高温富硫化物热泉中硫代砷化物存在形态的地球化学模拟：以云南腾冲热海水热区为例

庄亚芹; 郭清海; 刘明亮; 李洁祥; 周超

doi:10.3799/dqkx.2016.513

高温富硫化物热泉中硫代砷化物存在形态的地球化学模拟：以云南腾冲热海水热区为例

doi: 10.3799/dqkx.2016.513

庄亚芹^1,2,,
郭清海^1,2, ,,
刘明亮^1,2,
李洁祥^1,2,
周超^1,2

1.
中国地质大学生物地质与环境地质国家重点实验室，湖北武汉 430074
2.
中国地质大学环境学院，湖北武汉 430074

基金项目:

中国地质大学(武汉)生物地质与环境地质国家重点实验室自主研究课题项目 GBL11505

国家自然科学基金项目 41120124003

国家自然科学基金项目 41572335

国家自然科学基金项目 41521001

详细信息

作者简介:
庄亚芹(1990-)，女，硕士研究生，从事高温地热流体地球化学领域的研究工作.E-mail：359572236@qq.com

通讯作者:
郭清海, E-mail: qhguo2006@gmail.com

中图分类号: P66
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出版历程
- 收稿日期: 2016-01-20
- 刊出日期: 2016-09-15

Geochemical Simulation of Thioarsenic Speciation in High-Temperature, Sulfide-Rich Hot Springs: A Case Study in the Rehai Hydrothermal Area, Tengchong, Yunnan

Zhuang Yaqin^{1,2
,},
Guo Qinghai^{1,2
, ,},
Liu Mingliang^1,2,
Li Jiexiang^1,2,
Zhou Chao^1,2

1.
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China
2.
School of Environmental Studies, China University of Geosciences, Wuhan 430074, China

摘要

摘要: 天然水环境中地质成因砷的存在是世界范围内对人类威胁极大的环境问题之一.在高温富硫化物地热水中，硫代砷化物是砷的主要存在形态之一.在国内尚无硫代砷化物定量检测方法的背景下，以云南腾冲地热带的热海水热区为典型研究区，基于不同类型硫代砷化物的最新化学热力学数据wateq4f.dat，利用水文地球化学模拟软件PHREEQC开展了不同类型热泉中砷的存在形态的地球化学模拟.结果表明，热海热泉中砷的主要形态是硫代砷酸盐，砷酸盐和亚砷酸盐次之，硫代亚砷酸盐则含量极低；在各类硫代砷酸盐中，按平均百分含量降序依次为：一硫代砷酸盐→三硫代砷酸盐→四硫代砷酸盐→二硫代砷酸盐.pH、Eh和总硫化物含量是热泉中砷的形态分布的控制性因素.在酸性条件下，砷以硫代砷酸盐和亚砷酸盐为主要存在形式；而在中性/偏碱性条件下，砷的形态则以硫代砷酸盐为主，砷酸盐次之.偏还原环境和高硫化物含量是硫代砷化物、特别是三硫代砷酸盐和四硫代砷酸盐稳定存在的有利条件.
- 热泉 /
- 硫代砷化物 /
- 热海水热区 /
- 腾冲地热带 /
- 地球化学
Abstract: The occurrence of geogenic arsenic in natural water environment is one of the significant hazards to human beings in the world. In high-temperature, sulfide-rich geothermal waters, thioarsenicals are likely the major species of arsenic. In view that there has been so far no quantitative test method for thioarsenic species in China, a hydrogeochemical code, PHREEQC, with its wateq4f.dat database being updated by the latest thermodynamic data for thioarsenicals, was used for calculating the arsenic species distribution in various types of hot springs from the Rehai hydrothermal area located in the Tengchong geothermal belt, Yunnan Province. The results show that the major species of arsenic in the Rehai hot springs is thioarsenate, arsenate and arsenite comes second, and the thioarsenite concentrations are extremely low; the descending order of thioarsenate species in terms of their average percentages is: monothioarsenate, trithioarsenate, tetrathioarsenate, and dithioarsenate. pH, Eh and total sulfide concentration are the controlling factors for the arsenic speciation in hot springs. Under acidic condition, the main species of arsenic are thioarsenate and arsenite, whereas under neutral/weak alkaline conditions, thioarsenate is predominant with arsenate being the second most important species. Comparative reducing environment and high sulfide concentration in geothermal water are favorable for the stable existence of thioarsenicals, especially trithioarsenate and tetrathioarsenate.
- hot spring /
- thioarsenic species /
- Rehai hydrothermal area /
- Tengchong geothermal belt /
- geochemistry

