-proof Distributions of arsenic and other heavy metals, and health risk assessments for groundwater in the Guanzhong Plain region of China Jiangbo Qiao, Yuanjun Zhu, Xiaoxu Jia, Ming'an Shao, Xiaoqian Niu, Jinyue Liu PII:
S0013-9351(19)30754-6
DOI:
https://doi.org/10.1016/j.envres.2019.108957
Reference:
YENRS 108957
To appear in:
Environmental Research
Received Date: 25 September 2019 Revised Date:
13 November 2019
Accepted Date: 22 November 2019
Please cite this article as: Qiao, J., Zhu, Y., Jia, X., Shao, Ming'., Niu, X., Liu, J., Distributions of arsenic and other heavy metals, and health risk assessments for groundwater in the Guanzhong Plain region of China, Environmental Research (2019), doi: https://doi.org/10.1016/j.envres.2019.108957. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier Inc.
1
Distributions of arsenic and other heavy metals, and health risk assessments for
2
groundwater in the Guanzhong Plain region of China
3
Jiangbo Qiaoa,c,*, Yuanjun Zhua,c, Xiaoxu Jiab, Ming’an Shaoa,b, Xiaoqian Niub,
4
Jinyue Liu c
5
a
6
Northwest A&F University, Yangling 712100, China
|
b
8
Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences,
9
Beijing 100101, China
State Key Laboratory of Soil Erosion and Dryland Agriculture on the Loess Plateau,
Key Laboratory of Ecosystem Network Observation and Modeling, Institute of
10
c
11
Water Resources, Yangling 712100, China
Institute of Soil and Water Conservation, Chinese Academy of Sciences & Ministry of
12 13
Abstract: The aim of this study was to evaluate the quality of shallow groundwater
14
and deep groundwater in the Guanzhong Plain region of China, as well as the related
15
health risk to humans. In total, 130 groundwater samples were collected comprising
16
116 from shallow groundwater (dug wells) and 14 from deep groundwater (drilled
1|
wells). The water samples were analyzed to determine the levels of As and 12 other
18
heavy metals (Al, Cd, Mn, Cr, V, Fe, Ni, Cu, Zn, Co, Pb, and Mo). The results
19
showed that the concentrations of As and other heavy metals in the deep groundwater
20
samples were lower than the safe limits, but the Cr concentrations in some shallow
21
groundwater samples exceeded the safe limits. The heavy metal pollution index and
22
heavy metal evaluation index both showed that As and other heavy metals were
23
pollutants at low levels in all of the shallow and deep groundwater sample. Health risk
24
assessments showed that the deep groundwater samples had no associated
25
non-carcinogenic health risks, whereas the shallow groundwater samples had
26
non-carcinogenic health risks due to contamination with Cr and As. Some shallow
2|
groundwater samples had associated carcinogenic health risks due to contamination
28
with Cr and As, whereas the deep groundwater samples only had carcinogenic health
29
risks because of contamination with Cr. These results suggest that local residents and
30
government departments should be made aware of Cr and As pollution in shallow
31
groundwater.
32
Capsule: we assessed the quality of groundwater in the Guanzhong Plain region of
33
China, where we evaluated the levels of As and 12 other heavy metals.
34
Key words: groundwater, health risk assessment, heavy metal
35 36
1. Introduction
3|
Groundwater is an important and indispensable source of drinking water, and
38
one-third of all humans rely on this water source (Xing et al., 2013). Due to the rapid
39
development of society, many anthropogenic activities such as mining, industry, and
40
urbanization have affected the quality of groundwater (Griebler and Avramov, 2015;
41
Zahedi et al., 2017) by allowing its contamination with hazardous materials that are
42
harmful to human health, such as As (Ravindra and Mor, 2019), other heavy metals
43
(Singh et al. 2018), fluoride (Xu et al. 2019), nitrates (Li et al. 2018), and
44
polyaromatic hydrocarbons (Rajasekhar et al. 2018).
45
As and other heavy metal pollutants in groundwater can accumulate in the human
46
body over time and cause many diseases (Avigliano and Schenone, 2015), such as by
4|
damaging kidney functioning, the neurological system, and ossification process
48
(Lohani et al., 2008).
49
Therefore, it is very important to assess the quality of groundwater with respect to
50
As and other heavy metals in order to maintain the provision of safe drinking water
51
for people. Thus, many studies have assessed the quality of groundwater throughout
52
different areas of the world (Arslan and Turan, 2015; Wu et al., 2019; Bhattacharjee
53
et al., 2005; Phan et al., 2010). For example, Li et al. (2016) assessed the groundwater
54
quality and health risk due to contamination in a semiarid region of Northwest China.
