六六六在典型污染场地中空间分布研究

在受某六六六（HCH）生产企业污染的场地上采集土壤样品,分析和研究了土壤中六六六的污染水平和污染分布趋势。结果表明,六六六的浓度范围是0．34～2287．6mg·kg^-1,六六六污染主要集中在-1m土层,平均浓度高达467．75mg·kg^-1。在-3m和-5m土层中污染中心位置与-1m层土壤保持一致。通过Kriging法插值画出-1、-3、-5m土层等值线图,可清晰地看出六六六的分布趋势。六六六浓度随土壤深度增加迅速降低。然而,在-5m土层由于土壤类型为淤泥质粘土,六六六浓度相对于-3m土壤反而升高,该层的平均浓度为89．86mg·kg^-1。纵观整个污染场地六六六的污染分布情况,在地下水作用下污染物浓度向东南方向扩散,且六六六在垂直方向的迁移和残留浓度与土壤有机质含量有一定的相关性。     

场地土壤-地下水污染物多介质界面过程与调控研究进展与展望

近年来，中国重点行业场地土壤-地下水重金属和有机污染物污染十分突出，已成为土壤环境治理修复亟待解决的重要问题之一。多介质界面是控制场地系统复合污染物环境行为的关键。因此，开展场地土壤与地下水污染物多介质界面过程与调控机制研究，对于认知场地污染成因与治理修复具有重要的科学意义。系统分析了国内外场地土壤-地下水污染物多介质界面过程与调控研究进展与发展趋势，指出了目前该研究领域中存在的科学与技术问题，提出了我国场地土壤-地下水污染物多介质界面过程与调控原理的研究思路与重点方向，以推动我国场地土壤和地下水环境科学理论与技术的发展。     

污染场地研究现状与发展趋势：基于知识图谱的分析

为了解国内外污染场地相关研究状况,利用知识图谱工具VOSviewer、CiteSpace与Hist Cite对Web of Science核心合集数据库中发文的主要国家(地区)与机构、主要发文期刊、主要研究学者、重要文献和研究热点及其变化趋势等进行了计量分析。结果表明:(1)污染场地的研究涉及多个国家之间相互合作,发文机构中中国科学院、橡树岭国家实验室、滑铁卢大学、中国科学院大学与亥姆霍兹环境研究中心在该研究领域合作广泛。中国于近五年发文量超过美国,成为该领域发文最多的国家。(2)污染场地研究的主要发文期刊有Science of the Total Environment、Chemosphere、Environmental ScienceTechnology、Environmental Science and Pollution Research等,Naidu Ravi、Huang Guohe、Megharaj Mallavarapu等是该领域发文较多的研究学者。污染场地前十(TOP10)的重要文献中,生物修复相关内容中占据了较高比例。(3)关键词聚类网络主要可分为污染场地生物毒理研究、土壤重金属及修复技术、污染物环境行为及水体修复、有机污染物生物修复等4类。(4)文献计量的结果分析表明土壤与地下水均为污染场地有害物质重要承载体,污染场地中土壤和地下水具有一体性,如果忽视了对地下水中污染的修复,则可能会导致场地的二次污染。重金属与多环芳烃是污染场地重点关注的污染物,我国目前重金属污染防治工作依然不容乐观,需要进一步加强和落实相应工作。寻求高效绿色的修复技术仍是解决污染场地问题的一个重点,提升微生物修复技术在有机污染场地修复中的应用价值,具有重要意义。     

我国南方某典型有机化工污染场地土壤与地下水健康风险评估

以某典型有机化工污染场地为例,开展了多层次健康风险评估,推算了土壤与地下水的筛选值和修复目标值,确定了污染修复范围及修复量。结果表明:土壤与地下水均存在不同程度的有机污染,关注污染物氯仿、四氯化碳、苯、氯苯在0~1 m的土壤修复目标值分别为0.03、0.05、0.35、6.51 mg/kg;1~3 m的土壤修复目标值分别为0.07、0.30、0.90、13.49 mg/kg;3~5 m的土壤修复目标值分别0.14、0.46、1.69、20.45 mg/kg;5~9 m的土壤修复目标值分别为0.25、0.79、2.99、36.27 mg/kg,地下水修复目标值分别为0.32、0.51、3.43、21.80 mg/L。土壤中氯仿、四氯化碳、氯苯的超标点位随深度增加而增多,其风险或危害随之增大;地下水污染区域集中,GW6号点位4种污染物均超标,其中氯仿污染最严重,致癌风险高达1.11×10–3,非致癌危害商为9.8。     

