西方国家工业污染场地管理经验及其对中国的借鉴

近年来,随着＂退二进三＂、＂退城进园＂和＂产业转移＂等政策的实施,中国几乎所有的大中城市正面临着重污染工业企业关闭和搬迁问题,城市出现大量工业遗留和遗弃场地。这些受污染的工业场地多存在较为严重的土壤、地表水和地下水污染;另外,工业污染场地的延迟再开发,会产生生活环境变差、就业机会减少、甚至社会不稳定因素增加等社会影响。所以,城市工业污染场地严重威胁着城市人居环境安全和公众健康,阻碍着城市建设和经济发展。面对工业污染场地目前存在的问题,国家及部分地方政府已针对污染场地的管理、修复及其再开发颁布了诸多文件和技术规范标准。然而,由于工业场地类型的多样性和环境管理学科的交叉性,中国城市工业污染场地的环境管理工作仍处于起步阶段,亟需完善。美国、英国和加拿大经过20~30年的发展已经在工业污染场地管理方面积累了丰富的经验,他们不仅在环境管理中体现了人体健康风险评估的理念,而且还立足本国实际出台了相关的法律法规,明确了污染场地的责任主体,实现了＂污染者付费＂的原则,同时还建立了各自的污染场地治理优先名录,实现了污染场地管理的信息化和网络化。本文鉴于对这些经验的比较分析,结合我国实际,就城市工业污染场地的环境管理提出了现阶段亟须解决的两大问题。首先,制定工业污染场地管理的专门法律,明确污染场地的责任主体。我国现有的与污染场地有关的国家法律法规,都比较笼统地提出了污染场地的利益相关方,缺乏具有可操作性的细则和威慑力的责任追究条款。对于我国这样地域辽阔、自然地理条件差异大、经济水平不均衡的国家来说,通过地方法律法规的建立明确污染场地的责任主体是一个重要的尝试。其次,构建污染场地健康风险评估系统。我国城市工业污染场地涉及诸多工业行业、污染类型繁多复杂。因此,在全国范围内对城市工业污染场地进行排查、建立优先污染场地名录是构建污染场地风险评估系统的重要内容。此外,我国现有的土壤质量标准和场地评估规范仍存在诸多缺陷,无法满足当前国家城市工业污染场地的管理需要。所以,完善场地评估的技术规范和相关标准将为污染场地风险评估系统的构建提供基础性保障。本文的论述和观点可为我国工业企业关停或搬迁遗留地的决策管理和污染场地管理体系的建立提供有意义的参考和借鉴。     

土壤原位修复技术研究与应用进展

土壤原位修复技术是指不经挖掘,直接在污染场地就地修复污染土壤的土壤修复技术,具有投资低,对周边环境影响小的特点,是土壤修复的研究热点。土壤原位修复技术主要有淋洗,气相抽提（SVE）,多相抽提（MPVE）,气相喷射（IAS）,生物降解,原位化学氧化（ISCO）,原位化学还原,污染物固定,植物修复等。淋洗法主要用于治理高渗透性土壤中的重金属和难挥发降解的有机物。土壤气相抽提和喷射技术适用于处理土壤中的易挥发污染物,并有常与加热技术,生物处理技术等联用,可以起到促进污染物挥发,增氧促分解的作用。多相抽提法主要用于治理存在大量非水相流体的污染场地,可将土壤中有机相污染物直接抽出。生物降解有生物好氧降解、生物厌氧降解、生物还原降解多种,降解方式由污染物种类和地质条件决定。化学方法可将污染物氧化或还原为低毒无毒物质,周期一般较短。固定污染物可以直接加入药剂反应生成沉淀,也可制造合适条件使微生物生成可沉淀重金属的离子。植物修复主要用于富集重金属,成本低廉,但富集了重金属的植物体的有效利用尚待进一步研究。土壤原位修复需要因地制宜,灵活结合工期、污染情况、地质条件、地面设施等,得出最经济实用的修复方法,并在辅助提高技术上展开更多研究,使原位修复技术更经济有效。     