55
Ravindra and Mor (2019) evaluated the health risk due to arsenic and other heavy
56
metals in groundwater samples from Chandigarh, India. Bhuiyan et al. (2010)
5|
evaluated heavy metal pollution in irrigation and drinking water systems in the
58
vicinity of a coal mining area in northwestern Bangladesh. Lu et al. (2015) conducted
59
a human health risk assessment with respect to contamination by trace elements in
60
drinking water in Shenzhen, China. Singh and Subramanian (2018) investigated the
61
groundwater chemistry and human health risk in a mining region in East Singhbhum,
62
Jharkhand, India.
63
The Guanzhong plain is located in the middle of Shaanxi Province (with a total
64
area of ~1.9 × 104 km2), which is an important grain production base in China (Lei et
65
al., 2014). Groundwater resources are important as sources of drinking and irrigation
66
water for local residents in the Guanzhong Plain area. Therefore, assessing the
6|
groundwater quality is very important for local and national economic development.
68
In addition, the Guanzhong Plain region is characterized by arid and semiarid areas
69
where water resources are lacking and the groundwater level is deep. Thus, water
|0
quality assessments are necessary for the development of the Guanzhong Plain region.
|1
The objectives of this study were: (1) to estimate the spatial distributions of heavy
|2
metals in groundwater in the Guanzhong Plain region; (2) to compare the differences
|3
in the distributions of heavy metals in shallow groundwater and deep groundwater
|4
samples; (3) to assess the water quality and pollution status of groundwater; and (4) to
|5
assess the non-carcinogenic and carcinogenic risks for populations exposed to arsenic
|6
and other heavy metals.
|| |8
2. Materials and methods
|9 80
2.1. Study area description
81
The Guanzhong Plain is located in the central part of Shaanxi Province
82
(34°00′–35°40′N, 107°30′–110°30′E) (Figure 1a). This region has an area of about
83
1.9 × 104 km2 and it measures about 360 km from east to west. The area has a
84
temperate semiarid and semi-humid monsoon climate. The average annual
85
temperature is 12–13.6°C and the mean annual precipitation is 530–700 mm, where
86
about 45% of the precipitation falls from July to September. The annual evaporation
8|
is 1000–1200 mm.
88 89
2.2. Hydrogeology of the study area
90
The Guanzhong Plain located in the west of Fenwei Graben Basin is a Cenozoic
91
fault basin formed by Himalayan movement. The basin began to sag in the late
92
Eocene and continued to subside in the Miocene and Pliocene, thereby accumulating
93
very thick tertiary river lake facies in a clastic rock formation. After entering the
94
Quaternary period, it continued to settle and a thick layer of soft soil accumulated in
95
the rivers and lakes. The local area around the basin was uplifted due to the influence
96
of the secondary fault block. The Tertiary rock formation was denuded and flattened
9|
into plain terrain, and loess then accumulated to form the loess platform.
98
The Guanzhong Basin River mainly comprises the Weihe River system, which is
99
the largest tributary of the Yellow River originating from Wuyuan County, Gansu
100
Province, and entering the basin via Baoji Gorge. From the west to the east,
101
Guanzhong Basin River traverses the middle of the basin and flows into the Yellow
102
River at Tongguan city. Guanzhong Plain covers the middle and lower reaches of the
103
Weihe River. The river valley is open and the water flow is slow.
104 105
2.3. Collection of water samples and laboratory analysis
106
In total, during November 2018, 130 groundwater samples were collected from
10|
the sampling sites shown in Figure 1b, with 116 from dug wells (shallow groundwater
108
samples) and 14 from drilled wells (deep groundwater samples). The sampling sites
109
were mainly located in Xianyang, Baoji, Tongchuan, Xi’an, and Weinan, where the
110
groundwater levels were low and it was easy to find dug wells. The dug wells were
111
located in rural areas whereas most of the wells in towns were buried. The drilled
112
wells were constructed by the public water supply department. We collected
113
groundwater samples from dug wells at intervals of 10–20 km. The towns had a
114
centralized water supply, so we collected groundwater samples from drilled wells in
115
towns. At each site, we collected 500 mL of groundwater in a plastic bottle, Each
116
sample was sealed with plastic film after its collection and then placed in a freezer. In
11|
the laboratory, given their low concentrations in groundwater, As and other heavy
118
metals (Al, Cd, Mn, Cr, V, Fe, Ni, Cu, Zn, Co, Pb, and Mo) were determined using
119
inductively coupled plasma-mass spectrometry. The groundwater samples were
120
filtered through a Luer syringe filter (pore size: 0.22 µm) before their analysis. In
121
addition, distilled water was used for blank analyses in order to ensure the reliability
122
of the results.
