工业区周边农田土壤重金属与黏土矿物的关系及其生态健康风险评价

李文鹏; 史小龙; 刘建章; 陈爽; 蔡奎; 宋泽峰; 田浩飞

doi:10.12029/gc20211126003

工业区周边农田土壤重金属与黏土矿物的关系及其生态健康风险评价

1.
河北省地质矿产勘查开发局第六地质大队（河北省地质矿产勘查开发局航空测量应用中心）, 河北石家庄 050085

2.
河北地质大学河北省战略性关键矿产资源重点实验室, 河北石家庄 050031

3.
河北地质大学资源与环境工程研究所, 河北石家庄 050031

4.
韩国群山大学地质科学与工程学院, 韩国全北 573−701

基金项目: 河北省自然科学基金项目（D2020403003）和河北省自然资源厅科技项目联合资助（454−0601−YBN−P6GT）联合资助。

详细信息

作者简介: 李文鹏，男，1978年生，高级工程师，主要从事场地污染防治研究；E-mail：biIuochu2019@163.com

通讯作者: 蔡奎，男，1985年生，博士，副研究员，主要从事环境地球化学研究；E-mail：kcai@hgu.edu.cn。

中图分类号: X53; X826

收稿日期: 2021-11-26

修回日期: 2022-03-28

刊出日期: 2024-09-25

Relationship between heavy metals and clay minerals in farmland soil around industrial zone and health risk assessment

1.
The Sixth Geological Brigade, Hebei Bureau of Geology and Mineral Resources Exploration, Shijiazhuang 050085, Hebei, China

2.
Hebei Key Laboratory of Strategic Critical Mineral Resources, Hebei GEO University, Shijiazhuang 050031, Hebei, China

3.
Institute of Resources and Environmental Engineering, Hebei GEO University, Shijiazhuang 050031, Hebei, China

4.
Department of Geological Science & Engineering, Kunsan National University, Jeonbuk 573−701, South Korea

Fund Project: Supported by the project of Hebei Province Natural Science Foundation (No.D2020403003) and science and technology project of Department of Natural Resources of Hebei Province (No.454−0601−YBN−P6GT).

More Information

Author Bio: LI Wenpeng, male, born in 1978, engineer, engaged in the study of prevention and control of site pollution; E-mail: biluochu2019@163.com .

Corresponding author: CAI Kui, male, born in 1985, associate researcher, mainly engaged in environmental geochemistry investigation and research; E-mail: kcai@hgu.edu.cn.

Received Date: 26 November 2021

Revised Date: 28 March 2022

Publish Date: 25 September 2024

摘要

摘要: 研究目的
为了解工业区周边农田土壤重金属污染状况，采集了100件表层土壤样品，分析测试Pb、Cr、As、Cd和Hg等5种重金属元素总量、赋存形态以及黏土矿物含量。
研究方法
采用单因子指数法、土壤矿物评价法以及健康风险评估模型等，对石家庄无极皮革厂，辛集皮革厂，邯郸武安冶金、钢铁，广平化工厂，以及邢台内丘化工厂周边的农田土壤重金属污染状况、稳定性以及健康水平进行评价。
研究结果
无极皮革厂土壤的Cr，内丘、广平化工厂的Hg和武安冶金、钢铁的Cd和Hg污染程度高；以残渣态为主的重金属与黏土矿物具有显著正相关关系；土壤黏土矿物对Cd、Hg固持量高，对Pb和As的固持量低。无极2个土壤样品超出了黏土矿物对Cr的容纳能力；人体健康风险评估显示，在口和皮肤双重摄入途径下，土壤会对儿童造成非致癌风险（1.02）。但是，以小麦为摄入介质的癌症风险指数超过了成人（5.16×10⁻⁴）和儿童（6.44×10⁻⁴）的耐受限度（1×10⁻⁴）。
结论
重金属与黏土矿物存在积极的相关性，对生态健康风险影响大，当地以小麦为主食的居民对小麦Cd应更加关注。
- 工业区 /
- 重金属 /
- 赋存形态 /
- 黏土矿物 /
- 健康地质 /
- 环境地质调查工程
Abstract:
This paper is the result of environmental geological survey engineering.
Objective
This study aimed to understand the stability of heavy metal pollution in farmland soils surrounding industrial zones. A total of 100 surface soil samples were collected and analyzed for the total concentration and speciation of Pb, Cr, As, Cd, and Hg as well as their association with clay minerals.
Methods
The extent of pollution and stability of farmland soils and health risks associated with the soil and wheat cultivated in these soils around Wuji Tannery, Xinji Tannery, Handan and Wuan Metallurgy, Guangping Chemical Plant, and Neiqiu Chemical Plant were evaluated. The evaluation was conducted using the single−factor index method, soil mineral evaluation method, and health risk assessment model.
Results
The analysis revealed high concentrations of Cr in Wuji Tannery soil, Hg in Neiqiu and Guangping Chemical Plant soil, and Cd and Hg in Wuan Metallurgy soil. A significant correlation was observed between heavy metals, particularly those in the residual fraction, and clay minerals such as montmorillonite, chlorite, and illite. Clay minerals exhibited high retention of Cd and Hg but low retention of Pb and As. Additionally, clay minerals in two soil samples from Wuji exceeded the Cr retention capacity Human health risk assessments indicated that soils posed a noncarcinogenic risk (1.02) to children via oral and dermal exposure. Moreover, the cancer risk index, with wheat as the intake medium, exceeded the acceptable limit (1×10⁻⁴) for both adults (5.16×10⁻⁴) and children (6.44×10⁻⁴).
Conclusions
There is a positive relationship between heavy metals and clay minerals. Therefore, residents in industrial areas, particularly those who rely on wheat as a staple food, should pay close attention to the Cd content in wheat.
- industrial zone /
- heavy metals /
- speciation /
- clay minerals /
- healthy geology /
- environmental geological survey engineering

