Effect of Organic Matter in Water Samples on the Hydrogen Stable Isotope Ratio Determination by Thermal Conversion/Elemental Analysis-Isotope Ratio Mass Spectrometry
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摘要: 在研究水文水资源方面，水中氢稳定同位素比值（δ2H）是一项重要的检测参数，它的变化规律可以用于识别和量化水分来源、揭示水循环演化过程及形成机理，因此促进了水中δ2H检测技术的发展。热转换元素分析同位素比质谱法（TC/EA-IRMS）测定氢稳定同位素具有高效、准确的特点，适合检测含有机物的水样。本文以乙醇为例，利用TC/EA-IRMS检测方法，探究水样中有机物含量对δ2H值的影响。通过配制不同体积比的乙醇-水溶液，测定溶液的δ2H值，建立了乙醇体积比与δ2H值的线性方程，相关系数（R2）可达0.9996，说明水样中有机物会使δ2H值产生线性变化，随着有机物含量增加，水样测定的δ2H值逐渐向有机物的δ2H值方向偏移。利用该线性关系在已知有机物δ2H值和体积比的条件下，可以对样品中H2O的δ2H值进行修正。以乙醇实验为例，其修正结果与真值的相对误差为1.7%，通过修正可以得到真实水样中水分子的δ2H值，有助于准确掌握水循环的状态和规律。同时，利用有机物与δ2H值的线性关系也可以对有机物进行溯源，在模拟溯源乙醇的实验中其溯源的δ2H值与真值相对误差仅为0.4%，说明该线性关系在有机物溯源方面具有良好的应用前景。Abstract:
BACKGROUNDIn the study of hydrology and water resources, the hydrogen stable isotope ratio (δ2H) of water is an important detection parameter, and its changing patterns can be used to identify and quantify the source of water, and reveal the evolution process and formation mechanism of the water cycle. Therefore, the accuracy of δ2H value is very important, which promotes the development of isotope detection technology. High-temperature combustion pyrolysis-element analysis isotope ratio mass spectrometry is a highly efficient and accurate method for the determination of hydrogen isotopes. It is suitable for the detection of water samples containing organic matter. OBJECTIVESTo explore the influence of organic matter content in water on the hydrogen stable isotope ratio (δ2H) and establish a relationship curve between them. Use the relationship to modify the δ2H value of H2O and trace the organic source in organic polluted water. METHODSThermal conversion/elemental analysis-isotope ratio mass spectrometry (TC/EA-IRMS) was used as the main detection method. Ethanol water samples with different volume ratios (r) were prepared, and the δ2H values of the samples were determined by TC/EA-IRMS. Taking r and δ2H as variables, the curve relationship and equation were established. RESULTSA good linear relationship was established by using the ethanol content and the δ2H value as variable with R2 of 0.9996, indicating that the organic matter in the water sample will linearly change the δ2H value. As the organic matter content increased, the δ2H value measured by the water sample gradually shifted toward the δ2H value of the organic matter. Using this linear relation, the δ2H value of H2O in the sample can be corrected when the volume ratio of the organic matter is known. Taking the ethanol experiment as an example, the relative error between the corrected result and the true value was 1.7%. By correcting, the δ2H value of the water molecules in the water sample can be obtained, which helped to accurately understand the state and regularity of the water cycle. At the same time, the linear relationship can also be used to trace the source of the organic matter. In the ethanol experiment that simulated the traceability of the source ethanol, the relative error was only 0.4%. CONCLUSIONSThe linear relationship between organic matter and δ2H has a good application prospect in organic matter tracing. -
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表 1 不同乙醇体积比水样的配制
Table 1. Detailed information of samples with different concentrations of ethanol
待测水样编号 乙醇体积
(μL)水体积
(μL)r=乙醇体积/
(乙醇体积+水体积)S1 0 1000 0 S2 10 990 0.01 S3 50 950 0.05 S4 100 900 0.1 S5 200 800 0.2 S6 500 500 0.5 S7 1000 0 1 
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表 2 标准水样δ2H的测试结果
Table 2. Measrued δ2H values of standard samples
标准物质编号 标准偏差
(‰)δ2Hst-s平均值
(‰)δ2Hst标准值
(‰)GBW04458 0.65 271.4 -1.7 GBW04459 0.79 200.1 -63.4 GBW04460 0.47 102.5 -144.0 注：标准偏差和δ2Hst-s是由5次平行测定结果求得。
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表 3 不同乙醇体积比(r)水样δ2H的测试结果
Table 3. Measrued δ2H values of water samples with different ethanol volumetric ratios (r value)
待测水样编号 标准偏差
(‰)δ2Hsam-s平均值
(‰)δ2Hsam计算真值
(‰)S1 0.53 213.7 -50.9 S2 0.53 212.9 -51.6 S3 0.53 205.4 -57.9 S4 0.32 194.9 -66.7 S5 0.25 176.2 -82.4 S6 0.26 114.7 -134.2 S7 0.21 8.5 -223.5 注：标准偏差和δ2Hsam-s是由3次平行测定结果求得。
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