两种改性剂对多氯联苯污染土壤协同热脱附影响研究

采用热脱附技术处理多氯联苯污染土壤已经成为了一种主要的场地修复方式。为提高热脱附效率,降低能耗,以典型电力电容器污染土壤为对象,采用2种改性剂(零价纳米铁和氢氧化钠)研究协同热脱附下多氯联苯的去除效率、分布特性及毒性当量。结果表明纳米铁和NaOH存在的条件下,有效提高了多氯联苯和毒性当量的去除效率,在较低温度下尤其显著,因此添加改性剂能够有效地促进热脱附过程。纳米铁的协同热脱附机理为显著强化了热脱附过程的传质传热,同时伴有一定的脱氯降解。NaOH的添加在较低温度下实现了较强的脱氯降解作用,加氢脱氯机理可用来解释协同热脱附过程中多氯联苯的脱氯反应过程。上述研究结果为多氯联苯污染土壤的场地修复提供理论基础。     

农田重金属污染原位钝化修复研究进展

污染土壤重金属原位钝化修复是通过向土壤中施加一些活性钝化修复材料,通过溶解沉淀、离子交换吸附、氧化还原、有机络合等反应来改变重金属在土壤中的赋存状态,降低土壤中重金属的有效浓度、迁移性和生物有效性。这种方法成本较低、操作简单、见效快且适合大面积推广,在重金属污染土壤修复中有着不可替代的作用。尤其对主要由污水灌溉、大气沉降等造成的农田土壤面源污染,一些具有吸附固定土壤中重金属离子特性的天然物质和工业副产品都可运用在实地的钝化修复中,且不同类型的钝化修复剂对重金属污染土壤的钝化修复效果各不相同。采用实验室评价和实地应用评价,一方面可以评估钝化修复材料对污染土壤中重金属离子的固定效率;另一方面可以评估钝化修复材料对土壤理化性状、养分状况和生物活性的影响。对重金属污染土壤原位钝化修复中不同来源的钝化剂进行了分类,目前广泛使用的钝化修复剂主要包括硅钙物质、含磷材料、有机物料、黏土矿物、金属及金属氧化物、生物碳及新型材料等,概述了它们各自对重金属污染土壤的钝化修复效果。从研究方法、评价指标、环境影响因子、钝化机制以及环境风险评价等方面分析了该领域的研究现状以及存在的主要问题,今后应重点关注钝化修复剂对土壤-作物系统的潜在环境风险以及钝化材料修复效果的田间长期稳定性评价。     

Spatial health risk assessment and hierarchical risk management for mercury in soils from a typical contaminated site,China

Due to rapid urbanization and the implementation of ecological civilization construction in China, many industrial factories have been closed or relocated. Therefore, numbers of contaminated sites were generated with contaminated soils which may pose a risk to receptors living nearby. This study presented a spatial health risk assessment and hierarchical risk management policy making for mercury (Hg) in soils from a typical contaminated site in the Hunan Province, central China. Compared with the second class value (0.3 mg/kg) of the Chinese Environmental Quality Standard for Soils, the mean concentrations of Hg in the three soil depths exceeded the second class value. The non-carcinogenic risk of Hg probably posed adverse health effects in 41, 30 and 36 % of the surface soil, the moderate soil and subsoil, respectively, under a sensitive land scenario. The non-carcinogenic risk temporarily posed no adverse health effects in most areas under an insensitive land scenario except for the area around sampling site S29. Spatially, the central, southwest and northeast parts of the contaminated land under a sensitive land scenario should be regarded as the priority regions. For non-carcinogenic effects, the exposure pathways that resulted in the higher levels of exposure risk were ingestion and inhalation of vapors, followed by dermal contact and inhalation of particles. A risk-based integrated risk management policy including the hierarchical risk control values for different soil depths and the calculated remediation earthwork was proposed with consideration of the cost-benefit effect for the related decision-makers.     