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图 1 腾冲火山岩分布(a)和热海热田地热地质图及采样位置(b)

1.全新统；2.晚更新统；3.中更新统玄武岩；4.早更新统安山岩；5.中新统南林组；6.元古宙高黎贡山群；7.明矾石带；8.高岭石－玉髓或蛋白石带；9.高岭石－蒙脱石－玉髓带，高岭石－伊利石－蒙脱石混层矿物－玉髓石英带；10.伊利石－蒙脱石混层矿物－石英带；11.绿泥石－蒙脱石混层矿物带；12.蒙脱石－方解石带；13.伊利石－蒙脱石－高岭石－玉髓带；14.断层；15.取样点；16.热泉/高程(m)；图a据赵慈平等(2006)修改；图b据廖志杰和赵平(1999)修改

Fig. 1. Volcanic rock distribution in Tengchong (a) and geothermal geological map of the Rehai field and sampling locations (b)

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图 2 基于不同氧化还原电对实测含量计算出的热泉样品Eh值

Fig. 2. Calculated Eh values of the hot-spring samples according to the measured concentrations of various redox couples

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图 3 酸性热泉(a)和中性/偏碱性(b)热泉中砷的不同形态的百分含量随Eh、总砷浓度和总硫化物浓度的变化

Fig. 3. Percentage of different arsenic species vs. Eh, total arsenic, and total sulfide concentrations in acidic hot springs (a) and neutral/weak alkaline hot springs (b)

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图 4 中性/偏碱性热泉总砷浓度与Eh的关系

Fig. 4. Eh vs.total arsenic concentration in neutral/weak alkaline hot springs

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图 5 控制条件下砷的形态分布与总砷含量的关系

Fig. 5. Relationship between arsenic speciation and total arsenic concentration under controlled conditions

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图 6 不同形态硫代砷酸盐百分含量与Eh和总硫化物浓度的关系

Fig. 6. Percentage of mono-, di-, tri-and tetra-thioarsenates vs. Eh (a) and total sulfide concentration (b) in all hot springs

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表 1 热海热泉的水化学组成

Table 1. Hydrochemical compositions of hot springs from the Rehai geothermal field

