铬污染场地原位修复技术应用现状与展望

韩伟; 赵瑞锋; 石一辰; 刘婉蓉; 王玉晶; 聂晶磊

doi:10.12153/j.issn.1674-991X.20221240

铬污染场地原位修复技术应用现状与展望

doi: 10.12153/j.issn.1674-991X.20221240

生态环境部固体废物与化学品管理技术中心

基金项目: 国家重点研发计划项目（2019YFC1806001，2018YFC1800202）

详细信息

作者简介:
韩伟（1984—），男，高级工程师，博士，主要从事重金属污染防治，污染场地调查、风险评估与修复，hanv@163.com

通讯作者:
刘婉蓉（1985—），女，高级工程师，硕士，主要从事污染场地调查、风险评估与修复，liuwanrong@meescc.cn

中图分类号: X53
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出版历程
- 收稿日期: 2022-12-11
- 录用日期: 2023-04-03
- 修回日期: 2023-03-31
- 网络出版日期: 2023-09-20

Status and prospect of in-situ remediation technologies applied in hexavalent chromium contaminated sites

Solid Waste and Chemicals Management Center, Ministry of Ecology and Environment

摘要

摘要:
六价铬Cr(Ⅵ)是一种来源广泛的重金属污染物，因其形态、价态多样，地球化学反应过程极其复杂，同时国内Cr(Ⅵ)污染场地众多，对其修复具有很大的挑战性。原位修复因不开挖土方、对环境干扰小等诸多优势逐渐成为污染场地修复策略的主流。综述了国内外Cr(Ⅵ)不同类型原位修复技术研究进展，在结合大量原位修复工程案例的基础上重点分析了原位生物、原位化学修复技术与不同注入方式的应用效果。阐明了不同类型原位修复技术的适用地层条件、适用浓度范围、影响半径、修复工期、修复介质、药剂类型及用量与施加方式等关键参数。针对复杂的Cr(Ⅵ)污染场地，建立精准的污染场地概念模型，选取高效适宜的修复药剂和注入方式或者修复工艺组合，是确保修复效果的关键。通过分析现有Cr(Ⅵ)不同原位修复技术在实际应用中的优缺点，探索其在不同场景的适用性，同时对技术发展方向进行了展望。
- 六价铬 /
- 原位修复 /
- 注入 /
- 还原药剂材料 /
- 污染地块 /
- 土壤 /
- 地下水
Abstract:
Hexavalent chromium Cr(Ⅵ) is a typical heavy metal pollutant with a wide range of sources. Due to its diverse forms and valence states, the geo-chemical reaction process is extremely complicated. There are lots of Cr(Ⅵ) contaminated plots in China and the remediation of Cr(Ⅵ) contaminated sites is very challenging. In-situ remediation has gradually become the mainstream of remediation strategies for contaminated sites due to many advantages such as no excavation and less environmental interference. The latest research progress of different in-situ remediation technologies for Cr(Ⅵ) was reviewed. Based on a large number of in-situ remediation engineering cases at home and abroad, the application effects of in-situ biological, in-situ chemical and other remediation technologies and different injection methods were analyzed. The key parameters of different types of in-situ remediation technologies including applicable geological conditions, applicable concentration range, influence radius, remediation duration, remediation medium, agent type and dosage, and injection method were clarified. It played a key role to establish a precise contamination field concept model, and choose efficient chemicals and the best injection method or remediation process combinations for complex contaminated sites. The advantages and disadvantages of different in-situ remediation technologies of Cr(Ⅵ) were compared in examples, and their different applicable scenarios were explored. At the same time, the future development direction of technologies was prospected.
- hexavalent chromium /
- in-situ remediation /
- injection /
- reduction agents and materials /
- contaminated site /
- soil /
- groundwater

HTML全文

图 1 耐铬微生物细胞对Cr(Ⅵ)的解毒途径与机制示意^[30-31]

A—Cr(Ⅵ)利用染色体介导的硫酸盐摄取途径进入细胞，发生突变时，减少运移；B—细胞外还原和吸附；C—细胞内Cr(Ⅵ)还原产生氧化应激，损伤蛋白质和DNA；D—解毒酶抑制氧化应激，最大限度地减少Cr(Ⅵ)的毒性；E—质粒编码转运蛋白可能将铬酸盐从细胞质中排出；F—DNA修复系统保护受损细胞。