Engineering practice of mechanical soil aeration for the remediation of volatile organic compound-contaminated sites in China: Advantages and challenges

In recent years, many industrial enterprises located in the urban centers of China have been relocated owing to the rapid increase in urban development. At the sites abandoned by these enterprises, volatile organic compounds have frequently been detected, sometimes at high concentrations, particularly at sites abandoned by chemical manufacturing enterprises. With the redevelopment of sites and changes in land-use type associated with these sites, substantial amounts of contaminated soils now require remediation. Since China is a developing country, soil remediation warrants the usage of techniques that are suitable for addressing the unique challenges faced in this country. Land shortage is a common problem in China; the large numbers of contaminated sites, tight development schedules, and limited financial resources necessitate the development of cost-effective methods for land reclamation. Mechanical soil aeration is a simple, effective, and low-cost soil remediation technique that is particularly suitable for the remediation of large volatile organic compound-contaminated sites. Its effectiveness has been confirmed by conducting laboratory studies, pilot tests, and full-scale projects. This study reviews current engineering practice and developmental trends of mechanical soil aeration and analyzes the advantages and disadvantages of this technology for application in China as an emerging soil remediation market. The findings of this study might aid technology development in China, as well as assist other developing countries in the assessment and implementation of costeffective hazardous waste site soil remediation programs.

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Remediation of soil and groundwater contaminated with organic chemicals using stabilized nanoparticles: Lessons from the past two decades

▪ Overviewed evolution and environmental applications of stabilized nanoparticles. ▪ Reviewed theories on particle stabilization for enhanced reactivity/deliverability. ▪ Examined various in situ remediation technologies based on stabilized nanoparticles. ▪ Summarized knowledge on transport of stabilized nanoparticles in porous media. ▪ Identified key knowledge gaps and future research needs on stabilized nanoparticles. Due to improved soil deliverability and high reactivity, stabilized nanoparticles have been studied for nearly two decades for in situ remediation of soil and groundwater contaminated with organic pollutants. While large amounts of bench- and field-scale experimental data have demonstrated the potential of the innovative technology, extensive research results have also unveiled various merits and constraints associated different soil characteristics, types of nanoparticles and particle stabilization techniques. Overall, this work aims to critically overview the fundamental principles on particle stabilization, and the evolution and some recent developments of stabilized nanoparticles for degradation of organic contaminants in soil and groundwater. The specific objectives are to: 1) overview fundamental mechanisms in nanoparticle stabilization; 2) summarize key applications of stabilized nanoparticles for in situ remediation of soil and groundwater contaminated by legacy and emerging organic chemicals; 3) update the latest knowledge on the transport and fate of stabilized nanoparticles; 4) examine the merits and constraints of stabilized nanoparticles in environmental remediation applications; and 5) identify the knowledge gaps and future research needs pertaining to stabilized nanoparticles for remediation of contaminated soil and groundwater. Per instructions of this invited special issue, this review is focused on contributions from our group (one of the pioneers in the subject field), which, however, is supplemented by important relevant works by others. The knowledge gained is expected to further advance the science and technology in the environmental applications of stabilized nanoparticles.     

Enhanced electrokinetic remediation of chromium-contaminated soil using approaching anodes

As a new technology used for the cleaning of chromium-contaminated soil, worldwide interest in eletrokinetic (EK) remediation has grown considerably in recent times. However, owing to the fact that chromium exists as both cationic and anionic species in the soil, it is not an efficient method. This paper reports upon a study in which a process using approaching anodes (AAs) was used to enhance the removal efficiency of chromium by eletrokinetics. Two bench-scale experiments to remove chromium from contaminated soil were performed, one using a fixed anode (FA) and the other using AAs. In the AAs experiment, the anode moved toward the cathode by 7 cm every three days. After remediation, soil pH, total chromium, and fractionation of chromium in the soil were determined. The average removal efficiency of total chromium was 11.32% and 18.96% in the FA and AAs experiments, respectively. After remediation, acidic soil conditions throughout the soil were generated through the use of AAs, while 80% of the soil remained neutral or alkalic when using the FA approach. The acidic soil environment and high field intensity in the AAs experiment might have favored chromium desorption, dissolution and dissociation from the soil, plus the mobility of chromium in the soil was also enhanced. The results demonstrate that AAs used in the process of EK remediation can enhance the efficiency of chromium removal from soil.     