水样编号	泉名	T	pH	Eh	SO₄	Cl	F	NO₃	Na	K	Ca	Mg	Fe(Ⅱ)	Fe(Ⅲ)	As(Ⅴ)	As(Ⅲ)	As	硫化物	NH₄
酸性泉
DRTY-01	地热体验区1号泉	41.6	1.85	229.8	882.7	22.8	0.5	3.5	9.9	26.2	3.3	0.7	1.94	3.70	30.9	6.8	26.0	0.01	0.4
DRTY-02	地热体验区2号泉	65.4	1.85	199.8	776.1	22.6	0.7	4.5	4.2	4.6	8.4	0.9	1.22	2.30	35.1	7.1	35.9	0.02	3.2
DRTY-04	地热体验区4号泉	68.7	1.93	196.4	879.0	24.8	1.4	5.0	18.0	35.4	3.5	1.2	5.69	12.60	120.2	16.3	147.8	0.02	1.6
DRTY-06	地热体验区6号泉	85.4	2.04	168.1	1 634.0	22.9	0.5	5.1	5.6	20.0	3.5	1.1	2.64	7.70	108.6	9.0	98.2	0.03	13.5
DRTY-07	地热体验区7号泉	80.4	1.41	185.6	1 699.6	23.3	1.3	3.9	11.3	35.8	3.7	2.4	2.60	16.30	113.6	32.3	158.6	0.04	14.3
ZZQ-R	珍珠泉-右	86.8	2.96	128.5	135.1	41.9	1.4	0.2	56.4	26.5	2.1	0.5	0.03	0.51	11.7	47.0	62.8	0.03	6.0
ZZQ-C	珍珠泉-出	89.0	2.81	119.9	235.9	35.9	0.8	1.2	54.6	28.8	3.6	0.7	0.07	0.87	26.4	32.1	62.8	0.04	5.4
DGG-AS	大滚锅酸性泉	49.3	2.08	199.4	1 506.9	32.0	1.8	3.6	55.5	18.2	178.3	52.6	3.75	48.00	20.9	5.9	22.8	0.07	0.0
LGG-HT	老滚锅(高温)	66.1	2.73	160.6	653.8	58.1	2.6	3.6	161.1	29.4	10.1	1.8	0.56	0.58	12.6	17.9	27.9	0.02	0.0
中性/偏碱性泉
ZZQ-L	珍珠泉-左	90.1	5.10	-6.1	162.2	42.5	2.0	1.6	64.4	30.2	2.3	0.5	0.16	0.35	21.0	44.0	62.7	0.01	3.8
YJQ-C	眼镜泉汇	66.3	9.47	-404.6	34.0	561.7	14.7	3.0	793.8	139.7	1.0	0.1	0.01	0.00	107.4	597.6	958.8	0.35	0.1
YJQ-L	眼镜泉左	91.1	8.88	-435.3	33.1	594.0	15.3	2.9	771.0	133.8	1.2	0.1	0.00	0.03	31.6	574.8	347.8	3.40	0.3
YJQ-R	眼镜泉右	81.1	9.32	-439.8	33.7	612.0	15.6	3.0	786.0	136.6	1.0	0.1	0.00	0.02	49.7	628.4	768.8	2.60	0.2
ZXS	忠孝寺泉	46.3	6.09	-95.5	35.8	134.1	3.2	2.9	253.1	47.6	17.9	1.1	0.01	0.13	136.5	20.3	129.0	0.01	0.1
ZT07	澡塘河仙人澡塘	46.0	7.60	-180.4	73.2	236.8	7.5	2.9	369.6	66.7	7.6	0.3	0.28	0.00	86.4	161.5	267.4	0.04	0.2
DGG-NS	大滚锅	84.1	7.45	-334.4	40.3	715.9	19.2	2.8	893.4	153.6	1.0	0.1	0.03	0.01	940.6	104.6	548.9	0.21	0.0
HMZT-M	蛤蟆嘴亭中	57.5	7.40	-189.5	72.0	288.8	7.0	4.2	372.2	66.8	4.7	0.7	0.40	0.04	71.2	173.7	271.3	0.06	0.0
HMZT-L	蛤蟆嘴亭左	64.2	7.14	-213.1	63.7	332.0	8.1	4.6	420.9	76.5	3.6	0.5	0.45	0.01	115.3	249.3	425.5	0.13	0.0
HMZD	蛤蟆嘴池	91.6	7.13	-319.7	43.9	337.6	8.0	4.4	449.7	81.9	2.3	0.2	0.06	0.00	123.2	124.7	290.8	0.30	0.0
XKT-R	霞客亭右	95.0	7.53	-229.8	37.3	335.6	8.0	4.2	456.1	81.4	2.2	0.1	0.02	0.00	79.4	146.7	293.0	1.90	0.0
HTJ-L	怀胎井左	92.4	7.40	-385.1	33.3	560.7	13.8	4.2	692.6	124.5	1.0	0.1	0.00	0.02	127.9	461.4	573.8	2.60	0.0
HTJ-R	怀胎井右	85.4	6.88	-317.2	44.5	464.6	11.5	3.9	547.6	100.1	1.4	0.1	0.02	0.00	403.6	151.3	657.4	0.67	0.0
GMQ	鼓鸣泉	90.5	8.12	-424.2	32.2	593.9	14.5	4.2	716.2	127.9	1.3	0.1	0.01	0.01	50.7	346.9	314.6	5.00	0.0
TQL	听泉楼	82.3	7.96	-394.0	31.1	597.1	14.6	3.9	699.0	113.1	1.0	0.1	0.01	0.00	78.8	398.8	278.4	3.00	0.0
注：T的单位为℃；Eh的单位为mV；As(Ⅴ)、As(Ⅲ)和As的单位为μg/L；其他化学组分的单位为mg/L.