HTML全文

图 1 5个工业区表层土壤（0~20 cm）样品采集示意图

Figure 1.

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图 2 工业区单因子污染指数分级百分比柱状图

Figure 2.

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图 3 工业区农田土壤重金属元素与黏土矿物平均含量剖面（0~100 cm）分布图

Figure 3.

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图 4 重金属不同深度赋存形态相对含量分布图

Figure 4.

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表 1 各种暴露途径日摄入量计算公式

Table 1. Formulas of calculating daily intake of various exposure pathways

介质	暴露途径	计算公式
土壤	摄入/口	$ {{\mathrm{ADD}}}_{{\mathrm{ingestion}}}=\dfrac{{\mathrm{C}}_{{S}} \times {\mathrm{IR}}_{{S}} \times {\mathrm{EF}} \times {\mathrm{ED}}}{{\mathrm{BW}} \times {\mathrm{AT}}} \times {10}^{-6} $	（4）
土壤	皮肤/接触	$ {{\mathrm{ADD}}}_{{\mathrm{dermal}}}=\dfrac{{\mathrm{C}}_{{S}} \times {\mathrm{SA}} \times {\mathrm{AF}} \times {\mathrm{ABS}} \times {\mathrm{EF}} \times {\mathrm{ED}}}{{\mathrm{BW}} \times {\mathrm{AT}}} \times {10}^{-6} $	（5）
小麦	摄入/口	$ {{\mathrm{ADD}}}_{{\mathrm{ingestion}}}=\dfrac{C_{\mathrm{wheat}} \times {\mathrm{IR}}_{\mathrm{wheat}} \times {\mathrm{EF}} \times {\mathrm{ED}}}{{\mathrm{BW}} \times {\mathrm{AT}}} $	（6）

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表 2 健康风险计算参数的取值及意义

Table 2. Value and significance of health risk calculation parameters

参数	单位和取值	意义
C_s, C_W	mg/kg	暴露浓度
EF	365 d/a	年暴露频率
ED	成人 70 a; 儿童 6a	持续时间
ET	24 h/d	日暴露频率
AT	365 × ED day	（非）致癌物的平均时间
BW	成人 70 kg ; 儿童 18 kg	体重
SA	成人5700 cm²·day⁻¹, 儿童2800 cm²·day⁻¹	暴露皮肤面积
AF	成人0.07 mg·cm⁻², 儿童0.02 mg·cm⁻²	吸附因子
ABS	0.001	皮肤吸收分数
PEF	1.36×10⁹ m³∙kg⁻¹	粒子排放因子
CF	10⁻⁶ kg∙mg⁻¹	单位转换因子
IR_S	成人100 mg·d⁻¹ , 儿童200 mg·d⁻¹	土壤摄入率
IR_wheat	成人0.225 kg·d⁻¹, 儿童0.075 kg·d⁻¹	小麦摄入率
RFD−Cd	RFD 摄入: 0.001 mg ∙ kg⁻¹∙d⁻¹, RFD 呼吸: 0.00001 mg∙kg⁻¹∙d⁻¹, RFD皮肤: 0.00001 mg ∙ kg⁻¹∙d⁻¹	慢性参考剂量
RFD−As	RFD_ingestion: 3×10⁻⁴ mg∙kg⁻¹∙d⁻¹, RFD_inhale: 1.23×10⁻⁴ mg∙kg⁻¹∙d⁻¹, RFD_dermal: 1.23×10⁻⁴ mg∙kg⁻¹∙d⁻¹
RFD−Cr	RFD_ingestion: 3×10⁻³ mg∙kg⁻¹∙d⁻¹, RFD_inhale: 2.86×10⁻⁵ mg∙kg⁻¹∙d⁻¹, RFD_dermal: 6×10⁻⁵ mg∙kg⁻¹∙d⁻¹
SF	Cd：SF_摄入: 15 kg∙d∙mg⁻¹, SF_呼吸: 6.3 kg∙d∙mg⁻¹； As：SF_摄入: 1.5 kg∙d∙mg⁻¹, SF_呼吸: 15.1 kg∙d∙mg⁻¹, SF_皮肤: 3.66 kg∙d∙mg⁻¹；Cr：SF_呼吸: 42 kg∙d∙mg⁻¹	斜率因子

