Identification of Produced Water and Characteristics of Hydrochemistry and Stable Hydrogen−Oxygen Isotopes of Contaminated Groundwater
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摘要:
识别地下水污染来源、认识受该类污染源污染的地下水化学特征是地下水污染防治工作的重中之重。产出水作为石油、天然气工业的废水，具有组分复杂、危害性大的特点。针对受产出水污染的地下水研究较少，受污染地下水的特征以及识别该污染源的方法尚不明确的问题，笔者以延安某地下水污染场地为研究区，利用水文地球化学和氢氧稳定同位素的方法探讨受产出水污染的地下水的水化学和同位素特征，并通过对比地下水和油层水的钠氯系数、氯镁系数、脱硫系数和碳酸盐平衡系数对产出水进行识别。研究结果表明，该区域受产出水污染的地下水表现为高TDS和贫化的氢氧稳定同位素特征；其水化学类型以Cl−Na型、Cl−Mg·Ca·Na型为主，且随着受产出水影响程度降低，地下水由Cl−Na型转化为Cl−Mg·Ca·Na型，再到HCO3·SO4−Na·Ca·Mg型；离子比例关系较正常地下水混乱，无线性规律；受产出水污染的地下水的钠氯系数、氯镁系数、脱硫系数和碳酸盐平衡系数大小均在长6油层水的范围内，表明判断油气成藏条件的相关参数可以用来识别产出水污染。该研究探讨了受产出水污染的地下水的水化学特征和氢氧稳定同位素特征，提出对比地下水和油层水的相关参数来识别产出水污染的方法，对产出水污染场地的识别、认识、调查、监测、和修复具有重要意义。
Abstract:Identifying the source of pollution in groundwater and understanding the hydrochemical characteristics of contaminated groundwater by such pollution are very important for pollution prevention of groundwater. As the waste water of petroleum and natural gas industry, the produced water has the characteristics of complex components and great harmfulness. In view of the problems that there was less research on the contaminated groundwater by produced water, and the characteristics of the contaminated groundwater and the method to identify the pollution source were still unclear, the paper toke a polluted groundwater site in Yan’an as the research area, applied the methods of hydrogeochemistry and stable hydrogen−oxygen isotopes to describe the hydrochemical and isotopic characteristics of the groundwater contaminated by produced water, and compared the sodium−chloride coefficients, magnesium−chloride coefficients, desulfurization coefficients and carbonate balance coefficients of groundwater and reservoir water to identify the produced water. The results showed that the contaminated groundwater by produced water in this area was characterized by high TDS and depleted stable hydrogen−oxygen isotope; The chemical types were mainly Cl−Na type and Cl−Mg·Ca·Na type, and with the decrease of the influence of produced water, the groundwater changes from Cl−Na type to Cl−Mg·Ca·Na type and then to HCO3·SO4−Na·Ca·Mg type. The relationship of ion proportions was more chaotic than that of normal groundwater and had no linear law. The sodium−chloride coefficients, magnesium−chloride coefficients, desulfurization coefficients and carbonate balance coefficients of polluted groundwater by produced water were all within the range of Chang 6 reservoir water, indicating that the relevant parameters for judging the conditions of oil and gas accumulation could be used to identify produced water. This study described the hydrochemical and stable hydrogen−oxygen isotopic characteristics of contaminated groundwater by produced water, and proposed a method to identify produced water by comparing the relevant parameters of groundwater and reservoir water, which were of great significance to the identification, recognition, investigation, monitoring and repair of polluted sites by produced water.
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表 1 主要离子和TDS浓度统计表（mg/L）
Table 1. The concentrations of major ions and TDS (mg/L)
样品 时间 Na+ Ca2+ Mg2+ K+ Cl− HCO3− SO42− TDS Z1 2018 2 445 1 467 103 7.78 6 795 84.6 10.9 10 871 2019 1 150 627 37 6.63 2 853 85.4 158.2 4 875 Z2 2018 1 308 702 69 6.11 3 540 201 7.99 5 734 2019 669 312 26 8.04 1 530 293 40.8 2 733 2020 164 106 15.4 3.86 177 511 8.8 731 Z3 2018 1 368 567 73 5.47 3 391 153 7.7 5 488 2019 1 484 668 49 15.91 3 721 159 83.1 6 100 2020 1 460 616 55.8 4.26 3 250 149 1.3 5 462 Z4 2019 262 171 146 5.47 639 500 104.8 1 579 2020 286 207 166 3.31 778 665 94 1 867 Z5 2018 304 99 27 1.53 512 238 96.6 1 180 2019 329 112 30 1.98 542 287 89.1 1 247 Z6 2018 258 18 67 21.48 155 513 196.7 1 003 2019 303 104 90 25.53 195 824 228.6 1 358 2020 307 111 89 21.8 272 814 237 1 445 Z7 2018 241 69 32 2.42 236 370 131.3 912 2019 150 45 29 1.62 78 427 75.6 592 2020 167 51.9 28.4 1.80 110 437 83.2 661 H1 2018 59.5 33.2 18.8 4.66 35 196 59.6 309 2019 135.1 52.4 39.1 10.89 107.2 305.1 133.3 631 2020 144 45.1 34.1 9.99 131 271 138 638 H2 2018 69.3 29.4 18.6 3.54 45.6 196 64.2 329 2019 157.7 41 39.8 10.61 119.2 311.2 145.7 670 2020 149 43.4 33.7 8.63 121 295 143 646 注：Z代表地下水，H代表地表水。 
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表 2 2018～2020年样品 δD（‰）和 δ18O（‰）值
Table 2. The values of δD (‰) and δ18O (‰) from 2018 to 2020
采样时间 2018年 2019年 2020年 样品 δD（‰） δ18O （‰） δD （‰） δ18O （‰） δD （‰） δ18O （‰） Z1 −84.08 −11.32 −74.78 −9.65 − − Z2 −89.64 −11.74 −80.18 −10.67 −70.65 −9.19 Z3 −84.28 −11.53 −88.33 −12.03 − − Z4 − − −65.86 −8.55 −65.39 −8.60 Z5 −72.78 −9.47 −71.28 −9.84 − − Z6 −64 −8.72 −61.34 −8.43 −63.40 −8.66 Z7 −62.32 −8 −60.81 −8.21 −61.60 −7.69 H1 −53.71 −7.38 −56.08 −7.26 −55.36 −7.30 H2 −51.52 −7.39 −55.99 −6.98 −52.36 −7.13
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表 3 理想混合模型计算结果
Table 3. The results of ideal mixing
2018～2019年计算结果（mg/L） 混合分数 Na+ Ca2+ Mg2+ K+ Cl− HCO3− SO42- NO3− 以Na+ 计，x=0.5403 669.01 343.21 48.31 6.91 1 678.80 236.87 67.22 8.77 以Cl− 计，x=0.5835 617.92 314.52 46.66 6.98 1 529.99 239.74 71.96 9.23 实测值 669 312 26 8.04 1 530 293 40.8 1.86 2019～2020年计算结果（mg/L） 混合分数 Na+ Ca2+ Mg2+ K+ Cl− HCO3− SO42- NO3− 以Na+ 计，x=0.9289 164.0 57.43 30.38 7.63 197.26 269.22 112.16 12.77 以Cl− 计，x=0.9430 156.33 53.56 30.44 7.62 177.03 268.86 113.24 12.93 实测值 164 106 15.4 3.86 177 511 8.8 0.14
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