123 124
2.4. Evaluation indices
125
2.4.1. Heavy metal pollution index (HPI)
126 12|
HPI was employed to evaluate the total groundwater pollution with heavy metals and it was calculated using equation (1):
128
HPI=
∑
,
(1)
129
where Wi is the unit weight of the ith parameter, Qi is the sub-index of the ith
130
parameter, and n is the number of heavy metals measured. Qi was determined with
131
equation (2):
132
Qi=∑
*100,
(2)
133
where Mi is the value measured for the ith heavy metal and Ii is the ideal permissible
134
limit for the ith heavy metal. Ii was treated as 0 because the water quality standard in
135
China (2006) does not state ideal values. Si is the maximum allowable concentration
136
of the ith heavy metal according to the water quality standard in China (2006). Wi was
13|
computed as: 1/Si (Prasad and Bose, 2001; Hoaghia et al., 2016).
138 139 140 141 142
2.4.2. Heavy metal evaluation index (HEI) HEI was used to evaluate the overall quality of water in terms of heavy metals. HEI was calculated with equation (3):
HEI=∑ ,
(3)
143
where Ci is the measured concentration of the ith heavy metal and Si is the maximum
144
allowable concentration of the ith heavy metal.
145 146 14| 148
2.4.3. Human health risk assessment Health risk assessments are conducted to evaluate the risk to an individual's health caused by exposure to a factor by estimating the probability of adverse effects on the
149
human body. The risk types for the metal elements in groundwater that can harm
150
human health are classified according to the risk caused by exposure to carcinogenic
151
metals and non-carcinogenic metals. The health risk assessment models differ for
152
carcinogenic and non-carcinogenic metal elements. In this study, as defined by the
153
International Agency for Research on Cancer (IARC) (2011), As, Cd, and Cr were
154
treated as carcinogens, whereas the other heavy metals were considered
155
non-carcinogens. The two health risk assessment models were evaluated for the heavy
156
metals comprising As, Cd, and Cr by treating them as both carcinogens and
15|
non-carcinogens.
158 159 160
2.4.3.1. Non-carcinogenic health risk assessment The non-carcinogenic health risk assessments were conducted by evaluating the
161
chronic daily intake (CDI) and the hazard quotient (HQ). CDI was calculated with
162
equation (4): CDI = (C × IR × EF × ED)/(BW × AT),
163
(4)
164
where C is the contaminant concentration (mg/L), IR is the ingestion rate per day (2
165
L/day for adults), ED is the exposure duration (30 years), EF is the exposure
166
frequency (365 days/year), AT represent the average exposure time (ED × 365), and
16|
BW is the body weight (70 kg) (US Environmental Protection Agency, 1989). HQ was
168
calculated with the following equation:
169 1|0
HQ =
,
(5)
where RfD is the reference dose as the oral exposure level for a pollutant.
1|1 1|2 1|3 1|4 1|5 1|6 1||
2.4.3.2. Carcinogenic health risk assessment The carcinogenic potential of contaminated groundwater (C) was evaluated using equations (6) and (7): C = CDI × SF C = 1 – exp(–E × SF)
(6) (C ≥ 0.01),
(7)
where CDI was calculated using equation (5) and SF is the slope coefficient. Table 1
1|8
showed the detailed RfD and SF values for heavy metals (US Environmental
1|9
Protection Agency, 2002).
180 181 182
2.5. Statistical analysis Descriptive statistics (maximum, minimum, average, and coefficient of variation
183
(CV)) were calculated with SPSS (version 16.0). Spatial interpolation of the
184
distributions of heavy metals was conducted using ArcGIS 10.2.
185 186
3. Results and discussion
18| 188
3.1. Spatial distributions of heavy metals in groundwater
189
The inverse distance weighted method for spatial interpolation in ArcGIS was
190
employed to determine the spatial distributions of heavy metals (Figure 2) because
191
this approach obtains better results compared with the kriging method. The spatial
192
distributions of the heavy metals varied among the different sites (Figure 2).
193
Groundwater is influenced by natural factors and anthropogenic activities, and the
194
environmental conditions also varied among the different sites, thereby leading to the
195
diverse distributions of the heavy metals.
196
Table 2 shows descriptive statistics for heavy metals in the groundwater samples.
