Methylation and Thiolation of Arsenic in Tengchong Hot Springs
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摘要: 为了研究热泉中砷的形态及其分布、转化规律，针对云南腾冲热泉各种砷形态进行了IC-ICP-MS测试和水文地球化学分析.在91处热泉中检出了11种砷形态，包括（亚）砷酸盐、无机硫代砷和甲基（硫代）砷.其中（亚）砷酸盐含量>无机硫代砷含量>甲基砷含量.热泉中无机硫代砷含量及其巯基化程度与硫/砷比正相关.甲基砷含量低是富硫化物热泉中甲基硫代砷形成的主要限制因素，硫/砷摩尔比、总砷、温度、pH、Eh和TDS可影响甲基硫代砷的形成和转化.甲基硫代砷在热泉地表流径上可经历脱巯基、脱甲基然后被沉积物吸附，也可在流径下游重新形成.砷的巯基化和甲基化形态在热泉中广泛分布，甲基硫代砷在热泉环境中具有高迁移性和重现性，应引起相关研究重视.Abstract: In order to study the speciation of arsenic (As) in hot springs and their distribution and transformation patterns, IC-ICP-MS quantification and hydrogeochemical analyses were conducted for various arsenic species in Tengchong hot springs in Yunnan Province. In 91 hot spring samples, 11 As species were detected, which include arsenate, arsenite, inorganic thioarsenates, methylated oxyarsenates and methylated thioarsenates. Arsenate and arsenite were predominate species followed by inorganic thioarsenates, unlike inorganic species, methylated As occurred as minor species in Tengchong hot springs. The content of thioarsenates and their degree of thiolation are positively correlated with S/As molar ratios. The lack of methylated oxyarsenates was probably the reason for low methylated thioarsenate levels, besides, the S/As molar ratio, total As, temperature, pH, Eh and TDS can also affect the formation and transformation of methylated thioarsenates. Methylated thioarsenates may undergo a series of transformations and interfacial reactions on the surface drainage of hot springs such as de-thiolation, de-methylation and then adsorption by sediments. Other As species can be converted to methylated thioarsenate in downstream areas with relatively low temperatures, low flow rates and significant microbial activity. The thiolated and methylated species of As are widely distributed in hot springs, and the highly toxic methylated thioarsenates have high mobility and are likely to reappear in hot spring drainage environment, which should attract the attention of relevant studies.
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Key words:
- Arsenic species /
- methylated thioarsenates /
- hot spring /
- Tengchong /
- hydrogeology
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图 1 腾冲地热区地质图和采样点分布（参考自Guo et al., 2012）
Fig. 1. Sampling location and geological map of Tengchong geothermal area (modified from Guo et al., 2012)
图 2 As含量与现场指标(a)pH, (b)Eh, (c)TDS和(d)温度之间的关系
. 热海热泉；. 朗蒲热泉；. 瑞滇热泉；. 邦腊掌热泉；. 太和热泉；. 户蚌热泉；. 大塘热泉
Fig. 2. Relationship between As concentration and (a) pH, (b) Eh, (c)TDS, (d) Temperature
图 3 腾冲热泉中4种硫代砷比例与S/As之间的关系
Fig. 3. Relationship between four thioarsenate proportions and sulfide concentrations.
图 4 各地热区热泉中甲基硫代砷含量箱型图
a. 为甲基硫代砷占总As比例；b. 为甲基硫代砷绝对浓度
Fig. 4. Box and whisker plots of methylated thioarsenate contents in Tengchong geothermal areas
图 5 腾冲热泉中甲基硫代砷比例与水化学指标之间的关系
a. 甲基砷含量；b. S/As摩尔比；c. 总As含量；d. 温度；e. Eh；f. pH
Fig. 5. Relationships between methylated thioarsenate proportions and hydrochemical parameters
图 6 腾冲热泉流径上甲基化As形态含量的变化
Fig. 6. Content fluctuation of methylated As species along Tengchong geothermal drainages
表 1 水化学变量与甲基硫代砷摩尔比例之间的斯皮尔曼相关性分析
Table 1. Spearman's correlation analysis for methylated thioarsenate proportions (%) and hydrochemical parameters
变量 rs 变量 rs 甲基砷(%) 0.47 F-(mg/L) -0.24 无机硫代砷(%) -0.05 Cl-(mg/L) -0.74 硫化物(mg/L) -0.13 SO42-(mg/L) 0.05 S/As摩尔比 0.39 Na+(mg/L) -0.66 总As(μg/L) -0.77 K+(mg/L) -0.76 pH -0.09 Ca2+(mg/L) 0.38 Eh(mV) 0.45 Mg2+(mg/L) 0.19 温度(℃) -0.57 SiO2(mg/L) -0.10 TDS(mg/L) -0.74 三价铁(μg/L) -0.37 DOC(mg/L) -0.41 Li+(μg/L) -0.75 成熟度(MI) -0.49 Rb+(μg/L) -0.81 HCO3-(mg/L) -0.23 Cs+(μg/L) -0.60 注：n=43，加粗表示P值< 0.05. 
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