Characteristics of stable carbon isotopes and its implications on arsenic enrichment in shallow groundwater of the Jianghan Plain
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摘要: 溶解性有机碳（DOC）是地下水中砷释放过程的关键因素，为查明江汉平原高砷地下水稳定碳同位素特征，识别有机质的降解过程对砷富集的影响，采用稳定碳同位素分析测试技术并结合地下水化学特征，对江汉平原典型砷中毒病区的浅层地下水进行了区域采样分析。结果表明：浅层承压水的砷质量浓度为0.23~2 621 μg/L。地表水较地下水具有更负的δ13CDOC、δ13CDIC值。地下水中溶解性无机碳（DIC）的δ13CDIC值在-11.9‰~-3.99‰之间，溶解性有机碳的δ13CDOC值在-28.5‰~-19.6‰之间。地下水的δ13CDIC-δ13CDOC差值与ρ（As）呈一定负相关关系，表明微生物作用下有机质的降解促进了As的富集。δ13CDIC-δ13CDOC差值与δ13CDIC和ρ（DOC）均具有较显著的正相关关系，表明地下水中有机质的氧化分解是导致δ13CDIC贫化的重要过程，微生物作用下溶解性有机质的降解是地下水中无机碳的重要来源。此外，江汉平原少数高砷地下水呈现较大的δ13CDIC值，推断江汉平原高砷含水层强还原环境下可能存在的产甲烷过程导致了明显的碳同位素分馏。Abstract: Dissolved organic matter of groundwater is one of the most important factors controlling arsenic release. In order to elaborate the characteristics of stable carbon isotopes and the effects of degradation of organic matter on arsenic enrichment in groundwater, shallow groundwater samples were collected using hydrochemistry and stable carbon isotope analysis in typical arsenicosis areas of the Jianghan Plain. Results indicate that the concentration of As in the shallow groundwater range in 0.23-2621 μg/L. Surface water has lower values of δ13CDOC and δ13CDIC compared with groundwater. The value of δ13CDIC ranges from -11.9‰ to 3.99‰ and the values of δ13CDOC ranges from -28.5‰ to -19.6‰ in groundwater. There is a negative correlation between δ13CDIC-δ13CDOC and As concentration. It indicates that the degradation of organic matter promotes the enrichment of As. There is a positive correlation between δ13CDIC-δ13CDOC and δ13CDIC also between δ13CDIC-δ13CDOC and DOC concentration. It indicates that the microbially involving oxidative decomposition of organic carbon in groundwater leads to the fractionation of carbon isotopes, and the degradation of dissolved organic matter is the main source of inorganic carbon in groundwater. Moreover, some groundwater samples have high δ13CDIC values in the Jianghan Plain, which is significantly higher than other typical arsenic affected areas (Hetao Plain and Datong Basin). It is suggested that methanogenic process occurred in arsenic affected aquifer of the Jianghan Plain, which results in significant carbon isotope fractionation.
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Key words:
- Jianghan Plain /
- arsenic /
- stable carbon isotope /
- dissolved organic matter
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图 1 研究区及采样点分布
Figure 1. Location of the study area and sampling sites for surface water and groundwater
图 2 江汉平原地下水中As与DOC、HCO3-、Fe、NH4+质量浓度的关系图
Figure 2. Relationships between concentration of As and DOC, HCO3-, Fe2+, NH4+ concentrations in groundwater of the Jianghan Plain
图 3 江汉平原地表水和地下水中溶解性无机碳和有机碳中δ13C值的范围
Figure 3. Range of δ13C value of DIC and DOC in surface water and groundwater in the Jianghan Plain
图 4 承压水中δ13CDIC与ORP、As、HCO3-关系图
Figure 4. Relationships between δ13CDIC and ORP, As, HCO3- concentration in confined water
图 5 δ13CDIC-δ13CDOC分别与δ13CDIC(a)、ρ(As)(b)、ρ(DOC)(c)以及δ13CDIC与ρ(As)(d)关系图
Figure 5. Relationships between δ13CDIC-δ13CDOC and δ13CDIC(a), As(b), DOC(c) concentrations, and relationship between δ13CDIC and As concentrations (d)
表 1 江汉平原地下水主要水化学指标统计
Table 1. Statistics of groundwater chemistry in the Jianghan Plain
指标 pH Ca+ Mg2+ K+ Na+ Cl- SO42- NO3- HCO3- DOC Fe2+ NH4+ As ρB/(mg·L-1) ρB/(mg·L-1) ρB/(μg·L-1) 浅层潜水 6.52~7.00
(6.84)104~190
(136)20.30~29.00
(23.90)1.42~2.18
(1.84)7.50~36.6
(18.60)7.68~39.8
(21.60)3.36~129
(45.40)0.24~121
(40.60)452~595
(534)1.86~5.61
(3.13)0.15~12.00
(5.88)0.10~6.50
(3.43)0.38~97.7
(60.10)浅层承压水 6.51~7.51
(7.02)58.50~180
(125)12.10~32.4
(24.20)0.31~5.54
(1.83)5.10~31.50
(16.70)4.07~37.50
(9.30)3.58~67.10
(7.18)0.16~0.62
(0.34)418~917
(646)0.72~22.90
(3.81)0.06~12.70
(6.69)0.04~13.70
(3.58)0.23~2 621
(193.00)注：括号中为平均值 
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表 2 江汉平原、大同盆地、河套平原地下水中δ13CDIC及As、Fe质量浓度范围
Table 2. δ13CDIC values and As, Fe concentrations in Jianghan Plain, Datong Basin and Hetao Plain
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