Figure 1. Schematic diagram of detoxification pathways and mechanisms of Cr(Ⅵ) by chromium-resistant microbial cells

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图 2 Cr(Ⅵ)原位修复药剂材料、工艺特点及发展方向

Figure 2. Agent materials, process characteristics and development directions of Cr(Ⅵ) in-situ remediation

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图 3 不同类型药剂使用频次对比

Figure 3. Comparison of the use frequency of different chemicals

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图 4 不同原位修复技术使用数量对比

Figure 4. Comparison of application of Cr(Ⅵ) in-situ remediation technologies

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图 5 不同年份Cr(Ⅵ)原位修复工程案例数量变化

Figure 5. Variation of in-situ remediation cases for Cr(Ⅵ) in different years

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图 6 不同原位修复案例中Cr(Ⅵ)浓度污染水平

Figure 6. Contamination level of Cr(Ⅵ) in different in-situ remediation cases

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图 7 Cr(Ⅵ)原位修复技术在不同环境介质中的应用情况

Figure 7. Application of Cr(Ⅵ) in-situ remediation technologies in different environmental matrices

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表 1 国内Cr(Ⅵ)原位修复典型案例汇总

Table 1. Summaries of Cr(Ⅵ) in-situ remediation cases at home

类型	项目所在地	规模	岩性	修复介质	原始浓度	修复方式及关键参数	药剂与材料	修复时间	修复效果与存在的问题
原位化学	重庆^[46]	中试，修复深度 20 m	填土层、泥岩层、砂岩层	土壤	0.30~1.61 mg/kg	场地中部注入井，下游外侧高压旋喷联合工艺	还原药剂、稳定药剂	3 d	Cr(Ⅵ)浓度<0.3 mg/kg
	山东^[47]	中试	粉土和粉黏土	土壤	最高浓度4 570 mg/kg	原位注入，化学还原	多硫化钙	60 d	Cr(Ⅵ)浓度<9 mg/kg，去除效果明显，达标难
	天津^[44]	586 m²，污染深度2~6 m，土方量为4 282 m³；地下水修复范围为1 765 m²	粉黏土层，渗透性较差	土壤	17.1~26.8 mg/kg	高压旋喷技术，有效半径可达1.4 m	硫酸亚铁		Cr(Ⅵ)浓度<2.4 mg/kg
	重庆^[48]	修复面积为12 246 m²，修复方量为16 150.5 m³，回填土20 m 以下		土壤	最高浓度 1.61 mg/kg	加压注入井+高压旋喷，影响半径分别为2.5和1 m	还原剂与稳定剂		修复后Cr(Ⅵ)浓度<0.25 mg/kg
	南方某地^[49]	长15 m、宽 12 m、深4 m，720 m³		土壤	污染深度为3~12 m，试验区浓度为273~1 540 mg/kg	原位淋洗与水平井	清水、硫酸亚铁	10批次	Cr(Ⅵ)去除率为93.6%~98.1%，浓度为17.4~29 mg/kg
