化隆—循化盆地不同类型含水层组高氟地下水的分布及形成过程

doi:10.13745/j.esf.sf.2022.1.34

地学前缘 ›› 2022, Vol. 29 ›› Issue (3): 115-128.DOI: 10.13745/j.esf.sf.2022.1.34

化隆—循化盆地不同类型含水层组高氟地下水的分布及形成过程

邢世平¹(), 郭华明¹^,^*(), 吴萍²^,^*(), 胡学达¹, 赵振², 袁有靖²

1.中国地质大学(北京) 水资源与环境学院暨地下水循环与环境演化教育部重点实验室, 北京 100083
2.青海省环境地质勘查局青海九零六工程勘察设计院有限责任公司青海省环境地质重点实验室, 青海西宁 810001

收稿日期:2021-12-02 修回日期:2022-01-12 出版日期:2022-05-25 发布日期:2022-04-28
通信作者: 郭华明,吴萍
作者简介:邢世平(1991—),男,博士研究生,水文地质学专业。E-mail: spxing@cugb.edu.cn
基金资助:
国家自然科学基金项目(42130509);国家自然科学基金项目(41825017);青海省科学技术厅重点实验室创建平台建设专项(2021-ZJ-Y11)

Distribution and formation processes of high fluoride groundwater in different types of aquifers in the Hualong-Xunhua Basin

XING Shiping¹(), GUO Huaming¹^,^*(), WU Ping²^,^*(), HU Xueda¹, ZHAO Zhen², YUAN Youjing²

1. School of Water Resources and Environment & MOE Key Laboratory of Groundwater Circulation and Environmental Evolution, China University of Geosciences (Beijing), Beijing 100083, China
2. Key Labobratory of Geo-environment Qinghai Province, Qinghai 906 Engineering Survey and Design Institute Co., Ltd., Environmental Geological Exploration Bureau of Qinghai Province, Xining 810007, China

Received:2021-12-02 Revised:2022-01-12 Online:2022-05-25 Published:2022-04-28
Contact: GUO Huaming,WU Ping

摘要/Abstract

摘要：

天然成因的高氟地下水是世界范围内备受关注的环境问题和饮用水安全问题。前人对高氟地下水的形成过程已开展了大量研究,但是对于高原盆地复杂水文地质条件下不同类型含水层组(第四系松散层含水层、基岩裂隙或岩溶含水层以及新生代古近纪以来的碎屑岩含水层)高氟地下水的分布和形成过程尚不明确。本文以化隆—循化盆地为研究区,通过采集、测试研究区内的各类地下水样品,分析研究区内不同类型含水层中地下水的化学特征及同位素特征。结果表明,高氟地下水(1.007.73 mg/L)主要分布在沿黄河的河谷区域和巴燕低山丘陵区域的泉水和潜水中以及深部的承压水中,在垂向上高氟地下水无明显分布规律。接受黄河水入渗补给的河谷潜水中氟离子浓度较低,补给黄河的河谷潜水中氟离子浓度较高。贫钙富钠的弱碱性苏打型水有利于地下水中氟的富集。泉水和潜水中氟主要来源于萤石的溶解,而承压水中氟除了来源于萤石外,还来源于其他含氟矿物。对于潜水和第四系松散层泉水,蒸发浓缩作用促进了地下水中氟的富集。另外,阴离子竞争吸附作用、阳离子交换吸附作用是泉水(第四系松散层泉水和基岩裂隙泉水)和潜水中氟元素富集的主要原因,而承压水中氟离子浓度受竞争吸附作用影响较大,阳离子交换吸附作用影响较小。研究成果可为化隆—循化盆地低氟地下水的勘查和开发提供科学依据。

关键词: 氟, 地下水, 高原盆地, 水化学特征, 水-岩相互作用

Abstract:

High fluoride (F^-) groundwater of natural origin is an environmental and drinking water safety issue, which has attracted worldwide attention. Although many studies have focused on the formation process of high fluoride groundwater, the distribution and formation processes of high fluoride groundwater in different types of aquifers (Quaternary aquifer, bedrock fissure or karst aquifer, clastic aquifer) under complex hydrogeological conditions in the plateau basin are poorly understood. Phreatic groundwater, confined groundwater, and spring water (Quaternary aquifer spring water and bedrock fissure spring water) samples were obtained from the Hualong-Xunhua Basin for chemical and isotopic analyses to reveal the genesis of high fluoride groundwater. The fluoride concentrations in groundwater samples were found to range from 0.25 to 7.73 mg/L. High fluoride groundwater (F^->1.0 mg/L) was mainly distributed in spring water and phreatic water along the Yellow River Valley area and the Bayan low mountaineous and hilly areas, as well as in deep confined groundwater. However, the variation pattern of F^- concentration along the depth is complex. Phreatic water in the Yellow River Valley area that recharged the Yellow River generally has high F^- concentration, while phreatic water in the Yellow River Valley recharged by the Yellow River has low F^- concentration. Ca-poor and Na-rich alkaline soda water is beneficial to F^- enrichment in groundwater. Fluoride in spring water and phreatic water are mainly derived from the dissolution of fluorite. However, in confined groundwater, it is mainly derived from fluorite and other fluoride-containing minerals. For phreatic and Quaternary aquifer spring water, evaporative concentration processes promotes fluoride enrichment. In addition, competitive adsorption of coexisting anions and cation exchange are the causes of high fluoride in spring water (Quaternary aquifer spring water and bedrock fissure spring water) and phreatic water, while cation exchange contributes the most to fluoride enrichment in confined groundwater. This study provides a scientific basis for the exploration and development of safe (low fluoride) groundwater in the Hualong-Xunhua Basin.