19|
In the shallow groundwater samples, the mean concentrations of the heavy metals
198
were in the following order: Fe > Cr > Mo > Zn > V > Al > Mn > As > Pb > Cu > Co >
199
Ni > Cd. In the deep groundwater samples, the mean concentrations of the heavy
200
metals were in the following order: Zn > Fe > Mo > Cr > Mn > V > As > Al > Cu >
201
Ni > Pb > Co > Cd. Clearly, the concentrations of heavy metals varied among the
202
samples from different depths. In addition, in the shallow groundwater samples, the
203
variations in V, Fe, Zn, and Cd were moderate, but high for the remaining heavy
204
metals. In the deep groundwater samples, the variations in V, Fe, As, and Cr were
205
high but moderate for the remaining heavy metals. Thus, the spatial distributions of
206
the heavy metals were heterogeneous in the shallow and deep groundwater samples.
20|
According to the safe water standards defined by the World Health Organization
208
(WHO) (2017), which are similar to the China water quality standard (2006) (Table 3),
209
the concentrations of the heavy metals in the deep groundwater samples were all
210
below the WHO limits (2017), but the concentrations of some heavy metals in the
211
shallow groundwater samples exceeded the safe limits, such as those of Cr and Mo
212
(Figure 2). Thus, the shallow groundwater was polluted in some areas whereas the
213
deep groundwater was always safe to drink. In the shallow groundwater samples, the
214
concentration of Cr exceeded the safe limit in 14 groundwater samples, which were
215
mainly collected in Weinan city (Figure 2). Wang et al. (2012) assessed the Cr
216
concentration distributions in Weinan city and also found that the Cr concentrations
21|
exceeded the safe limits. The Cr pollution mainly came from industrial sources. In
218
addition, the concentration of Mo exceeded the safe standard in one groundwater
219
sample.
220
In addition, the concentrations of Pb and As were below the WHO limit in the
221
shallow groundwater samples but some were close to the WHO limit, e.g., 9.53 µg/L
222
for Pb (10 µg/L) and 8.12 (10 µg/L) for As (Figure 2). As, Cd, and Cr are carcinogens
223
according to the IARC (2011). Therefore, the concentrations of heavy metals in the
224
groundwater in some areas exceeded or were close to the WHO standard limit (2011),
225
and thus they were not suitable for drinking.
226 22| 228
3.2. Differences in heavy metal concentrations in shallow and deep groundwater
229
samples
230
In order to assess the groundwater quality in the Guanzhong Plain region, we
231
compared the heavy metal concentrations in 14 deep groundwater samples and 14
232
shallow groundwater samples from the same sites as the deep groundwater samples.
233
Table 4 shows descriptive statistics for the heavy metals in the shallow and deep
234
groundwater samples. There were no significant differences in the concentrations of V,
235
Mn, Fe, Ni, As, and Cd in the shallow and deep groundwater samples (P > 0.05). The
236
mean concentrations of Al, Cr, Pb, and Co were higher in the shallow groundwater
23|
samples than the deep groundwater samples, whereas the opposite results were
238
obtained for Cu, Zn, and Mo (P < 0.05). Clearly, there were no consistent trends in
239
the heavy metal concentrations at different depths. The heavy metal concentrations in
240
groundwater are influenced by the leaching of metals from the surface by rainwater,
241
and the geochemistry of aquifers also affects the availability of heavy metals in
242
groundwater (Khodapanah et al., 2009; Ravindra and Garg, 2007). Thus, these factors
243
affected the variable heavy metal concentrations found at different depths.
244
In addition, the variations in the concentrations of most heavy metals were lower
245
in the deep groundwater samples than the shallow groundwater samples (Table 4),
246
possibly because the shallow groundwater was more likely to be influenced by human
24|
activities compared with the deep groundwater.
248 249 250
3.3. HPI and HEI results HPI and HEI have been employed to evaluate the total heavy metal pollution in
251
groundwater samples in many previous studies (Yari and Sobhanardakani, 2016;
252
Sobhanardakani, 2017). Bhuiyan et al. (2010) assigned the HPI results to three
253
pollution categories comprising: low HPI < 50, medium HPI = 50–100, and high HPI >
254
100 (Siegel, 2002). Bhuiyan et al. (2010) also classified the HEI results into three
255
pollution categories comprising: HEI < 40 indicating a low degree of pollution, HEI =
256
40–80 indicating a medium degree of pollution, and HEI > 80 indicating a high
25|
degree of pollution. As shown in Figure 3, the HPI and HEI values determined for the
258
shallow and deep groundwater samples collected in the Guanzhong Plain region all
259
indicated a low degree of pollution. The low heavy metal concentrations in the
260
shallow and deep groundwater samples resulted in low HPI and HEI values. The Cr
261
concentrations exceeded the safe limit in some areas but the HPI and HEI evaluate the
262
total pollution degree, which was low in all areas.