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表 2 砷的不同形态的化学热力学数据

Table 2. Chemical thermodynamic data of arsenic species

砷的形态	化学结构式	化学反应式	lgK	来源
亚砷酸盐	H_nAsO₃^n-3	H₃AsO₃=H₂AsO₃^-+H⁺	-9.15	Parkhurst and Appelot (1999)
		H₂AsO₃^-=HAsO₃^2-+H⁺	-23.85	Parkhurst and Appelot (1999)
		HAsO₃^2-=AsO₃^3-+H⁺	-39.55	Parkhurst and Appelot (1999)
一硫代亚砷酸盐	H_nAsSO₂^n-3	H₃AsO₃+H₂S=H₃AsSO₂+H₂O	0.4	Helz and Tossell (2008)
		H₃AsSO₂=H₂AsSO₂^-+H⁺	-3.8	Zaksznova-Herzog and Seward(2012)
		H₂AsSO₂^-=HAsSO₂^2-+H⁺	≤-13.5	Zaksznova-Herzog and Seward(2012)
		HAsSO₂^2-=AsSO₂^3-+H⁺	≤-14.0	Zaksznova-Herzog and Seward(2012)
二硫代亚砷酸盐	H_nAsS₂O^n-3	H₃AsSO₂+H₂S=H₃AsS₂O+H₂O	3.8	Helz and Tossell (2008)
		H₃AsS₂O=H₂AsS₂O^-+H⁺	-3.8	Zaksznova-Herzog and Seward(2012)
		H₂AsS₂O^-=HAsS₂O^2-+H⁺	-6.5	Zaksznova-Herzog and Seward(2012)
		HAsS₂O^2-=AsS₂O^3-+H⁺	-14.0	Zaksznova-Herzog and Seward(2012)
三硫代亚砷酸盐	H_nAsS₃^n-3	H₃AsS₂O+H₂S=H₃AsS₃+H₂O	5.6	Helz and Tossell(2008)
		H₃AsS₃=H₂AsS₃^-+H⁺	-3.77	Zaksznova-Herzog and Seward(2012)
		H₂AsS₃^-= HAsS₃^2-+H⁺	-6.53	Zaksznova-Herzog and Seward(2012)
		HAsS₃^2-=AsS₃^3-+H⁺	-9.29	Zaksznova-Herzog and Seward(2012)
砷酸盐	H_nAsO₄^n-3	H₃AsO₄=H₂AsO₄^-+H⁺	-2.3	Parkhurst and Appelot (1999)
		H₂AsO₄^-=HAsO₄^2-+H⁺	-9.46	Parkhurst and Appelot (1999)
		HAsO₄^2-=AsO₄^3-+H⁺	-21.11	Parkhurst and Appelot (1999)
一硫代砷酸盐	H_nAsSO₃^n-3	H₃AsO₄+H₂S=H₃AsSO₃+H₂O	11.0	Helz and Tossell(2008)
		H₃AsSO₃=H₂AsSO₃^-+H⁺	-3.3	Thilo et al.(2004)
		H₂AsSO₃^-= HAsSO₃^2-+H⁺	-7.2	Thilo et al.(2004)
		HAsSO₃^2-= AsSO₃^-3+H⁺	-11.0	Thilo et al.(2004)
二硫代砷酸盐	H_nAsS₂O₂^n-3	H₃AsSO₃+H₂S=H₃AsS₂O₂+H₂O	0.1	Helz and Tossell (2008)
		H₃AsS₂O₂=H₂AsS₂O₂^-+H⁺	2.4	Helz and Tossell (2008)
		H₂AsS₂O₂^-=HAsS₂O₂^2-+H⁺	-7.1	Thilo et al.(2004)
		HAsS₂O₂^2-= AsS₂O₂^-3+H⁺	-10.8	Thilo et al.(2004)
三硫代砷酸盐	H_nAsS₃O^n-3	H₃AsS₂O₂+H₂S=H₃AsS₃O+H₂O	3.5	Helz and Tossell (2008)
		H₃AsS₃O=H₂AsS₃O^-+H⁺	1.7	Helz and Tossell (2008)
		H₂AsS₃O^-= HAsS₃O^2-+H⁺	-1.5	Helz and Tossell (2008)
		HAsS₃O^2-= AsS₃O^3-+H⁺	-10.8	Thilo et al.(2004)
四硫代砷酸盐	H_nAsS₄^n-3	H₃AsS₃O+H₂S=H₃AsS₄+H₂O	2.6	Helz and Tossell (2008)
		H₃AsS₄=H₂AsS₄^-+H⁺	2.3	Helz and Tossell (2008)
		H₂AsS₄^-=HAsS₄^2-+H⁺	-1.5	Helz and Tossell (2008)
		HAsS₄^2-= AsS₄^3-+H⁺	-5.2	Thilo et al.(2004)