Key words: fluoride, groundwater, the plateau basin, hydrochemical characteristics, groundwater-rock interaction

中图分类号:

X523
X131

邢世平, 郭华明, 吴萍, 胡学达, 赵振, 袁有靖. 化隆—循化盆地不同类型含水层组高氟地下水的分布及形成过程[J]. 地学前缘, 2022, 29(3): 115-128.

XING Shiping, GUO Huaming, WU Ping, HU Xueda, ZHAO Zhen, YUAN Youjing. Distribution and formation processes of high fluoride groundwater in different types of aquifers in the Hualong-Xunhua Basin[J]. Earth Science Frontiers, 2022, 29(3): 115-128.

图/表 14

图1 采样点位置和分布以及地下水中氟离子浓度分布图

Fig.1 (a) Locations and distribution of sampling sites in the study area and (b-g) variation patters of groundwater (spring water, phreatic water and confined groundwater) fluoride concentrations in various sections of the study area

图2 甘都沟水文地质纵剖面图(a)街子沟水文地质纵剖面图(b)

Fig.2 Hydrogeological sections of Gandu (I-II) (a) and Jiezi (III-IV) (b)

表1 地下水样中各理化指标统计结果

Table 1 Statistics of various physical and chemical indicators in groundwater samples

指标/样品编号		pH值	ORP/mV	EC/(μS·cm^-1)	ρ/(mg·L^-1)
指标/样品编号		pH值	ORP/mV	EC/(μS·cm^-1)	Na⁺	K⁺	Ca²⁺	Mg²⁺
泉水(n=47)	最小值	6.57	87.2	336	2.81	0.53	30.8	7.26
	中位数	7.45	130	531	14.0	1.86	69.2	20.8
	最大值	8.85	212	3 540	601	9.93	168	79.2
	平均值	7.53	133	738	53.5	2.37	74.9	25.0
潜水(n=22)	最小值	6.75	33.3	439	14.7	1.63	57.0	12.6
	中位数	7.28	114	1 190	93.4	4.16	119	47.2
	最大值	7.88	164	13 040	2 480	15.6	450	286
	平均值	7.34	107	1 950	232	4.49	161	59.2
承压水(n=2)	HL-CG-1	9.91	-217	7 040	1 150	11.9	419	1.33
承压水(n=2)	HL-CG-2	9.11	-288	3 090	576	10.6	82.9	0.12
指标/样品编号		ρ/(mg·L^-1)					δ¹⁸O/‰	δD/‰
指标/样品编号		Cl^-	$NO 3 -$	$SO 4 2 -$	$HCO 3 -$	F^-	δ¹⁸O/‰	δD/‰
泉水(n=47)	最小值	3.85	0.00	15.8	128	0.25	-10.7	-73.4
	中位数	12.8	14.1	50.0	245	0.50	-8.80	-60.8
	最大值	472	102	1 370	388	2.32	-6.46	-46.6
	平均值	44.3	18.9	128	258	0.69	-8.87	-60.5
潜水(n=22)	最小值	14.53	3.31	43.2	220	0.32	-10.9	-80.2
	中位数	73.5	32.0	229	389	1.11	-9.52	-70.4
	最大值	1 580	90.4	5 210	683	3.78	-8.13	-57.2
	平均值	168	33.2	590	403	1.25	-9.56	-68.7
承压水(n=2)	HL-CG-1	2 045	1.54	1 090	17.5	5.06	-9.44	-80.3
承压水(n=2)	HL-CG-2	599	1.51	679	52.5	7.73	-10.0	-87.0

表1 地下水样中各理化指标统计结果

Table 1 Statistics of various physical and chemical indicators in groundwater samples