263 264 265
3.4. Human health risk assessment Tables 5 and 6 show the health risk assessment results in terms of the
266
non-carcinogenic and carcinogenic health risks associated with heavy metals in the
26|
groundwater samples. In terms of the non-carcinogenic health risks, the HQ values for
268
heavy metals in the deep groundwater samples were all < 1, whereas the HQ values
269
for the shallow groundwater samples from some areas were >1 for Cr and As (Table
2|0
5). If HQ ≥ 1, heavy metals may be associated with a potential non-carcinogenic risk
2|1
(Giri and Singh, 2015). Thus, the deep groundwater samples did not have associated
2|2
non-carcinogenic health risks, whereas the shallow groundwater sample from some
2|3
areas had associated non-carcinogenic health risks. In terms of the carcinogenic health
2|4
risks, the ranges of Cr, As, and Pb in the deep groundwater samples were 0 to 1.09 ×
2|5
10–2, 9.85 × 10–7 to 4.77 × 10–5, and 5.93 × 10–7 to 2.71 × 10–6, respectively. Thus, the
2|6
carcinogenic health risks for As and Cd were lower than the maximum acceptable
2||
level of 5 × 10–5 a–1 recommended by ICRP, but the Cr concentrations in some areas
2|8
exceeded the acceptable level (Table 6). Similarly, Cd had no associated carcinogenic
2|9
health risks in the shallow groundwater samples, whereas Cr and As had associated
280
carcinogenic health risks in some areas (Table 6). Therefore, pollution with Cr and As
281
should be addressed by the local government to ensure the safety of groundwater
282
supplies in the affected areas.
283 284 285 286 28|
4. Conclusion
288
In this study, we collected 130 groundwater samples and assessed the groundwater
289
quality in the Guanzhong Plain region in terms of As and 12 other heavy metals based
290
on various evaluation indices in order to evaluate the potential health risks for humans.
291
The main conclusions are as follows.
292
(1) Cr concentrations in the shallow groundwater of some areas exceeded the safe
293
limit, whereas the concentrations of all heavy metals were safe in deep groundwater.
294
Thus, Cr pollution in shallow groundwater should be investigated.
295 296 29|
(2) The HPI and HEI values indicated that the shallow and deep groundwater samples all had low levels of pollution with heavy metals. (3) Some shallow groundwater samples had non-carcinogenic health risks and
298
carcinogenic health risks associated with Cr and As. Some deep groundwater samples
299
only had carcinogenic health risks due to Cr. Our results may provide an important
300
reference for the management of local groundwater drinking supplies in the
301
Guanzhong Plain region.
302 303 304
Acknowledgments This study was supported by the National Natural Science Foundation of China
305
for a major international cooperation program between China and England
306
(415711300781), the National Natural Science Foundation of China (41371242 and
30|
41530854), and the Key Deployment Project of the Chinese Academy
308
(KFZD-SW-306). The authors thank the editor and reviewers for their valuable
309
comments and suggestions.
310 311 312 313 314 315 316 31| 318 319 320 321 322 323 324 325 326 32|
328 329 330 331 332 333 334 335 336 33| 338 339 340 341 342 343 344 345 346 34| 348 349 350 351 352 353 354 355 356 35| 358 359 360 361 362 363 364 365 366 36| 368 369 3|0 3|1