	湖南^[50]	20 m²（4 m×5 m），8个注射点，修复深度为地下1~6 m		土壤	1 060~1 540 mg/kg	高压旋喷注射：3%药剂投加比，注射压力10 MPa，影响半径0.5 m，提升速率10 cm/min	硫铁矿物复配稳定化剂	7 d	Cr(Ⅵ)浓度<0.5 mg/kg，Cr(Ⅵ)浸出浓度<0.004 mg/L
	山东^[51]	21 900 m²，最深污染深度48 m	填土层、强风化、中风化、弱风化闪长岩层	地下水	0.12~25 900 mg/L	注入井原位化学还原	硫酸亚铁	400 d	150 d后Cr(Ⅵ)浓度降至0.1 mg/L，第250~400天一直稳定在0.1 mg/L以下，中间出现反弹
	国内某地^[42]	中试规模		地下水	40~160 mg/L	注入井，影响半径2~4 m	柠檬酸+多硫化钙	20 d	下游Cr(Ⅵ)去除率接近100%，两侧去除率为12.92%~82.22%，下游修复效果明显优于两侧修复效果
	北京^[43]	6 m×6 m		地下水	1.93 mg/L	直推式注入：GP钻机加压泵注入300 L 5 mg/L的纳米零价铁，影响半径3 m	零价铁	26 d	Cr(Ⅵ)浓度为0.001 mg/L，去除率大于99%
	西北地区^[17]	注射区域面积20 m×10 m，修复深度为17 m	黄土、砾砂、粉黏、粉砂、圆砾	土壤和地下水	地下水：12.15 mg/L；土壤：100.51 mg/kg	锚固旋喷钻机原位注入，压力30 MPa，钻杆提升速度小于0.14 m/min，药剂注入量250 L/m，药剂影响扩散半径0.75 m，钻孔间距1.3 m	石硫合剂		地下水Cr(Ⅵ)浓度<0.01 mg/L；修复后土壤Cr(Ⅵ)浓度平均值为2.7 mg/kg
化学+微生物	山东^[47]	中试	粉土和粉黏土	土壤	土壤最高浓度2 730 mg/kg	原位注入，生物化学还原	还原剂、生物营养剂	60 d	土壤Cr(Ⅵ)浓度<70 mg/kg，去除效果明显，达标难
	江苏^[52]	600 m²，修复深度8 m	粉黏土、黏粉土、砂土	地下水	土壤：200~500 mg/L；地下水：390~456 mg/L	注入井，井间距5 m	还原剂（多硫化钙）、渗透剂、营养剂（乳酸乙酯）、微生物调节剂	37 d	下游地下水Cr(Ⅵ)浓度明显下降，观测井最高去除率为94%~95%。两侧及上游区域修复效果差
	山东^[53]		杂填土、粉黏土、淤泥质粉黏土	土壤和地下水	土壤60~890 mg/L；地下水：2.0~12 mg/L	高压旋喷，影响半径0.8~1.0 m	硫酸亚铁+自制生物药剂	7 d	Cr(Ⅵ)还原率为97.33%~98.96%，土壤和地下水Cr(Ⅵ)浓度为未检出。局部土壤承载力下降，地面下沉
原位微生物	湖南^[54]	500 m²，修复深度 24 m	砂/卵石、基岩裂隙	地下水	1 000~2 000 mg/L	原位生物刺激+地下水循环井（抽注结合）	乙醇	52 d	修复后Cr(Ⅵ)浓度<0.1 mg/L
PRB (物化)	湖南^[55]		松散岩类孔隙和基岩裂隙	地下水	0.08~323.24 mg/L	PRB：长50 m ，宽2 m，深20 m	填料：零价铁、陶瓷、活性炭	6个月	运行24周，Cr(Ⅵ)浓度均低于修复目标限值0.1 mg/L，25周开始，Cr(Ⅵ)浓度超过目标限值，更换吸附填料
	河南^[45]	中试	0~8 m和12~15 m岩性为粉黏土至黏土；8~12 m为中细砂	地下水	4~32.4 mg/L	PRB：长15 m，宽2.8 m，深12 m	填料：铸铁、活性炭、河沙	10个月	墙体内部Cr(Ⅵ)无检出，去除效果明显；下游浓度由西向东呈高、低、高、低变化，浓度为4~20 mg/L
	湖南^[56]	240 m²	回填层、黏土层、砂土层、砾石层	地下水	27.29~242.65 mg/L	PRB：长27 m，宽3.4 m，深15 m	填料：零价铁、砾石、细沙	6个月（该时间为示范周期，非修复时间）	填料区Cr(Ⅵ)去除率为69%~100%，下游监测井D1、D2和D3的Cr(Ⅵ)浓度分别为16.54~84.75、26.94~96.71和3.65~ 130.27 mg/L，有消减未达标

