Remediation Strategies for Contaminated Groundwater at Chemical Industrial Sites in the Beijing-Tianjin-Hebei Region
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摘要: 京津冀化工场地地下水污染问题突出，严重威胁当地饮水安全和可持续发展，亟待开展修复治理.针对京津冀化工场地地下水污染现状，分析了化工场地地下水污染修复面临的挑战，提出了分区分级的修复治理对策.结果表明：①针对可能存在NAPL(非水相液体污染物)的高风险污染源区，采取高强度修复措施，以实现污染物总量的快速削减；②针对中度污染区，采取单位能耗强度更低的长效修复措施，降低修复成本和二次污染风险；③针对低风险的轻度污染区，采取风险管控措施.结合对典型化工场地地下水污染修复技术的分析，提出的分区分级修复治理对策具有以下特点：①多技术耦合，形成互补效应，可提高修复效率；②节约修复成本，降低二次环境影响；③体现基于风险的原则，避免过度修复.Abstract: Groundwater contamination at chemical industrial sites in the Beijing-Tianjin-Hebei Region poses a great risk to local drinking water safety and sustainable development. In order to accelerate the groundwater remediation progress, the status and challenges of groundwater contamination at chemical industrial sites in the Beijing-Tianjin-Hebei Region were analyzed, and remediation strategies were proposed: (1) Intensive remediation technologies with high mass removal efficiencies could be applied to heavily polluted area where NAPL exist; (2) Technologies with lower energy demand and long-effectiveness could be applied to the aquifers; (3) Risk control technologies could be applied to slightly polluted area under condition that the land use was not affected. By analyzing the typical groundwater remediation technologies, the advantages of the proposed strategy were summarized as followings: (1) Improved remedial efficiency with treatment trains applied; (2) Lower remediation cost and secondary environmental impact; (3) Lower risk of over-engineering due to risk-based principles.
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图 1 京津冀化工场地地下水污染概况
Figure 1. General situation of groundwater contamination at chemical industrial sites in the Beijing-Tianjin-Hebei Region
图 3 分区分级的化工场地地下水污染治理对策
Figure 3. Groundwater remediation strategies for chemical industrial sites
图 4 SDS-正丁醇复配体系增溶增流效果
Figure 4. Nitrobenzene removal promotion by SDS-n-butanol system
种类 典型污染物 特征 苯系物 苯、甲苯、二甲苯等 迁移性强、挥发性强、易降解 氯代烃 四氯化碳、三氯乙烯、二氯乙烷、氯乙烯 易迁移、挥发性强、难降解、高毒性 石油烃 汽油、柴油、机油等 生态毒性大 持久性有机物 氯酚、多氯联苯、多环芳烃、滴滴涕、六六六、氯丹、林丹 挥发性弱、难降解、高毒性 重金属 六价铬、镉、砷、铅 迁移性差(除六价铬外)、难去除 
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项目 参数 适宜范围 污染物性质 污染物类型 VOCs和石油烃 亨利系数(20 ℃) ＞0.01 蒸气压(20 ℃) ＞1.00 mmHg 场地条件 抽水量 可使液位下降(双泵系统); ＜5 gpm (单泵系统) 最大污染深度 无限制(双泵系统)；6~15 m (双泵系统) 含水层介质 砂土至黏土 LNAPL厚度 >15 cm
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污染物 NAPL区域土壤性质 修复周期/d 加热方式 加热温度/℃ 修复前平均浓度/(mg/kg) 修复后平均浓度/(mg/kg) 去除率/% 四氯乙烯 致密黏土 120 传导加热 100 2 700.00 0.01 >99.85 三氯乙烯 裂隙黏土 150~180 传导加热 99 99.70 0.07 三氯乙酸 裂隙黏土 150~180 传导加热 99 31.90 0.04 四氯乙烯 黏土、粉砂、砂土 330 传导加热 100 2 864.00 4.20 四氯乙烯 黏土、砂土、砾石 169 传导加热 100 78.00 0.01 四氯乙烯 黏土、砂土、砾石 107 传导加热 100 337.00 0.05 四氯乙烯 煤渣、砂土、淤泥 192 传导加热 150 125.00 0.04
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项目 参数 适宜范围 污染物 污染物种类 苯系物、MTBE、石油烃、氯代烃、部分PAHs 渗透系数 ＞10-6 cm/s 场地条件 土壤有机质含量 ＜0.1%(以干质量计) 地下水水位深度 ＞1.5 m LNAPL厚度 ＜15 cm
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表 5 缓释材料在实际场地的应用案例
Table 5. Field applications of slow-release materials for groundwater remediation
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目标污染物 土壤类型 注气井间距/m 注气方式 修复周期/月 削减率/% 修复结束 后期监测 四氯乙烯、三氯乙烯、二氯乙烷 — 12 连续 7.5 98.3 97.2 三氯乙酸、三氯乙烯、二氯乙烷 — 8 脉冲为6 h/循环 8 98.2 95.3 三氯乙烯 砂土 24 脉冲为4 h/循环 15 98.5 99.4 苯系物 砂土 12~18 连续 4 >99.9 >99.9 苯系物 砂土、粉土 12 脉冲为16 h/循环 6 -20.5 99.7 苯 砂土、黏土 24 脉冲 10 98.4 99.8 石油烃 砂土 10~14 脉冲为12 h/循环 16 90 93.1 苯系物 砂土、粉土 4~6 脉冲为12 h/循环 7 96.4 46.9 苯系物 砾石、粉土、黏土 9 脉冲为28 d/循环 20 99.9 91.5
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生物修复技术 目标污染物 降解途径 好氧生物修复 非卤代有机化合物 氧作为电子受体，直接代谢 厌氧氧化生物修复 部分类石油污染物 硝酸盐和硫酸盐作为电子受体，直接代谢 厌氧还原生物修复 氯化溶剂(四氯乙烯、三氯乙烯和三氯乙酸等)、六价铬 生物可利用有机碳作为电子供体，直接代谢
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表 8 典型生物修复与其他技术耦合修复地下水方式[47]
Table 8. Typical groundwater remediation combining bioremediation and other remedies[47]
耦合技术组合 目标污染物 修复策略 ISCO+好氧/厌氧生物修复 苯、MTBE 以过硫酸盐/过氧化钙作为氧化剂修复高浓度污染羽，过氧化钙的释氧作用和硫酸盐作为电子受体可分别促进好氧和厌氧生物降解作用 ISTD+好氧生物修复 苯并[a]芘、五氯苯酚和四氯二苯并对二英 前期采用蒸汽热脱附，当修复效率开始下降时，结合生物通风或生物曝气技术促进好氧生物降解作用 ISCR+厌氧生物修复 含氯挥发性有机物 前期采用ISCR将高浓度污染物修复至较低浓度后，利用厌氧生物修复去除污染物至修复目标值 ISTD+生物修复 苯、甲苯和萘 前期采用蒸汽热脱附，当污染物降至一定浓度时ISTD修复效率开始降低，利用生物修复去除污染物
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