References Arslan, H., Turan, N.A., 2015. Estimation of spatial distribution of heavy metals in groundwater using interpolation methods and multivariate statistical techniques; its suitability for drinking and irrigation purposes in the Middle Black Sea Region of Turkey. Environmental Monitoring & Assessment. 187, 1-13. Avigliano, E., Schenone, N.F., 2015. Human health risk assessment and environmental distribution of trace elements, glyphosate, fecal coliform and total coliform in Atlantic Rainforest mountain rivers (South America). Microchemical Journal. 122, 149-158. Bhattacharjee, S., Chakravarty, S., Maity, S., Dureja, V., Gupta, K.K., 2005. Metal contents in the groundwater of Sahebgunj district, Jharkhand, India, with special reference to arsenic. Chemosphere. 58, 1203-17. Bhuiyan, M.A.H., Islam, M.A., Dampare, S.B., Parvez, L., Suzuki, S., 2010. Evaluation of hazardous metal pollution in irrigation and drinking water systems in the vicinity of a coal mine area of northwestern Bangladesh. Journal of Hazardous Materials. 179, 1065-1077. China water quality standard, 2006. Standards for drinking water quality. GB5749-2006. Giri, S., Singh, A.K., 2015. Human health and ecologic risk assessement of metals in fishes, shrimps and sediment from a tropical river. Int. J. Environ. Sci. Technol. 12, 2349–2362. Griebler, C., Avramov, M., 2015. Groundwater ecosystem services: a review. Freshwater Science. 34, 355-367. Khodapanah, L., Sulaiman, W.N.A., Khodapanah, N., 2009. Groundwater quality assessment for different purposes in Eshtehard district, Tehran, Iran. Eur. J. Sci. Res. 36 (4), 543-553. Lei, L.M., Yu, D.S., Chen, Y.P., Song, W.W., Liang, D.L., Wang, Z.H., 2014. Spatial distribution and sources of heavy metals in soils of Jinghui Irrigated Area of Shaanxi, China. Transactions of the Chinese Society of Agricultural Engineering. 30, 88-96. Hoaghia, M.A., Roman, C., Kovacs, E.D., Tanaselia, C., Ristoiu, D., 2016. The evaluation of the metal contamination of drinking water sources from Medias town, Romania using the metal pollution indices. Stud. Univ. Babes-Bol. Chem. 3, 461–471. IARC, 2011. IARC Monographs on the evaluation of carcinogenic risks to humans [M]. Lyon, France: World Health Organisation, IARC Press. Lohani, M.B., Singh, A., Rupainwar, D.C., Dhar, D.N., 2008. Seasonal variations of heavy metal contamination in river Gomti of Lucknow city region. Environmental Monitoring & Assessment. 147, 253-263. Phan, K., Sthiannopkao, S., Kim, K.W., Ming, H.W., Sao, V., Hashim, J.H., Yasin, M.S.M., Aljunid, S.M., 2010. Health risk assessment of inorganic arsenic intake of Cambodia residents through groundwater drinking pathway. Water Research. 44, 5777-5788. Prasad, B., Bose, J., 2001. Evaluation of the heavy metal pollution index for surface and spring water near a limestone mining area of the lower Himalayas. Environmental Geology. 41, 183-188. Rajasekhar, B., Nambi, I.M., and Govindarajan, S.K., 2018. Human health risk assessment of ground water contaminated with petroleum PAHs using Monte Carlo simulations: A case study of an Indian metropolitan city. Journal of Environmental Management. 205, 183-191. Ravindra, K., Garg, V.K., 2007. Hydro-chemical Survey of Groundwater of Hisar City and
3|2 3|3 3|4 3|5 3|6 3|| 3|8 3|9 380 381 382 383 384 385 386 38| 388 389 390 391 392 393 394 395 396 39| 398 399 400 401 402 403 404 405 406 40| 408 409 410
Assessment of Defluoridation Methods Used in India. Environmental Monitoring & Assessment. 132, 33-43. Ravindra, K., Mor, S., 2019. Distribution and health risk assessment of arsenic and selected heavy metals in Groundwater of Chandigarh, India. Environ Pollut. 250, 820-830. Li, P.Y., He, X.D., Li, Y., Xiang, G., 2018. Occurrence and Health Implication of Fluoride in Groundwater of Loess Aquifer in the Chinese Loess Plateau: A Case Study of Tongchuan, Northwest China. Exposure and Health. 11(2), 95-107. Li, P.Y., Li X.Y., Meng, X.Y., Li, M.N., Zhang, Y.T., 2016. Appraising Groundwater Quality and Health Risks from Contamination in a Semiarid Region of Northwest China. Exposure and Health. 8(3), 361-379. Lu, S.Y., Zhang, H.M., Sojinu, S.M., Liu, G.H., Zhang, J.Q., Ni, H.G., 2015. Trace elements contamination and human health risk assessment in drinking water from Shenzhen, China. Environmental Monitoring & Assessment. 