污染土壤的修复技术研究进展

分析了当前我国严峻的土壤环境状况，并从重金属和有机污染物两个方面，全面介绍了当前污染土壤的各种修复技术，包括物理化学修复方法、植物修复方法和微生物修复方法等；对各种方法的修复原理、已取得的研究进展、存在的优缺点及其将来的发展趋势进行了较全面的综述和展望。文章认为，污染土壤修复将是一项非常具有挑战性同时又是一项非常有前途的修复技术，将会对人类健康和经济可持续发展发挥重要作用。     

2种毒性评估方法对PAHs污染场地人体健康风险的比较研究

毒性评估是人体健康风险评价的重要部分,目前主要存在2种方法,一种基于PAHs相对于苯并[a]芘(BaP)的毒性当量因子,采用Ba P致癌斜率因子参数(方法 1),另一种直接采用各PAHs致癌斜率因子和非致癌参考剂量等参数(方法 2)。然而2种毒性评估方法得到的风险及修复量是否存在差异以及引起差异的原因等问题鲜有讨论。针对苏南某焦化厂PAHs污染土壤,采用分层土壤健康风险评价模型,对比了2种毒性评估方法确定的PAHs风险、修复目标污染物及土方量的差异,并对引起差异的关键因素进行探讨。结果表明:对于0.0~1.0 m表层土壤,方法 1和方法 2确定的致癌风险最大值分别1.48E-05和1.32E-05,均超过可接受致癌风险,修复土方量分别为27 846 m~3和28 667 m3,修复目标污染物均为Ba P和二苊烃(Acy)。对于1.0~3.0 m深层土壤,方法 1确定的致癌风险最大值为3.36E-08,低于可接受致癌风险,不需要修复;而方法 2确定的致癌风险最大值为3.73E-04,非致癌危害指数最大值为6.96E+01,分别超过可接受致癌风险和非致癌危害商,需要修复,修复目标污染物为萘(NaP),修复土方量为35 944 m~3。最终,方法 2确定的总修复土方量(64 611 m~3)为方法 1确定土方量(27 846 m~3)的2.45倍,而这种差异主要是由于方法 1低估了深层土壤中高挥发性PAH单体尤其是NaP的风险所致。因此,从保守角度建议采用方法 2进行PAHs风险评价。     

Full scale amendment of a contaminated wood impregnation site with iron water treatment residues

Iron water treatment residues are a free by-product with high concentration of iron oxides Iron water treatment residues has a large potential for arsenic sorption Soils are highly contaminated by arsenic at wood preservation sites Iron water treatment residues were added to hot spots contaminated with arsenic The addition led to significant decrease in leaching of arsenic from the contaminated soil Iron water treatment residues (Fe-WTR) are a free by-product of the treatment of drinking water with high concentration of iron oxides and potential for arsenic sorption. This paper aims at applying Fe-WTR to a contaminated site, measuring the reduction in contaminant leaching, and discussing the design of delivery and mixing strategy for soil stabilization at field scale and present a cost-effective method of soil mixing by common contractor machinery. Soil contaminated by As, Cr, and Cu at an abandoned wood impregnation site was amended with 0.22% (dw) Fe-WTR. To evaluate the full scale amendment a 100 m² test site and a control site (without amendment) were monitored for 14 months. Also soil analysis of Fe to evaluate the degree of soil and Fe-WTR mixing was done. Stabilization with Fe-WTR had a significant effect on leachable contaminants, reducing pore water As by 93%, Cu by 91% and Cr by 95% in the upper samplers. Dosage and mixing of Fe-WTR in the soil proved to be difficult in the deeper part of the field, and pore water concentrations of arsenic was generally higher. Despite water logged conditions no increase in dissolved iron or arsenic was observed in the amended soil. Our field scale amendment of contaminated soil was overall successful in decreasing leaching of As, Cr and Cu. With minor improvements in the mixing and delivery strategy, this stabilization method is suggested for use in cases, where leaching of Cu, Cr and As constitutes a risk for groundwater and freshwater.     

