Molecular Characterization of Dissolved Organic Matter (DOM) in Shallow Aquifer along Middle Reach of Yangtze River and Its Implications for Iodine Enrichment
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摘要: 长期摄入高碘地下水（碘浓度＞100 μg/L）会造成人体甲状腺机能损伤.天然有机质被认为是影响高碘地下水形成的关键组分，为研究地下水中溶解性有机质（DOM）分子组成对碘富集的影响，选取长江中游沿岸浅层地下水作为研究对象，运用傅立叶变换离子回旋共振质谱仪（FT-ICR-MS）表征不同碘浓度地下水中DOM分子组成差异.研究发现碘易富集在还原环境的浅层地下水中，地下水中碘的浓度与溶解性有机碳（DOC）浓度无显著关系，DOM分子总数越多碘浓度越高；高碘地下水较低碘水DOM分子均一性、多样性更强，氧化程度和不饱和程度更高，含更多芳香性结构.长江中游沿岸高碘地下水的形成受DOM分子组成控制，主要与不饱和程度高尤其是含芳香性结构的大分子DOM有关，含芳香性结构的DOM分子与碘络合在高碘地下水的形成过程中起重要作用.Abstract: Long-term uptake of high iodine groundwater (iodine concentration > 100 μg/L) leads to thyroid dysfunction. Natural organic matter is considered to be the key factor affecting the formation of high iodine groundwater. In order to figure out the impact of molecular composition of dissolved organic matter(DOM) on iodine enrichment in groundwater, the DOM in shallow groundwater with different iodine concentrations along the Middle Reach of the Yangtze River was characterized by FT-ICR-MS. Results indicate that iodine was easily enriched in strong reducing environment, and iodine concentrations in groundwater had no significant relationship with DOC concentrations, but had a significant positive correlation with numbers of DOM molecules. Compared with low iodine groundwater, DOM in high iodine groundwater characterized with greater uniformity and diversity, more oxidized and unsaturated molecular composition, containing more aromatic structures. The enrichment of iodine in shallow groundwater along the Middle Reach of the Yangtze River was closely related to the molecular composition of DOM. Complexation of DOM molecules containing aromatic structure with iodine plays an important role in the formation of high iodine groundwater.
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Key words:
- groundwater /
- iodine /
- dissolved organic matter /
- molecular composition /
- FT-ICR-MS /
- hydrogeology
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图 1 研究区采样点位置和地下水碘浓度分布情况
Fig. 1. Location of sampling sites and spatial distribution of iodine concentration in shallow groundwater in the study area
图 2 地下水中碘浓度与DOC浓度的关系
Fig. 2. Relationship between iodine concentration and DOC concentration in groundwater
图 3 不同碘浓度的地下水中DOM分子总数柱状图
Fig. 3. Histogram of the total number of DOM molecules in groundwater with different iodine concentrations
图 4 不同碘浓度的地下水DOM的质谱分析谱图
a，b，c，d分别对应碘浓度为24.6 μg/L，33.5 μg/L，93.1 μg/L和230 μg/L的地下水样
Fig. 4. Mass spectrum analysis of DOM in groundwater with different iodine concentrations
图 5 地下水中DOM分子组成的相对丰度分布
a，b，c，d分别对应碘浓度为24.6 μg/L，33.5 μg/L，93.1 μg/L和230 μg/L的地下水样
Fig. 5. Relative abundance distribution of DOM in groundwater
图 6 不同碘浓度地下水中DOM基本参数指标箱型图
Fig. 6. DOM diagrams of DOM basic parameters and indicators
a. H/C; b. O/C; c.DBE
图 7 不同碘浓度地下水中DOM分子DBE和氧原子个数之间的关系
Fig. 7. Relationship between DBE and oxygen atom number of DOM molecules in groundwater with different iodine concentrations
图 8 高碘地下水和低碘地下水样品中DBE-O的频数分布
Fig. 8. Frequency distribution of DBE-O in high iodine groundwater and low iodine groundwater samples
图 9 地下水中C原子数与DOM摩尔质量（范围在300~600 m/z之间）的关系
a，b，c，d分别对应碘浓度为24.6 μg/L，33.5 μg/L，93.1 μg/L和230 μg/L的地下水样
Fig. 9. The relationship between the number of C atoms in groundwater and the molar mass of DOM (ranging from 300 m/z to 600 m/z)
表 1 研究区地下水主要水化学组分特征统计
Table 1. Statistical summary of basic groundwater hydrochemistry in the study area
样品数(n=32) 最大值 最小值 平均值 I (μg/L) 1 590.0 2.2 189.0 pH 8.04 6.85 7.19 Eh (mV) 157.0 ‒171.0 ‒104.1 TDS(mg/L) 1 308.0 90.0 503.0 Ca2+(mg/L) 273.0 41.7 154.0 Na+(mg/L) 98.0 9.7 20.9 K+(mg/L) 136.0 0.4 6.4 Mg2+(mg/L) 128.0 10.1 42.1 NO3-(mg/L) 79.6 0.3 5.1 NO2-（mg/L） 3.0 < 0.01 ‒ Cl- (mg/L) 77.4 0.3 7.6 HCO3-（mg/L） 1 753.0 127.0 769.0 SO42-（mg/L） 880.0 < 0.01 ‒ NH4+（mg/L） 22.7 0.01 7.0 As (μg/L) 588 2.4 171.0 注：“‒”指绝大多数水样的浓度低于检测限. 
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表 2 不同碘浓度地下水DOM芳香指数计算结果
Table 2. Results of DOM aromatic index in groundwater samples with different iodine concentrations
地下水碘浓度 DBE-O=3 (%) DBE-O=7 (%) DBE-O=11 (%) AImod > 0. 5 AImod≥0. 67 AImod > 0. 5 AImod≥0. 67 AImod > 0. 5 AImod≥0. 67 24.6 μg/L 6.25 ‒ 60.22 4.304 60.00 40.00 33.5 μg/L 11.67 0.57 75.86 10.34 ‒ ‒ 93.1 μg/L 13.28 0.59 68.42 11.96 93.33 68.89 230 μg/L 36.12 4.90 86.34 28.29 92.86 35.71
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