Research advances on the influence of typical geochemical and hydrogeological characteristics on the natural attenuation of pollutants
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摘要:
监测自然衰减技术(MNA)作为污染场地有效的风险防控手段在世界范围内得到广泛应用, 该技术应用的核心是确定污染物衰减能力及效率。而其衰减能力及效率会受到污染物本身特性, 以及场地典型地球化学、水文地质条件等固有特征影响，明确场地固有性质对污染物自然衰减的影响对该技术的合理应用具有更为重要的实际意义。以场地典型地球化学特征与水文地质特征为重点, 阐述了两者对地下水中污染物自然衰减过程的影响及其作用机理。沉积物有机质和矿物组成等典型地球化学特征控制污染物的吸附络合行为, 同时参与电子传递过程从而影响污染物的生物降解及化学转化过程；水文地质条件方面, 含水层岩性及结构特征会导致渗透性、吸附解吸能力有所差异，从而影响污染物的自然衰减能力, 地下水流速控制污染物对流弥散作用, 同时影响污染物从沉积物固相向地下水的溶解释放以及生物降解动力学过程。总体上, 由于有机质、矿物、微生物组分的复杂性, 加之水文地质条件的不均质性, 场地固有性质对污染物自然衰减的影响研究还有待进一步加强, 尤其要通过长期的场地监测, 识别污染物衰减的时空动态规律, 深化对场地典型地球化学、水文地质条件与污染物相互作用机制的认识。
Abstract:As an effective risk prevention and control tool for contaminated sites, Monitoring Natural Attenuation (MNA) has been applied worldwide. The core of this technology is to determine the ability and efficiency of pollutant attenuation, which are influenced by the nature of the pollutants themselves, as well as the typical geochemical and hydrogeological conditions and other inherent characteristics of the site. It is of greater practical importance to clarify the influence of the inherent properties of the site on the natural attenuation of pollutants for the rational application of the technology. The authors address the influence of typical site geochemical characteristics and hydrogeological characteristics on the natural attenuation process of pollutants in groundwater and its mechanism. The typical geochemical characteristics, such as the organic matter and mineral composition of sediments, control the adsorption and complexation behavior of pollutants, and participate in the electron transfer process to influence the biodegradation and chemical transformation of pollutants. Hydrogeological characteristics influence the ability of natural attenuation through the differences in permeability, adsorption and desorption capacity caused by the lithologic characteristics of sediments. Groundwater flow rate controls the convection and dispersion of pollutants and affects the dissolution and release of pollutants from sediment to groundwater as well as the kinetic process of biodegradation. In general, due to the complexity of organic matter, mineral and microbial components and the heterogeneity of hydrogeological conditions, the study of the influence of site intrinsic properties on the natural attenuation of pollutants needs to be further strengthened. In particular, we need to identify the spatial and temporal dynamics of pollutant attenuation through long-term site monitoring, and deepen the understanding of the mechanisms underlying the interaction between typical site geochemistry, hydrogeological conditions and pollutants.
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图 1 自然衰减的常见作用途径(改编自文献[3])
NAPL.非水相液体；LNAPL.轻质非水相液体；DNAPL.重质非水相液体；a.挥发; b.吸附; c.稀释; d.弥散; e.化学转化; f.生物降解
Figure 1. Common pathways on natural attenuation processes of pollutants
图 3 在含还原细菌、金属氧化物、黏土矿物和天然有机质(NOM)体系中增强污染物还原降解的途径[29]
a.微生物直接还原; b.天然有机质介导还原; c.金属氧化物和黏土矿物间接还原; d.天然有机质结合金属氧化物和黏土矿物间接还原
Figure 3. Pathways for enhanced pollutant reduction in systems containing reducing bacteria, metal oxides, clay minerals and natural organic matter (NOM)
图 4 影响自然衰减破坏性作用过程的场地特征
Figure 4. Site characteristics affecting the destructive process of natural attenuation
图 5 岩性颗粒大小影响污染物自然衰减的物理化学和微生物过程[71]
RDA1.冗余分析主成分1；RDA2.冗余分析主成分2
Figure 5. Effects of medium particle size on physicochemical and microbiological processes of the natural attenuation of pollutants
表 1 MNA修复地下水污染的典型场地案例
Table 1. Typical site cases of groundwater pollution remediation by MNA
场地名称 污染原因 污染时长/a 监测时段 监测污染物 主要降解途径 主要过程 资料来源 澳大利亚某农场 地下储油罐泄露 30 2004-2010年 总石油烃、萘、苯系物 生物作用 硫酸盐还原 文献[8] 韩国某军事基地 地下储油罐泄露 / 2008-2009年 苯系物 生物作用 反硝化 文献[9] 中国某农药厂 原辅料储罐泄露 >7 2016-2020年 氯代烃 生物作用 共代谢、还原脱氯 文献[10] 挪威某垃圾填埋场 渗滤液下渗 >5 1992-2015年 铁、锰等 化学、生物作用 氧化沉淀 文献[11] 美国某燃气厂 焦油储罐泄露 25 1991-2005年 单/多环芳烃 生物作用、吸附 矿化 文献[12] 
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表 2 不同岩性等特征下有机污染物的衰减效率
Table 2. Attenuation efficiency of organic polluants under different lithology and other characteristics
实验室数据 污染物 污染水平/(g·kg-1) 衰减条件 砂∶粉砂: 黏土(wB/%) 衰减程度/% 衰减时间/d 备注 资料来源 石油 21.1 pH=7.8, 含水量60% 30∶45∶25 61 210 文献[38] 石油烃 11.5 pH=6.4，含水量15% 砂>91 20~30 270 文献[60] 石油烃 10.4 pH=6.0，含水量50% 粉砂 17 28 文献[61] 石油烃 140.0 pH=7.6，含水量30% 砂92 38 80 文献[62] 柴油 50.0 pH=5.6, 含水量50%~60% 76∶12∶12 21 75 文献[63] 柴油 3.50 pH=7.1, 含水量60% 黏土>90 84 7 文献[7] 93 56 4.25 92 28 94 56 场地数据 污染物 污染水平 衰减条件 砂∶粉砂∶黏土(wB/%) 衰减程度/% 天数/d 备注 资料来源 柴油 1 L/m2 pH=7.7 30∶42∶28 56 4 土壤表层0~10 cm 文献[64] 年均降雨量620 mm 99 400 平均值 石油烃 15 mg/L 年均降雨量436 mm 砂 65 300 可监测的最高浓度 文献[65] 石油烃 2.3 mg/L / 砂 87 1 460 可监测的最高浓度 文献[66] 苯系物 3.45 kg/m2 pH=5.0~5.3
年均降雨量1 600 mm黏土 < 5 85 985 污染羽总质量 文献[67]
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