Fu-ning Lan; Yi Zhao; Jun Li; Xiu-qun Zhu

doi:10.26599/JGSE.2024.9280005

doi: 10.26599/JGSE.2024.9280005

^{1, 2},
^{1, 2},
^3, ,,
⁴

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出版历程
- 收稿日期: 2023-09-26
- 录用日期: 2023-12-18
- 网络出版日期: 2024-03-15
- 刊出日期: 2024-03-15

Health risk assessment of heavy metal pollution in groundwater of a karst basin, SW China

Fu-ning Lan^{1, 2},
Yi Zhao^{1, 2},
Jun Li^{3
, ,},
Xiu-qun Zhu⁴

1.
Karst Ecosystem, National Observation and Research Station, Pingguo 531406, Guangxi, China
2.
Institute of Karst Geology, International Research Centre on Karst, Under the Auspices of UNESCO, Guangxi Karst Resources and Environment Research Center of Engineering Technology, Chinese Academy of Geological Sciences, Karst Dynamics Laboratory, MNR and Guangxi, Guilin 541004, China
3.
Hebei Key Laboratory of Water Quality Engineering and Comprehensive Utilization of Water Resources, Hebei University of Architecture, Zhangjiakou 075000, Hebei Province, China
4.
College of Hydrology and Water Resources, Hohai University, Nanjing 210098, China

More Information

Corresponding author: lipshydro@163.com

摘要

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Abstract: To investigate the presence of metal elements and assess their health risk for the populace in the Nandong Underground River Basin (NURB), we conducted an analysis of eleven common heavy metals in the water body. A Health risk assessment (HRA) model was employed to analyze 84 water samples from the NURB. The detection results revealed the following order of heavy metals concentrations: Fe > Al > Mn > Zn > As > Cd > Pb > Cr > Ni > Cu > Hg. Correlation analysis indicated a certain similarity in material source and migration transformation among these eleven metal elements. Our study identified that the health risks for local residents exposed to metal elements in the water of NURB primarily stem from carcinogenic risk (10⁻⁶–10⁻⁴ a⁻¹) through the drinking water pathway. Moreover, the health risk of heavy metal exposure for children through drinking water was notably higher than for adults. The maximum health risks of Cr in both underground and surface water exceeded the recommendation standard (5.0×10⁻⁵ a⁻¹) from ICRP, surpassing the values recommended by the Swedish Environmental Protection Agency, the Dutch Ministry of Construction and Environment and the British Royal Society (5.0×10⁻⁶ a⁻¹). The results of the health risk assessment indicate that Cr in the water of NURB is the primary source of carcinogenic risk for local residents, followed by Cd and As. Consequently, it is imperative to control these three carcinogenic metals when the water was used as drinking water resource.
- Water Pollution /
- Correlation Analysis /
- Toxicity of Heavy Metal Elements /
- Underground River Basin /
- Carcinogenicity Potential

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Figure 1. Surface-underground water system of Nandong Undeground River Basin and sampling sites in our study

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Figure 2. Piper diagram of water samples in NURB

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Figure 3. Distributions and dynamic changes of metal elements in surface and groundwater samples in NURB

*GW means groundwater, SW means surface water

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Figure 4. Monthly maximum health risks exposure to metal elements from different water sources for adults through: (a) Drinking; (b) Skin penetration

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Figure 5. Monthly maximum health risks exposure to metal elements from different water sources for children through: (a) Drinking; (b) Skin penetration

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Table 1. Values of parameters related to health risk assessment

Metal		PC (10⁻³/cm·h⁻¹)	SF/(kg·d)·mg⁻¹		RfD/mg·(kg·d)⁻¹
Metal		PC (10⁻³/cm·h⁻¹)	Drinking water	Skin penetration	Drinking water	Skin penetration
Carcinogenic	As	1.8	1.5	3.66	/	/
	Cr	2	41	41	/	/
	Cd	1	6.1	6.1	/	/
Non-carcinogenic	Al	10	/	/	0.14	0.14
	Cu	0.6	/	/	0.04	0.012
	Pb	0.004	/	/	0.0014	0.00042
	Zn	0.6	/	/	0.3	0.01
	Fe	0.1	/	/	0.3	0.045
	Ni	0.1	/	/	0.02	0.0054
	Mn	0.1	/	/	0.046	0.0018
	Hg	1.8	/	/	0.0003	0.0003
Note: ^*No reference standard value; PC, permeability coefficient; SF, slope factor; RfD, reference daily intake.