187, 4220.Siegel, F.R., 2002. Environmental Geochemistry of Potentially Toxic Metals. Singh, U.K., Ramanathan, A.L., Subramanian, V., 2018. Groundwater chemistry and human health risk assessment in the mining region of East Singhbhum, Jharkhand, India. Chemosphere. 204, 501-513. Sobhanardakani, S., 2017. Arsenic health risk assessment through groundwater drinking (Case study: Qaleeh Shahin agricultural region, Kermanshah province, Iran). Pollution. 4 (1), 77-82. USEPA (US Environmental Protection Agency), 1989. Risk Assessment Guidance for Superfund, Vol. I: Human Health Evaluation Manual (Part A) (EPA 540/1-89/002). US Environmental Protection Agency, Office of Emergency and Remedial Response, Washington, DC. USEPA (US Environmental Protection Agency), 2002. Risk-based concentration table. Washington, DC: US Environmental Protection Agency. Wang, Y.Q., He, L.X., Ma, Y.G., Li, B.Q., Li, J.N., Zan, B.Y., 2012. Study on distribution of chromium (VI) and its migration characters in Shaanxi district in Weihe River. Journal of Northwest A&F University (Nat. Sci. Ed.). 40, 129-134. WHO (2017) Guidelines for drinking water quality: fourth edition incorporating the first addendum. World Health Organization, Geneva. Wu, J.H., Zhou, H., He, S., Zhang, Y.X., 2019. Comprehensive understanding of groundwater quality for domestic and agricultural purposes in terms of health risks in a coal mine area of the Ordos basin, north of the Chinese Loess Plateau. Environmental Earth Sciences 78: 446. Xing, L., Guo, H., Zhan, Y., 2013. Groundwater hydrochemical characteristics and processes along flow paths in the North China Plain. Journal of Asian Earth Sciences. 70-71, 250-264. Xu, B., Zhang, Y., Wang, J.F., 2019. Hydrogeochemistry and human health risks of groundwater fluoride in Jinhuiqu irrigation district of Wei river basin, China. Human and Ecological Risk Assessment: An International Journal. DOI: 10.1080/10807039.2018.1530939. Yari, A.R., Sobhanardakani, S., 2016. Water quality assessment of groundwater resources in Qaleeh Shahin plain based on Cd and HEI. Int. Arch. Health Sci. 3 (3),101-106.
411
Zahedi, S., Azarnivand, A., Chitsaz, N., 2017. Groundwater quality classification derivation using
412
Multi-Criteria-Decision-Making techniques. Ecological Indicators. 78, 243-252.
Table 1 RfD and SF values for As and other heavy metals. Non-Carcinogen Cr Ni Cd Pb As Cu Zn Fe Mn V Mo Al Co Unit: mg (kg*d)–1
RfD 0.003 2 × 10–2 0.0005 1.4 × 10–3 0.0003 5 × 10–3 3 × 10–1 3 × 10–1 1.4 × 10–1 0.007 0.005 0.14 0.0003
Carcinogen Cr Cd As
SF 41 6.1 1.5
Table 2 Descriptive statistics for heavy metals in groundwater samples. Shallow groundwater samples Deep groundwater samples Heavy metal No. Min Max Mean CV No. Min Max Mean CV Al (µg/L) 116 0 66.47 2.46 2.68 14 0 6.55 0.79 0.46 V (µg/L) 116 0.035 15.68 2.93 0.94 14 0.054 5.21 1.98 1.12 Cr (µg/L) 116 0 174.76 21.27 1.6 14 0.000 21.80 5.54 0.68 Mn (µg/L) 116 0.001 43.37 1.21 4.39 14 0.320 19.43 3.30 0.63 Fe (µg/L) 116 2.156 116.61 27.38 0.84 14 2.804 28.63 16.10 2.07 Ni (µg/L) 116 0 1.79 0.07 3.2 14 0 1.82 0.29 0.56 Cu (µg/L) 116 0.003 1.13 0.15 1.24 14 0 3.61 0.56 0.57 Zn (µg/L) 116 0.374 21.11 3.6 0.85 14 2.953 424.22 92.05 0.79 Co (µg/L) 116 0.004 0.62 0.09 1.22 14 0.006 0.24 0.03 0.57 Pb (µg/L) 116 0 9.53 0.3 3.03 14 0 0.38 0.09 0.69 As (µg/L) 116 0.027 8.12 1.2 1.07 14 0.054 2.60 0.99 1.25 Mo (µg/L) 116 0.075 74.08 5.26 1.9 14 0.576 26.09 7.30 0.85 Cd (µg/L) 116 0.006 0.16 0.04 0.72 14 0.008 0.04 0.02 2.03 No., number; Min, minimum; Max, maximum; CV, coefficient of variation
Table 3 Heavy metal concentration limits specified by the WHO and in China. Heavy metals
Al
V
Cr Mn
Fe
Ni
Cu
Zn
Co Pb As Mo
Cd
WHO (µg/L)
200
10 10
70
5
China (µg/L)
200 50 50 100 300 20 1000 1000 50
10 10
70
5
50 500 300 20 1000 5000
Table 4 Descriptive statistics for heavy metals in 14 shallow and 14 deep groundwater samples. Shallow groundwater samples
Deep groundwater samples
Heavy metal
No.