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表 3 工业区周边农田表层土壤重金属含量（μg/g）统计

Table 3. Statistics of heavy metal content (μg/g) in surface soil of farmland around industrial zone

地名/性质	元素	最大值	最小值	平均值	标准差	变异系数/%	河北省背景值	富集系数
辛集工业区（皮革） N=20	Pb	32.1	17.2	22.23	3.79	17.03	21.1	1.05
	Cr	84	56.8	66.7	6.75	10.12	68.1	0.98
	Cd	0.22	0.08	0.15	0.04	26.42	0.09	1.67
	As	11.6	7.01	8.98	1.05	11.68	13	0.69
	Hg	0.097	0.013	0.045	0.02	44.17	0.04	1.13
广平工业区（化工） N=20	Pb	25.9	20.4	23.23	1.53	6.59	21.1	1.10
	Cr	76.1	58.9	67.19	4.6	6.84	68.1	0.99
	Cd	0.3	0.12	0.17	0.04	23.81	0.09	1.89
	As	12.9	8.82	10.74	1.25	11.61	13	0.83
	Hg	0.231	0.022	0.049	0.05	97.76	0.04	1.23
无极工业区（皮革） N=20	Pb	36.9	17.7	23.98	3.64	15.19	21.1	1.14
	Cr	165	58	78.87	23.96	30.38	68.1	1.16
	Cd	0.25	0.1	0.15	0.03	19.97	0.09	1.67
	As	9.21	6.85	8.53	0.61	7.14	13	0.66
	Hg	0.084	0.015	0.055	0.02	35.50	0.04	1.38
内丘工业区（化工） N=20	Pb	41.2	20.6	24.06	4.36	18.11	21.1	1.14
	Cr	72.6	59.4	64.35	3.88	6.03	68.1	0.94
	Cd	0.32	0.12	0.16	0.04	26.15	0.09	1.78
	As	10.5	6.96	8.633	0.91	10.49	13	0.66
	Hg	0.18	0.022	0.066	0.04	59.24	0.04	1.65
武安工业区（冶金、钢铁） N=20	Pb	38.1	23.4	32.43	3.53	10.88	21.1	1.54
	Cr	74.6	56.3	66.91	4.57	6.83	68.1	0.98
	Cd	0.25	0.12	0.21	0.03	15.58	0.09	2.33
	As	13.4	8.93	11.16	1.29	11.51	13	0.86
	Hg	0.184	0.034	0.09	0.04	47.40	0.04	2.25

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表 4 黏土矿物与重金属元素相关性

Table 4. Correlation of clay minerals and heavy metal elements

表层黏土矿物与重金属元素相关性
矿物类型	As	Hg	Cd	Cr	Pb
蒙脱石	−0.116	0.307	−0.101	−0.307	−0.118
伊利石	0.632*	0.168	0.354	−0.625	0.345
高岭石	−0.389	−0.112	−0.168	0.458	−0.153
绿泥石	−0.694*	0.004	−0.509	0.56	−0.281
伊/蒙混层	−0.247	−0.573	−0.021	0.646*	−0.304
剖面黏土矿物与重金属元素相关性
蒙脱石	0.632*	0.45	0.717**	−0.275	0.634*
伊利石	0.728**	0.278	0.366	−0.684**	0.355
高岭石	0.567*	−0.312	−0.326	0.838**	−0.341
绿泥石	−0.808**	−0.24	−0.444	0.33	−0.405
伊/蒙混层	0.065	−0.133	−0.178	−0.009	−0.104
注：*表示P< 0.01 水平上显著相关；表示P < 0.05 水平上显著相关。

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表 5 不同暴露方式下土壤和小麦的非致癌风险（HQ）和致癌风险（CR）（成人为−a，儿童为−c）