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Table 2. Concentrations of metals in the water of Nandong Groundwater River Basin (μg·L⁻¹)

Metals n=84	Scope	Average	Standard deviation	Variation coefficient	Exceed standard limitation (%)
Al	9.90–5,274.00	440.04	913.09	2.08	38.10
Cu	nd–26.70	2.34	4.75	2.03	0
Pb	nd–124.00	3.62	15.43	4.26	2.38
Zn	nd–1,311.00	82.39	211.24	2.56	1.19
Fe	nd–7,790.00	486.83	1,127.61	2.32	26.19
Cr	1.10–10.70	3.47	2.08	0.60	0
Cd	nd–61.00	3.63	10.34	2.85	7.14
Ni	0.78–13.90	2.99	2.22	0.74	0
Mn	2.44–2,035.00	113.13	276.85	2.45	15.48
As	nd–54.70	6.13	8.01	1.31	17.86
Hg	nd–0.94	0.41	0.26	0.63	40.48
Metals n=84	China			US EPA	WHO
Metals n=84	Drinking water (Limits)	Surface water（Ⅲ）	Ground water（Ⅲ）	Drinking water	Drinking water
Al	200	–	200	–	200
Cu	1,000	1,000	1,000	1,300	2,000
Pb	10	50	10	15	10
Zn	1,000	1,000	1,000	–	–
Fe	300	–	300	–	300
Cr	50	50	50	100	50
Cd	5	5	5	5	3
Ni	20	–	20	–	70
Mn	100	100	100	–	400
As	10	50	10	10	10
Hg	1	0.1	1
^*nd means not detected, –means no corresponding reference value.

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Table 3. Pearson correlation matrix for metal elements and pH in the water samples

n=84	EC	pH	Al	Cu	Pb	Zn	Fe	Cr	Cd	Ni	Mn	As	Hg
EC	1.000	0.164	−0.042	0.083	0.031	0.177	−0.064	0.033	0.124	0.140	0.023	0.163	0.060
pH		1.000	0.045	0.040	0.134	−0.022	0.032	0.179	−0.070	0.109	0.024	−0.041	−0.147
Al			1.000	0.746^**	0.579^**	0.240^*	0.929^**	0.632^**	0.037	0.916^**	0.652^**	0.290^**	−0.201
Cu				1.000	0.756^**	0.692^**	0.700^**	0.479^**	0.171	0.805^**	0.920^**	0.282^**	−0.172
Pb					1.000	0.285^**	0.490^**	0.351^**	0.112	0.690^**	0.486^**	0.268^*	−0.103
Zn						1.000	0.166	0.210	0.469^**	0.327^**	0.757^**	0.060	0.016
Fe							1.000	0.641^**	0.014	0.836^**	0.659^**	0.447^**	−0.207
Cr								1.000	0.199	0.643^**	0.431^**	0.169	−0.292^**
Cd									1.000	0.095	0.141	0.032	0.297^**
Ni										1.000	0.657^**	0.206	−0.237^*
Mn											1.000	0.294^**	−0.154
As												1.000	−0.014
Hg													1.000
^* Significant at 0.05 level. ^{* *} Significant at 0.01 level. EC means Electrical Conductivity

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Table 4. Annual per capita health risks caused by metals in different types of water though drinking water and skin penetration, respectively (a⁻¹)