指标/样品编号		pH值	ORP/mV	EC/(μS·cm^-1)	ρ/(mg·L^-1)
指标/样品编号		pH值	ORP/mV	EC/(μS·cm^-1)	Na⁺	K⁺	Ca²⁺	Mg²⁺
泉水(n=47)	最小值	6.57	87.2	336	2.81	0.53	30.8	7.26
	中位数	7.45	130	531	14.0	1.86	69.2	20.8
	最大值	8.85	212	3 540	601	9.93	168	79.2
	平均值	7.53	133	738	53.5	2.37	74.9	25.0
潜水(n=22)	最小值	6.75	33.3	439	14.7	1.63	57.0	12.6
	中位数	7.28	114	1 190	93.4	4.16	119	47.2
	最大值	7.88	164	13 040	2 480	15.6	450	286
	平均值	7.34	107	1 950	232	4.49	161	59.2
承压水(n=2)	HL-CG-1	9.91	-217	7 040	1 150	11.9	419	1.33
承压水(n=2)	HL-CG-2	9.11	-288	3 090	576	10.6	82.9	0.12
指标/样品编号		ρ/(mg·L^-1)					δ¹⁸O/‰	δD/‰
指标/样品编号		Cl^-	$NO 3 -$	$SO 4 2 -$	$HCO 3 -$	F^-	δ¹⁸O/‰	δD/‰
泉水(n=47)	最小值	3.85	0.00	15.8	128	0.25	-10.7	-73.4
	中位数	12.8	14.1	50.0	245	0.50	-8.80	-60.8
	最大值	472	102	1 370	388	2.32	-6.46	-46.6
	平均值	44.3	18.9	128	258	0.69	-8.87	-60.5
潜水(n=22)	最小值	14.53	3.31	43.2	220	0.32	-10.9	-80.2
	中位数	73.5	32.0	229	389	1.11	-9.52	-70.4
	最大值	1 580	90.4	5 210	683	3.78	-8.13	-57.2
	平均值	168	33.2	590	403	1.25	-9.56	-68.7
承压水(n=2)	HL-CG-1	2 045	1.54	1 090	17.5	5.06	-9.44	-80.3
承压水(n=2)	HL-CG-2	599	1.51	679	52.5	7.73	-10.0	-87.0

图3 地下水(泉水、潜水和承压水)Piper三线图以及不同类型地下水中氟离子浓度

Fig.3 Piper diagram of spring water, phreatic water and confined groundwater samples with varying fluoride concentrations

图4 化隆—循化盆地各类水样中δD与δ18O之间的关系

Fig.4 Bivariate plots of δD and δ18O values in groundwater samples with varying floride concentrations for three water types in the Hualong-Xunhua Basin

图5 潜水与承压水中F-浓度沿垂向变化

Fig.5 Variations of F- concentration along the sampling depth in phreatic water and confined groundwater samples

图6 泉水和潜水中Ca2+(a)、Na+(b)的质量分数与氟离子浓度之间的关系

Fig.6 Bivariate plots of fluoride concentration and mass percent of Ca2+ (a) or Na+ (b) in spring water and phreatic water samples

图7 泉水、潜水和承压水中Mg2+/Na+和Ca2+/Na+(物质的量浓度之比)(a)、 HCO 3 -/Na+和Ca2+/Na+(物质的量浓度之比)(b)之间的关系图

Fig.7 Molar ratio bivariate plots of (a) Na-normalized Ca+ and Mg+ and (b) Na-normalized Ca+ and HCO 3 - in spring water, phreatic water and confined groundwater samples, revealing the dissolution of silicate and carbonate as the main source of ions in groundwater

图8 地下水中F-与Ca2+离子活度之间的关系(a),地下水中F-与萤石饱和指数(SIfluorite)之间的关系(b), 地下水萤石饱和指数与方解石饱和指数之间的关系(c),地下水萤石饱和指数与白云石饱和指数之间的关系(d)

Fig.8 Bivariate plots of various hydogrochemical indicators in spring water, phreatic water and confined groundwater samples with varying fluoride concentrations

图9 泉水、潜水和承压水中Cl-与Na+之间的关系(a),Ca2++Mg2+- SO 4 2 -- HCO 3 -/2与Na++K+-Cl-之间的关系(b)

Fig.9 Bivariate plots of molar concentrations of the major ions in spring water, phreatic water and confined groundwater samples

图10 泉水与潜水中F-浓度与Na+-Cl-(a)以及Na/Ca(质量分数之比)(b)之间的关系

Fig.10 Scatter plots showing the relationships between F- concentration and Na+-Cl- (a) or Na/Ca (mass percent ratio) (b) in spring water and phreatic water samples

图11 地下水中的F-与pH值(a)以及 HCO 3 -(b)之间的关系

Fig.11 Scatter plots showing the relationships between F- concentration and pH (a) or HCO 3 - (b) in spring water, phreatic water and confined groundwater samples

图12 化隆—循化盆地地下水Gibbs图 (Na+/(Na++Ca2+)为质量分数比)

Fig.12 Gibbs diagram of groundwater in the Hualong-Xunhua Basin (Na+/(Na++Ca2+) is the mass percent ratio)

图13 泉水和潜水中F-与F-/Cl-(质量分数比)之间的关系(a), 潜水中F-与δ18O(图4中蓝色虚线圈内潜水样品)的关系图(b)

Fig.13 Bivariate plots of (a) F- concentration and F-/Cl- (mass percent ratio) in spring water and phreatic water samples showing the effects of evaporative concentration on F enrichment in groundwater, and (b) scatter plot showing the relationship between F- concentration and δ18O in phreatic water samples (same samples as in the green dashed circle in Fig.4)

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化隆—循化盆地不同类型含水层组高氟地下水的分布及形成过程

Distribution and formation processes of high fluoride groundwater in different types of aquifers in the Hualong-Xunhua Basin

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