Natural Attenuation Mechanisms of Petroleum Hydrocarbons in a Fractured Karst Aquifer
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摘要: 石油类有机物污染是地下水环境领域亟须解决的关键课题.本次研究耦合数值模拟和水文地球化学技术模拟岩溶裂隙含水层中石油类有机物的自然衰减过程并定量计算其自然衰减机制.基于BIOSCREEN模型的模拟计算可知，近30年对流、弥散、稀释等物理过程和生物降解过程对石油类有机物衰减贡献率的平均值分别为31.53%和68.47%，生物降解作用是岩溶裂隙含水层自然修复能力的主要机制.利用质量守恒定律分析水化学（HCO3-、NO3-）和同位素（δ15NNO3、δ18ONO3和δ13CDIC）之间的相关关系可知石油类有机物生物降解贡献地下水HCO3-的平均值为33.93%；石油类有机物生物降解消耗主要电子受体NO3-贡献地下水δ13CDIC的百分率为30.77%且其占总生物降解的90.69%.Abstract: It is vital to prevent the pollution of petroleum hydrocarbons in the groundwater environment globally. In the paper it uses numerical simulation method and hydrogeochemical techniques to simulate the natural attenuation processes of petroleum hydrocarbons in the fractured aquifer and calculate the natural attenuation mechanisms quantitatively. BIOSCREEN model was used to simulate the natural attenuation processes of petroleum hydrocarbons, the contribution rates of physical processes and biodegradation processes to the total natural attenuation are 31.53% and 68.47%, respectively, and biodegradation was the main mechanism for the natural remediation ability of fractured karst aquifer. Inter-relationships between water chemistries (HCO3-, NO3-) and isotopes (δ15NNO3, δ18ONO3 and δ13CDIC) were analyzed by the principle of quality conservation in the research. The average contribution rate of biodegradation to the concentration of HCO3- in the groundwater system was 33.93%. Ion of NO3- was the main electron acceptor in the anaerobic biodegradation processes of petroleum hydrocarbons without methanogenic activity. The process of petroleum hydrocarbon biodegradation consuming NO3- contributes 30.77% to the δ13CDIC in the groundwater system, which accounts for 90.69% of total biodegradation of petroleum hydrocarbons in the fractured karst aquifer.
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图 1 研究区水文地质简图
1.松散岩类孔隙水， < 100 m3/d2.松散岩类孔隙水，100~1 000 m3/d; 3.松散岩类孔隙水， > 1 000 m3/d; 4.碳酸盐岩类裂隙岩溶水， < 100 m3/d; 5.碳酸盐岩类裂隙岩溶水，100~1 000 m3/d; 6.碳酸盐岩类裂隙岩溶水，1 000~5 000 m3/d; 7.碳酸盐岩类裂隙岩溶水， > 5 000 m3/d; 8.裸露碎屑岩裂隙水、层间岩溶裂隙水， < 100 m3/d; 9.裸露碎屑岩裂隙水、层间岩溶裂隙水，100~1 000 m3/d; 10.取样点; 11.断层；12.富水线；13.石化厂区；14.径流方向
Fig. 1. The schematic hydrogeological map of the study area
图 3 水化学离子和同位素间相关关系
Fig. 3. Graphs of correlations among hydrochemical ions and isotopes
a.NO3--δ15NNO3; b.NO3--δ18ONO3; c.δ15NNO3-δ18ONO3; d.HCO3--NO3-; e.HCO3--δ13CDIC; f.NO3--δ13CDIC; g.HCO3--δ15NNO3; h.δ15NNO3-δ13CDIC; i.δ18ONO3-δ13CDIC
表 1 模型输入值
Table 1. Parameter values for the model
序号 参数 取值 序号 参数 取值 1 模拟面积长度(m) 18 000 9 土壤密度(g/m3)(刘姝媛，2016) 2.43 2 模拟面积宽度(m) 7 000 10 分配系数(mL/g)(刘姝媛，2016) 0.12 3 污染源宽度(m) 2 000 11 一级衰减系数(d-1)(Guo et al., 2010) 3.76×10-3 4 污染源深度(m)(刘新华等，1996) 20 12 ΔNO3-(mg/L) (a)：14.86；(b)：44.97；(c)：10.06 5 纵向弥散度(m) 5 13 ΔSO4-(mg/L) (a)：50.13；(b)：9.89；(c)：1.97 6 横向弥散度(m) 0.5 14 UFNO3 (Guo et al., 2020) 4.81 7 垂向弥散度(m) 0.05 15 UFso4 (Guo et al., 2020) 4.65 8 渗透速度(m/d)(Zhu et al., 2000) 152.70 16 CO(mg/L) (a)：51.86；(b)：10.26；(c)：3.52 
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表 2 不同时期石油类有机物实测浓度值
Table 2. The measured concentrations of petroleum hydrocarbons in different periods
年份(a) 石油类有机物浓度(mg/L) D4 D5 D7 D12 D13 1999 14.60 12.40 7.56 6.70 1.20 2009 1.577 0.361 0.018 0.008 0.004 2019 - 0.356 0.011 0.005 0.001
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表 3 一级衰减过程和生物降解过程贡献率汇总
Table 3. The summary of contribution rates of first-decay processes and mixing reaction processes
贡献率 1994—1999年平均值 1999—2009年平均值 2009—2019年平均值 总平均值 一级衰减过程(%) 47.15 22.02 25.43 31.53 生物降解过程(%) 52.85 77.98 74.57 68.47
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表 4 3种NO3-来源的同位素变化范围及其来源比例统计
Table 4. Isotopic variation ranges and contribution rates of three sources for NO3-
类型 同位素变化范围(‰) 来源比例(%) δ15NNO3 δ18ONO3 最小值 平均值 最大值 铵肥 -7.08~5.09 -5.42~14.79 10.44 37.50 48.62 土壤氮 -2.31~8.30 -5.42~14.79 16.78 42.13 66.87 污废水 0~24.72 -5.42~14.79 16.45 20.37 22.70
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