Exposure way	Metals		Groundwater		Surface Water
Exposure way	Metals		Adults	Children	Adults	Children
Drinking water	Carcinogenesis	As	/–1.93×10⁻⁵	/–2.30×10⁻⁵	6.91×10⁻⁷– 4.30×10⁻⁵	8.24×10⁻⁷– 5.12×10⁻⁵
		Cr	5.11×10⁻⁵– 2.30×10⁻⁴	6.09×10⁻⁵– 2.74×10⁻⁴	2.36×10⁻⁵– 2.30×10⁻⁴	2.81×10⁻⁵– 2.74×10⁻⁴
		Cd	/–1.95×10⁻⁴	/–2.32×10⁻⁴	/–4.67×10⁻⁶	/–5.56×10⁻⁶
	No-carcinogenesis	Al	4.53×10⁻¹¹– 1.97×10⁻⁸	5.39×10⁻¹¹– 2.35×10⁻⁸	3.70×10⁻¹¹– 1.69×10⁻⁸	4.41×10⁻¹¹– 2.01×10⁻⁸
		Cu	/–3.50×10⁻¹⁰	/–4.16×10⁻¹⁰	2.23×10⁻¹²– 2.70×10⁻¹⁰	2.65×10⁻¹²– 3.21×10⁻¹⁰
		Pb	/–4.64×10⁻⁸	/–5.53×10⁻⁸	/–1.64×10⁻⁸	/–1.95×10⁻⁸
		Zn	/–2.29×10⁻⁹	/–2.73×10⁻⁹	/–7.67×10⁻¹¹	/–9.13×10⁻¹¹
		Fe	/–8.31×10⁻⁹	/–9.90×10⁻⁹	/–1.36×10⁻⁸	/–1.62×10⁻⁸
		Ni	3.85×10⁻¹¹– 3.64×10⁻¹⁰	4.59×10⁻¹¹– 4.34×10⁻¹⁰	2.04×10⁻¹¹– 2.86×10⁻¹⁰	2.43×10⁻¹¹– 3.40×10⁻¹⁰
		Mn	2.78×10⁻¹¹– 2.31×10⁻⁸	3.31×10⁻¹¹– 2.76×10⁻⁸	6.07×10⁻¹¹– 1.44×10⁻⁸	7.23×10⁻¹¹– 1.72×10⁻⁸
		Hg	/–1.54×10⁻⁹	/–1.83×10⁻⁹	/–1.64×10⁻⁹	/–1.96×10⁻⁹
Drinking water	Carcinogenesis	As	/–4.40×10⁻⁷	/–3.37×10⁻⁷	1.57×10⁻⁸– 9.78×10⁻⁷	1.21×10⁻⁸– 7.49×10⁻⁷
		Cr	5.30×10⁻⁷– 2.38×10⁻⁶	4.06×10⁻⁷– 1.83×10⁻⁶	2.45×10⁻⁷– 2.38×10⁻⁶	1.87×10⁻⁷– 1.83×10⁻⁶
		Cd	/–1.01×10⁻⁶	/–7.74×10⁻⁷	/–2.42×10⁻⁸	/–1.85×10⁻⁸
	No-carcinogenesis	Al	2.35×10⁻¹²– 1.02×10⁻⁹	1.80×10⁻¹²– 7.83×10⁻¹⁰	1.92×10⁻¹²– 8.75×10⁻¹⁰	1.47×10⁻¹²– 6.71×10⁻¹⁰
		Cu	/–3.62×10⁻¹²	/–2.78×10⁻¹²	2.31×10⁻¹⁴– 2.80×10⁻¹²	1.77×10⁻¹⁴– 2.14×10⁻¹²
		Pb	/–3.21×10⁻¹²	/–2.46×10⁻¹²	/–1.13×10⁻¹²	/–8.68×10⁻¹³
		Zn	/–2.14×10⁻¹⁰	/–1.64×10⁻¹⁰	/–7.15×10⁻¹²	/–5.48×10⁻¹²
		Fe	/–2.87×10⁻¹¹	/–2.19×10⁻¹¹	/–4.70×10⁻¹¹	/–3.59×10⁻¹¹
		Ni	7.39×10⁻¹⁴– 6.99×10⁻¹³	5.66×10⁻¹⁴– 5.35×10⁻¹³	3.92×10⁻¹⁴– 5.48×10⁻¹³	3.00×10⁻¹⁴– 4.20×10⁻¹³
		Mn	3.68×10⁻¹³– 3.07×10⁻¹⁰	2.82×10⁻¹³– 2.35×10⁻¹⁰	8.04×10⁻¹³– 1.91×10⁻¹⁰	6.16×10⁻¹³– 1.46×10⁻¹⁰
		Hg	/–1.43×10⁻¹¹	/–1.10⁻¹¹	/–1.53×10⁻¹¹	/–1.17×10⁻¹¹
“/”means no calculation results.

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