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表 3 热泉中各种硫代砷化物的含量

Table 3. Concentrations of different thioarsenate in the hot springs

样品编号	亚砷酸盐		砷酸盐		硫代亚砷酸盐		硫代砷酸盐		总砷(μg /L)	一硫代砷酸盐		二硫代砷酸盐		三硫代砷酸盐		四硫代砷酸盐
样品编号	(μg/L)	%	(μg/L)	%	(μg/L)	%	(μg/L)	%	总砷(μg /L)	(μg/L)	%	(μg/L)	%	(μg/L)	%	(μg/L)	%
DRTY-01	2.54E+01	97.96	2.42E-05	0.000	1.99E-05	0.000	5.28E-01	2.04	25.91	0.52	98.95	0.01	1.04	0.00	0.00	0.00	0.00
DRTY-02	1.99E+01	55.56	5.11E-04	0.001	2.10E-05	0.000	1.59E+01	44.44	35.86	15.71	98.61	0.22	1.39	0.00	0.00	0.00	0.00
DRTY-04	1.10E+02	74.28	4.29E-03	0.003	3.28E-05	0.000	3.79E+01	25.71	147.50	37.77	99.60	0.15	0.40	0.00	0.00	0.00	0.00
DRTY-06	3.34E+01	33.98	1.22E-02	0.012	6.01E-06	0.000	6.49E+01	66.01	98.31	64.71	99.73	0.18	0.27	0.00	0.00	0.00	0.00
DRTY-07	7.22E+01	45.53	1.19E-02	0.008	1.74E-05	0.000	8.64E+01	54.46	158.65	86.12	99.66	0.29	0.34	0.00	0.00	0.00	0.00
ZZQ-R	2.28E-01	0.36	1.96E-02	0.031	5.65E-08	0.000	6.26E+01	99.61	62.89	61.53	98.23	1.10	1.76	0.00	0.00	0.00	0.00
ZZQ-C	8.85E-02	0.14	3.82E-03	0.006	8.96E-08	0.000	6.28E+01	99.85	62.89	59.22	94.30	3.56	5.67	0.02	0.04	0.00	0.00
DGG-AS	1.35E+01	59.17	6.14E-05	0.000	7.31E-05	0.000	9.31E+00	40.83	22.80	8.55	91.83	0.75	8.09	0.01	0.08	0.00	0.00
LGG-HT	1.35E+00	4.83	2.49E-03	0.009	9.40E-07	0.000	2.66E+01	95.16	27.96	25.63	96.35	0.97	3.63	0.00	0.02	0.00	0.00
ZZQ-L	1.58E-04	0.000	3.94E+01	62.74	3.22E-13	0.000	2.34E+01	37.26	62.79	23.39	100.00	0.00	0.00	0.00	0.00	0.00	0.00
YJQ-C	5.30E-17	0.000	4.90E+02	50.92	5.94E-22	0.000	4.72E+02	49.08	962.30	472.28	99.99	0.03	0.01	0.00	0.00	0.00	0.00