Ökotoxikologische und humantoxikologische Risikobewertung PAK-belasteter Böden vor und nach biologischer Behandlung

The goal of the present work is to assess the adverse effects of soil bound polycyclic aromatic hydrocarbons (PAH) which remain in soils after biological remediation. We focus on risk assessment for mammalian species with respect to the oral uptake of contaminated soil particles and compare the results of a biomarker test with those of an ecotoxicological assay, the bioluminescence inhibition test withVibrio fischeri. As a biomarker effect in mammals, we determined the liver microsomal cytochrome P450 enzyme CYP1A1 which is induced by PAH in exposed rats. After biological soil treatment, different amounts of PAH remain in the soil depending on the soil properties and initial pollutant composition. Particularly, higher condensated PAH resists biological treatment due to its hydrophobicity. In addition, high amounts of organic carbon in the soils affect remediation efficiency. In the bioluminescence inhibition test, eluates of all biologically treated soils studied do not reveal any or only low inhibitory effects. In contrast, the oral uptake of biologically treated contaminated soils leads to induction levels for CYP1A1 similar to those in the untreated samples. A good correlation is obtained between CYP1A1 levels and the amount of 5 and 6-ring PAH in the soil samples. The main result is that the remediation efficiency determined by the luminescence test is not reflected by the biomarker test, a finding which indicates the high bioavailability of residual PAH in soils. Consequently, new criteria for human risk assessment can be delineated.     

污染场地土壤重金属空间异常值识别及其点源效应的分离

由点源污染导致的土壤重金属空间异常值的分布及点源效应的大小将影响场地风险评估和修复方案的制定,进而影响场地的环境管理.以某典型重金属污染场地为研究区域,以表层土壤Cd含量为研究对象,引入稳健变异函数模型,并筛选出合适的变异函数模型,结合平尾化方法对表层土壤Cd含量空间异常值进行识别和处理,并有效地分离出点源效应.研究表明：研究区表层土壤Cd含量空间变异大且存在明显的空间异常值;CressieHawkins稳健变异函数更适用于对研究区表层土壤Cd含量半方差函数的估计,采用稳健变异函数和平尾化方法能够有效地识别空间异常值和分离点源效应,空间异常值主要分布在受人为活动影响较大的区块;由于准点过程导致的变异较大,分离出的点源效应解释了异常值点位表层土壤Cd含量的大部分.     

Stabilization-based soil remediation should consider long-term challenges

Soil remediation is of increasing importance globally, especially in developing countries. Among available remediation options, stabilization, which aims to immobilize contaminants within soil, has considerable advantages, including that it is cost-effective, versatile, sustainable, rapid, and often results in less secondary pollution. However, there are emerging challenges regarding the long-term performance of the technology, which may be affected by a range of environmental factors. These challenges stem from a research gap regarding the development of accurate, quantitative laboratory simulations of long-term conditions, whereby laboratory accelerated aging methods could be normalized to real field conditions. Therefore, field trials coupled with long-term monitoring are critical to further verify conditions under which stabilization is effective. Sustainability is also an important factor affecting the long-term stability of site remediation. It is hence important to consider these challenges to develop an optimized application of stabilization technology in soil remediation.     

不同国家基于生态风险的土壤筛选值研究及启示

本文介绍了土壤生态筛选值的定义以及国外一些国家在污染土壤生态风险评估领域的相关土壤筛选值。由于地理生态、社会文化、行政法规以及标准制定的科学基础等差异使各国基于生态风险的土壤筛选值的制定方法各有特色,导致各国基于生态风险的土壤筛选值名称和筛选值之间存在较大差异。我国的生态风险评价研究起步较晚,目前还没有国家权威机构发布的诸如土壤生态筛选值、生态风险评价技术导则等文件。本文就目前国外一些权威机构推出的并得到广泛认可的相关标准、方法做简要介绍,就国际上不同国家的土壤生态筛选值的制定方法、理论体系、使用策略等进行详细描述,为我国制定相关筛选值的方法体系提供参考,旨在推动我国基于生态风险的污染土壤筛选值的建立和生态风险评估研究。     