基于知识图谱分析的污染场地研究现状与发展趋势

为了解国内外污染场地相关研究状况,利用知识图谱工具VOSviewer、CiteSpace与HistCite对Web of Science核心合集数据库中发文的主要国家（地区）与机构、主要发文期刊、主要研究学者、重要文献和研究热点及其变化趋势等进行了计量分析。结果表明：（1）污染场地的研究涉及多个国家之间相互合作,发文机构中中国科学院、橡树岭国家实验室、滑铁卢大学、中国科学院大学与亥姆霍兹环境研究中心在该研究领域合作广泛。中国于近五年发文量超过美国,成为该领域发文最多的国家。（2）污染场地研究的主要发文期刊有Science of the Total Environment、Chemosphere、Environmental Science & Technology、Environmental Science and Pollution Research等,Naidu Ravi、Huang Guohe、Megharaj Mallavarapu等是该领域发文较多的研究学者。污染场地前十（TOP 10）的重要文献中,生物修复相关内容中占据了较高比例。（3）关键词聚类网络主要可分为污染场地生物毒理研究、土壤重金属及修复技术、污染物环境行为及水体修复、有机污染物生物修复等4类。（4）文献计量的结果分析表明土壤与地下水均为污染场地有害物质重要承载体,污染场地中土壤和地下水具有一体性,如果忽视了对地下水中污染的修复,则可能会导致场地的二次污染。重金属与多环芳烃是污染场地重点关注的污染物,我国目前重金属污染防治工作依然不容乐观,需要进一步加强和落实相应工作。寻求高效绿色的修复技术仍是解决污染场地问题的一个重点,提升微生物修复技术在有机污染场地修复中的应用价值,具有重要意义。     

基于保护水环境的场地地下水风险评估模拟应用研究

以江苏省某溶剂化工场地为例，利用英国污染地块水文地质风险评估模型研究了该场地地下水污染物对场地内及周边水环境的影响。比较了稳态和非稳态地下水溶质迁移模型(Ogata Banks、Domenico、Time variant Domenico)对污染物在自然衰减条件下从污染源向场地边界迁移过程模拟。结果表明：该场地的地下水中苯、乙苯、氯苯、1,2-二氯苯、1,4-二氯苯、氯仿超过了地下水质量Ⅲ类标准，但场地内污染物对场地边界地下水的潜在环境风险基本可以忽略。Ogata Banks与Domenico模型对于污染物在含水层的自然衰减下的迁移模拟表明污染物在30 m内的迁移过程中浓度下降较快，在30 m外的迁移过程中污染物的浓度较低且衰减不明显。Domenico模型计算较为简洁，在风险评估中具有较强的适用性；敏感性分析表明合规点至污染源距离x、含水层容重ρ、含水层孔隙度n、有机碳含量f_oc、有机碳分配系数K_oc、水力传导系数K、水力梯度i均影响污染物在含水层的自然衰减迁移过程，通过精细化水文地质调查获取上述参数将有助于提高风险评估结果的精确度。     

我国有机氯农药场地污染现状与修复技术研究进展

有机氯农药是一类毒性大、残留期长,较难处理的一类化学品。有机氯农药生产企业搬迁遗留的污染场地是我国城市发展进程中面临的新环境问题。本文分析了我国有机氯农药污染场地中主要污染物种类及其残留特征,介绍了欧美发达国家应用于此类污染场地的修复技术,着重评述了我国有机氯农药污染场地的修复技术研发与应用情况,并就今后该类场地修复发展提出建议。     

基于Web of Science数据库的污染场地可持续修复领域的文献计量分析

实现碳达峰、碳中和目标是我国经济社会深刻的系统性变革,“双碳”目标的提出将对我国土壤污染修复领域产生重要影响,并促进研发更多符合绿色可持续修复的新技术和新产品。为了解污染场地可持续修复领域的研究进展和发展动态,采用CiteSpace和VOSviewer科学图谱绘制软件对Web of Science数据库核心集中2000 ~ 2020年污染场地可持续修复领域的相关文献进行了计量分析,通过合作、共现和共被引等网络分析,探索该领域的研究热点和前沿趋势。结果表明:1）近年来世界范围内该领域发文数量总体呈增长趋势;2）该领域发文量前三的国家是美国、英国和中国;3）该领域的主要发文机构有清华大学、剑桥大学和中国科学院;4）Hou、Norrman和Rosen是该领域发文数量较多的研究人员;5）载文量较多的期刊有Science of the Total Environment、Journal of Environmental Management和Journal of Cleaner Production;6）目前污染场地多采用异位修复的方式修复,原位修复技术及各类耦合修复技术的研究将会增多;7）对土壤修复的可持续研究逐渐增多,地下水修复的可持续研究较少。制定科学合理的具有中国特色的污染场地可持续修复方法势在必行;降低污染修复全过程的环境影响和二次污染是响应碳减排号召的重要过程,环境友好型材料研发、绿色可持续修复技术的实施是污染场地可持续修复领域的重要措施。     