Table 5. Non-carcinogenic and carcinogenic risks of soil and wheat under different exposures （−a for adults and −c for children）

重金属	介质	暴露方式	ADD−a	ADD−c	HQ−a	HQ−c	CR−a	CR−c
Cd	土壤	皮肤	3.47 × 10⁻⁸	6.65 × 10⁻⁸	2.83 × 10⁻⁴	5.40 × 10⁻⁴	—	—
	土壤	摄入/口	2.11 × 10⁻¹⁰	3.43× 10⁻¹⁰	7.05 × 10⁻⁷	1.44 × 10⁻⁶	3.17 × 10⁻¹⁰	5.15 × 10⁻¹⁰
	小麦	摄入/口	1.03 × 10⁻⁷	1.29 × 10⁻⁷	3.44 × 10⁻⁵	4.29 × 10⁻⁵	5.16× 10⁻⁴	6.44 × 10⁻⁴
As	土壤	皮肤	1.69× 10⁻⁶	3.23× 10⁻⁶	1.37× 10⁻²	2.63 × 10⁻²	6.19× 10⁻⁶	1.18 × 10⁻⁵
	土壤	摄入/口	8.06× 10⁻⁸	1.67 × 10⁻⁸	2.69× 10⁻⁴	5.57× 10⁻⁵	1.21 × 10⁻⁷	2.50 × 10⁻⁸
	小麦	摄入/口	9.03 × 10⁻⁸	1.13 × 10⁻⁷	3.01× 10⁻⁴	3.75× 10⁻⁴	1.35 × 10⁻⁷	1.69 × 10⁻⁷
Cr	土壤	皮肤	2.35 × 10⁻³	4.48 × 10⁻³	1.56 × 10⁻³	2.99 × 10⁻³	—	—
	土壤	摄入/口	3.00 × 10⁻⁸	4.87 × 10⁻⁸	2.00 × 10⁻⁵	3.25 × 10⁻⁸	1.26 × 10⁻⁶	2.04 × 10⁻⁶
	小麦	摄入/口	1.05 × 10⁻⁷	1.30 × 10⁻⁷	6.97 × 10⁻⁸	8.69 × 10⁻⁸	4.39 × 10⁻⁶	5.48 × 10⁻⁶
Pb	土壤	皮肤	2.01 × 10⁻³	3.85× 10⁻³	0.50	0.96	—	—
	土壤	摄入/口	2.57 × 10⁻⁸	4.18 × 10⁻⁵	6.43 × 10⁻⁶	1.04 × 10⁻⁵	—	—
	小麦	摄入/口	1.95 × 10⁻⁷	2.43 × 10⁻⁷	4.87 × 10⁻⁵	6.07 × 10⁻⁵	—	—
Hg	土壤	皮肤	4.90 × 10⁻⁶	9.30 × 10⁻⁶	1.62 × 10⁻²	3.10 × 10⁻²	—	—
	土壤	摄入/口	6.22 × 10⁻¹¹	1.01 × 10⁻¹⁰	1.04 × 10⁻⁷	3.37 × 10⁻⁷	—	—
	小麦	摄入/口	6.88 × 10⁻⁹	8.57 × 10⁻⁹	2.29 × 10⁻⁵	2.86 × 10⁻⁵	—	—
			ADD−a/总	ADD−c/总	HQ		TCR
小计	土壤		4.37× 10⁻³	8.44× 10⁻³	0.53	1.02	7.57×10⁻⁶	1.39×10⁻⁵
小计	小麦		5.00 × 10⁻⁷	6.24× 10⁻⁷	4.07×10⁻⁴	5.07×10⁻⁴	5.20×10⁻⁴	6.5×10⁻⁴
合计			4.37× 10⁻³	8.39× 10⁻³	0.53	1.02	5.28×10⁻⁴	6.64×10⁻⁴

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中国地质调查局中国地质科学院	主办
科学出版社	出版

工业区周边农田土壤重金属与黏土矿物的关系及其生态健康风险评价

作者简介: 李文鹏，男，1978年生，高级工程师，主要从事场地污染防治研究；E-mail：biIuochu2019@163.com

通讯作者: 蔡奎，男，1985年生，博士，副研究员，主要从事环境地球化学研究；E-mail：kcai@hgu.edu.cn。

Relationship between heavy metals and clay minerals in farmland soil around industrial zone and health risk assessment

Author Bio: LI Wenpeng, male, born in 1978, engineer, engaged in the study of prevention and control of site pollution; E-mail: biluochu2019@163.com .

Corresponding author: CAI Kui, male, born in 1985, associate researcher, mainly engaged in environmental geochemistry investigation and research; E-mail: kcai@hgu.edu.cn.

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