Min
Max
Mean
CV
Min
Max
Mean
CV
Al (µg/L)
14
0
4.95
1.59
0.85
0
6.55
0.79
0.46
V (µg/L)
14
0.255
7.74
2.19
0.89
0.054
5.21
1.98
1.12
Cr (µg/L)
14
0
38.11
10.92
1.27
0.000
21.80
5.54
0.68
Mn (µg/L)
14
0.011
25.83
2.68
2.64
0.320
19.43
3.30
0.63
Fe (µg/L)
14
3.159
47.86
19.81
0.73
2.804
28.63
16.10 2.07
Ni (µg/L)
14
0
0.84
0.14
1.99
0
1.82
0.29
0.56
Cu (µg/L)
14
0.006
0.76
0.19
1.18
0
3.61
0.56
0.57
Zn (µg/L)
14
0.374
12.13
3.95
0.76
2.953 424.22 92.05 0.79
Co (µg/L)
14
0.007
0.33
0.11
0.80
0.006
0.24
0.03
0.57
Pb (µg/L)
14
0
0.74
0.18
1.15
0
0.38
0.09
0.69
As (µg/L)
14
0.027
3.29
0.96
0.82
0.054
2.60
0.99
1.25
Mo (µg/L)
14
0.267
6.18
2.24
0.91
0.576
26.09
7.30
0.85
Cd (µg/L)
14
0.018
0.08
0.04
0.60
0.008
0.04
0.02
2.03
No., number; Min, minimum; Max, maximum; CV, coefficient of variation
Table 5 HQ values obtained from the health risk assessments for non-carcinogenic metals. Heavy metal No.
Min
Max
Mean
No.
Min
Max
Mean
Al (µg/L)
116
0
0.013
0.0005
14
0
0.0013 0.0002
V (µg/L)
116
0.0001
0.0640
0.0120
14
0.0002
0.0213 0.0081
Mn (µg/L)
116 2.490E-07
0.009
0.0002
14
Fe (µg/L)
116
0.0002
0.011
0.0026
14
0.0003
0.0027 0.0015
Ni (µg/L)
116
0
0.003
9.72E-05
14
0
0.0026 0.0004
Cu (µg/L)
116 1.486E-05
0.006
0.0009
14
0
0.0207 0.0032
Zn (µg/L)
116 3.563E-05
0.002
0.0003
14
0.0003
0.0404 0.0088
Co (µg/L)
116
0.0004
0.059
0.0082
14
0.0006
0.0232 0.0033
Pb (µg/L)
116
0
0.195
0.0061
14
0
0.0077 0.0018
Mo (µg/L)
116
0.0004
0.423
0.0301
14
0.0033
0.1491 0.0417
Cr (µg/L)
116
0
1.664
0.2026
14
0.0000
0.2076 0.0527
As (µg/L)
116
0.0038
1.161
0.1718
14
0.0077
0.3710 0.1412
Cd (µg/L)
116
0.0003
0.009
0.0022
14
0.0005
0.0021 0.0010
No., number; Min, minimum; Max, maximum
6.53E-05 0.0040 0.0007
Table 6 Carcinogenic potential of groundwater in the Guanzhong Plain region. Heavy metals
No.
Min
Max
Mean
No.
Min
Max
Mean
Cr (µg/L)
116
0
0.0845
0.0105
14
0
0.0109
0.0028
As (µg/L)
116
4.91E-07
0.0001
2.21E-05
14
9.85E-07
4.77E-05
1.81E-05
Cd (µg/L)
116
4.23E-07
1.22E-05
2.94E-06
14
5.93E-07
2.71E-06
1.32E-06
No., number; Min, minimum; Max, maximum
Figure 1. Location of the Guanzhong Plain in China (a) and the sampling sites (b).
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
Figure 2. Spatial distributions of heavy metals in the shallow groundwater (a) and deep groundwater samples (b).
(a)
(b)
(a)
(b)
Figure 3. HPI and HEI values for shallow groundwater (a) and deep groundwater (b) samples in the Guanzhong Plain region.
1. Spatial distributions of heavy metals in groundwater in Guanzhong Plain, China. 2. Differences in heavy metals compared in shallow and deep groundwater samples. 3. Groundwater quality evaluated using two water quality indices. 4. Non-carcinogenic and carcinogenic health risks due to heavy metals assessed.
Declaration of Interest Statement No conflicts of interest exist regarding the submission of this manuscript and manuscript has been approved for publication by all of the authors. On behalf of my co-authors, I declare that the work described is original research that has not been published previously and it is not under consideration for publication elsewhere, in whole or in part. All the authors have approved the submitted manuscript.