YJQ-L	2.19E-18	0.000	3.04E+00	0.87	1.28E-21	0.000	3.46E+02	99.13	349.09	336.98	97.38	2.46	0.71	5.59	1.62	1.02	0.29
YJQ-R	3.50E-18	0.000	4.67E+01	6.05	4.09E-22	0.000	7.25E+02	93.95	771.63	723.88	99.86	0.77	0.11	0.25	0.03	0.02	0.00
ZXS	8.33E-05	0.000	1.06E+02	81.89	8.64E-13	0.000	2.34E+01	18.11	129.25	23.41	100.00	0.00	0.00	0.00	0.00	0.00	0.00
ZT07	8.97E-10	0.000	1.74E+02	65.10	7.90E-16	0.000	9.35E+01	34.90	268.03	93.53	100.00	0.00	0.00	0.00	0.00	0.00	0.00
DGG-NS	7.75E-12	0.000	6.03E+01	10.93	6.09E-17	0.000	4.91E+02	89.07	551.15	490.62	99.94	0.24	0.05	0.03	0.01	0.00	0.00
HMZT-M	7.86E-10	0.000	1.32E+02	48.45	8.12E-16	0.000	1.40E+02	51.55	271.94	140.18	99.99	0.01	0.01	0.00	0.00	0.00	0.00
HMZT-L	2.68E-09	0.000	1.22E+02	28.66	3.44E-15	0.000	3.04E+02	71.34	426.56	304.27	99.98	0.05	0.02	0.00	0.00	0.00	0.00
HMZD	1.37E-13	0.000	1.43E-01	0.05	6.56E-17	0.000	2.91E+02	99.95	291.57	158.50	54.39	9.29	3.19	120.57	41.37	3.06	1.05
XKT-R	9.49E-19	0.000	4.01E-05	0.00	1.84E-20	0.000	2.94E+02	100.00	293.78	0.64	0.22	0.59	0.20	148.51	50.55	144.03	49.03
HTJ-L	9.01E-19	0.000	1.07E-05	0.00	2.99E-20	0.000	5.76E+02	100.00	575.75	0.31	0.05	0.52	0.09	229.58	39.88	345.33	59.98
HTJ-R	2.82E-12	0.000	2.02E-01	0.03	1.08E-15	0.000	6.59E+02	99.97	659.35	304.61	46.21	23.36	3.54	324.55	49.24	6.63	1.01
GMQ	2.72E-19	0.000	1.06E-03	0.00	4.37E-21	0.000	3.16E+02	100.00	315.71	4.92	1.56	1.46	0.46	132.25	41.89	177.06	56.08
TQL	7.50E-19	0.000	3.34E-04	0.00	1.52E-20	0.000	2.79E+02	100.00	279.36	2.19	0.78	0.94	0.34	119.58	42.80	156.66	56.08
注：百分比为相对于总砷浓度的百分含量.

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