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表 2 国外Cr(Ⅵ)原位修复典型案例汇总

Table 2. Summaries of Cr(Ⅵ) in-situ remediation cases abroad

类型	项目所在地	规模	岩性	修复介质	原始浓度	修复方式及关键参数	药剂与材料	修复时间	修复效果与存在的问题
原位化学	美国内华达州^[57]	污染深度8~10 m	粉土、粉砂、砂粉	地下水	0.012~0.029 mg/L	原位化学还原：组井注入，分层监测。影响半径5~6 m	多硫化钙	2月	Cr(Ⅵ)去除率为67%~99%
	奥地利^[58]	约1000 m²	砾石、细砂、粉黏土	地下水	0.2~2 mg/L	上游建注入井	连二亚硫酸钠	240 d	Cr(Ⅵ)浓度从2 mg/L降低至0.1 mg/L以下，但是停止注入后出现反弹
	美国南卡罗来纳州^[22]	修复深度5 m		地下水	5~52 mg/L	Geoprobe直推式注入；影响半径1.75~2.5 m	连二亚硫酸钠+硫酸亚铁	40 d	影响半径范围内地下水Cr(Ⅵ)未检出
	美国南卡罗来纳州^[21]	150 m²；修复深度3.0~4.5 m		地下水	4.8 ~7.4 mg/L	Geoprobe直推式注入，注入压力0.20 MPa	硫酸亚铁 + 连二亚硫酸钠	120 d	120 d后检测，地下水中Cr(Ⅵ)浓度<0.01 mg/L，修复797 d后土壤中仍有检出，平均浓度为0.382 mg/kg
	意大利东北部^[59]			地下水	4 500 μg/L	自然衰减		6 a	自然衰减6 a后无检出。但是再过由于锰的氧化作用5 a后出现反弹。地下水Cr(Ⅵ)浓度达到1 560 μg/L
	英国肖菲尔德^[19]	中试25 m²，113 m³，修复深度1.5~6 m		土壤和地下水	土壤：148 mg/kg；地下水：7.42 mg/L	地下水循环井，抽提处理后回注	多硫化钙	23 d	土壤中Cr(Ⅵ)降低了86%，地下水去除率接近100%
	英国肖菲尔德^[19]	中试24 m²，230 m³，深度0.4~9.6 m		土壤和地下水	土壤：354 mg/kg；地下水：0.835 mg/L	直推式注入，影响半径1 m	多硫化钙	21 d	Cr(Ⅵ)去除率接近100%
	英国肖菲尔德^[19]	中试25 m²，250 m³，深度0~10 m		土壤和地下水	土壤：342 mg/kg；地下水：143 μg /L	高压旋喷	多硫化钙	18 d	土壤修复效果好，Cr(Ⅵ)去除率100%
原位生物	瑞士图恩^[60]	30 m²，深度7 m，污染羽长度250 m	河流冲击砂层	地下水	2.5~4 mg/L	原位生物刺激：注入井注入，分批次间歇式注入	糖蜜	1 a	注入2个月，Cr(Ⅵ)浓度降低至为0.005~0.5 mg/L，停止注药后稳定
	美国内华达州^[52]	最深18 m	粉土、粉砂、砂粉	地下水	11 mg/L	原位生物还原/刺激：组井注入，分层监测，注入压力0.12 MPa。影响半径5~6 m	碳源：糖粒，糖蜜，糖业废水；氮磷助剂：磷酸二氢钠，尿素，碳酸氢钠	2月，3批次注药	Cr(Ⅵ)浓度从11 mg/L降至0.01 mg/L
	美国华盛顿^[29]	30 m×30 m，修复深度15.84 m	0~12.2 m粗砂，以下为粉土、粉黏土	地下水	10 mg/L	循环井原位生物刺激：注入井注入，下游设置抽提井（不连续抽提）。影响半径5 m	甘油、聚乳酸	1 a	地下水Cr(Ⅵ)未检出，注药3 a后依然稳定
	比利时法兰德斯^[61]	中试规模8~12 m		地下水	最高浓度 80 000 µg/L	注入井，原位生物刺激	糖蜜和乳酸盐	410 d	修复后Cr(Ⅵ)浓度低于50 µg/L
PRB	瑞士图恩^[62]		高渗透地层，碳酸盐砾石含水层	地下水	4 mg/L	PRB，单桩直径1.3 m，修复深度 13 m	铁屑、砾石	2 a	运行2 a内大部分Cr(Ⅵ)绕流PRB，下游无修复效果
	瑞士维利绍^[63]	中试规模，12~ 23 m		地下水	0~2.5 mg/L	PRB，填充桩直径1.3 m	零价铁	4 a	双排桩可有效治理下游地下水Cr(Ⅵ)，单排桩修复效果差
	美国北卡罗来纳州^[64-65]			地下水	5 mg/L	PRB，反应墙长45.7 m、深7.3 m、厚0.6 m	零价纳米铁	2 a	修复后Cr(Ⅵ)浓度降至未检出

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