土著微生物原位修复石油污染土壤试验研究

利用当地土著微生物优势菌群,辅以物理和化学的方法,结合当地地质微环境特点,开展了陕北某油井旁的石油污染黄土土壤修复研究。设置两个试验区、一个空白区和一个对照区,在两个试验区中分别加入3%的土著优势菌群制剂,选择优化出的土著菌群经鉴定,主要有：假单胞菌属（Pseudomonas）、微球菌属（Micrococcus）、放线菌属（Actinomayces）、真菌类的青霉属（Penicillium）、曲霉属（Aspergillus）等。试验结果显示：土著优势菌剂一般需要3-7d的延滞期（lag phase）,然后进入对数期（logarithmic phase）;两个试验区土壤中人为添加石油含量分别为1542、1886mg·kg^-1时,经过11-32d原位土著优势微生物菌剂的修复,土壤中的石油污染物降解率可达69.52%-88.11%,而对照区土壤中人为添加的石油含量变化不大,降解率基本在10%以内,说明在自然条件下土壤中石油降解是缓慢的。谷糠黍糠、麦麸两种添加剂对优化菌液的修复效果的作用基本相同。试验过程中对土壤温度、水分、氧和营养物质等影响因素进行了调控,起到了良好的作用。     

Microwave enhanced stabilization of copper in artificially contaminated soil

Microwave processing was used to stabilize copper ions in soil samples. Its effects on the stabilization efficiency were studied as a function of additive, microwave power, process time, and reaction atmosphere. The stabilization efficiency of the microwave process was evaluated based on the results of the toxicity characteristic leaching procedure (TCLP) test. The results showed that the optimal experimental condition contained a 700W microwave power, 20 min process time and 3 iron wires as the additive, and that the highest stabilization efficiency level was more than 70%. In addition, the different reaction atmospheres showed no apparent effect on the stabilization efficiency of copper in the artificially contaminated soil. According to the result of the Tessier sequential extraction, the partial species of copper in the contaminated soil was deduced to transform from unstable species to stable states after the microwave process.     

重金属污染土壤属性区间识别模型的赋权分析

土壤重金属污染评价为土壤重金属污染的及时防范和综合治理提供重要的理论依据。文章在属性区间识别理论的基础上,构建土壤重金属污染评价的属性区间识别模型：选取土壤重金属污染中普遍存在的Hg、Cd、As、Pb、Cu、Zn作为评价指标,采用均化系数将各评价指标的属性测度区间转化为综合属性测度;为避免主观因素,利用主成分分析法、熵权法、CRITIC法对各评价指标进行3次客观赋权;最后根据置信度准则和分级标准进行土壤重金属污染的综合评价。对3种赋权法得到的权重和评价结果进行比较,表明：属性识别模型在土壤重金属污染评价中适用且有利于评价结果准确性的提高;3种客观赋权法算得的权重合理,且其优异程度为主成分分析法〈熵权法〈CRITIC法。     

沉积物质量综合评价及应用证据权重法的案例分析

水体沉积物是水生生态系统重要的组成部分,沉积物污染将影响整个水生生态系统,因此有必要构建科学全面的水体沉积物质量评价方法,为环境污染修复与监管提供科学依据。已有文献报道了多种沉积物质量评价方法。其中,证据权重法通过对不同的证据进行测定与整合,弥补了传统评价方法的不足,可以对沉积物质量进行科学全面的评价。本文对证据权重法中化学分析、生物毒性和底栖生物群落结构3种证据的测量方法、赋权方法、证据整合与信息解译方法进行了系统评述,并以淡水河为例介绍了用多目标决策理想点法(TOPSIS)整合数据进行沉积物质量综合评价的方法。     

An emerging market for groundwater remediation in China: Policies,statistics, and future outlook

There is a rapidly emerging and potentially huge market for the remediation of contaminated groundwater in China. The Chinese government published a Water Action Plan in April 2015, a Soil Action Plan in May 2016, and a draft Soil Pollution Prevention and Control Law in June 2017. All of these new policies and regulations put pressures on local governments and contaminated site owners, obliging them to conduct site investigation and to cleanup contaminated groundwater. The Chinese population in northern regions heavily depend on groundwater, with nearly 70% of water supply coming from aquifer sources in the Beijing-Tianjin-Hebei region. However, poor groundwater quality due to natural geochemical background and anthropogeic pollution is a serious concern, with poor or very poor quality water observed in nearly 80% of groundwater monitoring wells in 17 northern provinces. Shallow groundwater in many areas has been contaminated by toxic pollutants such as heavy metals and chlorinated organic compounds. There is an urgent need to better understand the situation and to conduct groundwater remediation at contaminated sites. The Chinese government is investing heavily in the research and development for groundwater remediation, which is expected to greatly add to the quality and quantity of groundwater remediation projects in the near future.