土壤苯并[a]芘多次叠加污染对蚯蚓体腔细胞抗氧化酶的毒性效应

苯并[a]芘(B[a]P)是具有典型"三致"效应的持久性有机污染物,在土壤中逐步累积,对土壤环境质量造成潜在的威胁。一次污染条件下,B[a]P进入土壤的过程与较低剂量逐步累积的污染过程存在一定差异,在一定程度上会高估B[a]P的环境风险。本试验采用一次污染和多次累积污染2种方法,模拟污染物在土壤中逐步累积的过程,研究土壤B[a]P叠加污染的有效性特征及其在蚯蚓(Eisenia foetida)体内的富集规律,分析蚯蚓体腔细胞超氧化物歧化酶(SOD)和过氧化物酶(POD)的毒性效应。结果表明,随着土壤中B[a]P培养时间的延长,B[a]P有效含量、蚯蚓富集量和蚯蚓体腔细胞SOD、POD活性均呈逐渐下降的趋势。在多次叠加污染和一次污染条件下,土壤B[a]P有效含量在培养前期(1~28 d)下降速率分别为2.37μg·kg-1·d-1和3.35μg·kg-1·d-1,后期(28~56 d)下降速率逐步减缓为0.24μg·kg-1·d-1和0.53μg·kg-1·d-1;蚯蚓体内B[a]P富集量在培养前期(1~28 d)下降速率分别为6.94μg·kg-1·d-1和14.84μg·kg-1·d-1,后期(28~56 d)逐步减缓为0.73μg·kg-1·d-1和1.64μg·kg-1·d-1。蚯蚓体内B[a]P富集量与土壤B[a]P有效含量(Tenax吸附提取量)之间呈极显著正相关(P0.01),相关系数(R2)为0.914 7。蚯蚓体腔细胞SOD和POD活性与土壤B[a]P有效含量和蚯蚓体内B[a]P富集量之间分别呈极显著正相关(P0.01),相关系数(R2)分别为0.754 3(SOD)、0.829 6(POD)和0.704 0(SOD)、0.727 1(POD)。在叠加污染条件下,土壤B[a]P有效含量比一次污染低17.1%~38.6%(P0.05),蚯蚓富集量比一次污染低22.6%~46.8%(P0.05),蚯蚓体腔细胞SOD和POD活性分别为一次污染酶活性的49.6%~82.7%和75.5%~109.6%,差异达到显著水平(P0.05)。这表明土壤B[a]P多次叠加污染对蚯蚓体腔细胞的毒性效应低于一次污染。     

工业遗留场地复合型污染分层健康风险评估研究

以某典型有机物-重金属复合型污染场地为研究对象,根据该场地水文地质特征将土层划分为回填土(0~4.1 m)、粉质黏土(4.1~6.5 m)、粉土(6.5~8.5 m)和粉砂(8.5~13.8 m)等4层,运用HERA软件分别进行健康风险评估,推算了土壤和地下水的风险值及修复目标值,并以此划分修复范围和确定修复技术。结果表明,土壤中存在严重的有机污染(苯和甲苯)和重金属(Cr(Ⅵ))污染,苯的最大致癌风险为0.000 155,甲苯的最大非致癌危害商为2.14;Cr(Ⅵ)在下层土壤中不存在暴露途径危害人体健康,而仅在表层回填土中存在致癌和非致癌危害商(0.014 2和97.6);地下水中关注污染物健康风险在可接受范围内;苯、甲苯在各土层中的修复目标值分别为:回填土层0.434、708 mg/kg;粉质黏土层0.807、2 460 mg/kg;粉土层1.42、4 440 mg/kg;粉砂层2.51、8 140 mg/kg;Cr(Ⅵ)仅在回填土层计算出修复目标值为0.251 mg/kg。苯、甲苯等挥发性有机物分层修复目标值随土层深度增加而变大,Cr(Ⅵ)等重金属修复目标值不遵循这个规律,因此,分层健康风险评估更适用于挥发性有机物健康风险评价。     

An Empirical Model for Estimating Remediation Costs at Contaminated Sites

A model for estimating the remediation costs at contaminated sites is developed, in which the predictor variable is a composite of surface, subsurface, and contaminant risk factors. Calibration of the model is performed at 83 sites in an urbanized watershed with diverse surface geology in southeastern Michigan. These test sites exhibited different extents of contamination, including some where only soil was contaminated, and others where soil and groundwater were contaminated. The model was then applied to 79 sites with multiple contamination extents within different watersheds in North America, Europe, Australia, and Africa. The results indicate a very high correlation between the estimated and actual remediation costs at these sites. This model thus has the potential for providing reliable estimates of remediation costs across a broad array of soil and groundwater contamination scenarios, including dense nonaqueous phase liquid (DNAPL) contamination in sandy soil and lead in clay soil.     

On Morphometric Properties of DNAPL Sources: Relating Architecture to Mass Reduction

The fundamental step in the identification of the most appropriate strategy for the remediation of sites contaminated with dense nonaqueous phase liquids (DNAPLs) is a comprehensive characterization of the contaminated source region as the morphology of DNAPL strongly governs the mass transfer processes. The influence of DNAPL distribution geometry and groundwater flow velocity on mass reduction was explored through the evaluation of a series of laboratory studies conducted in a two-dimensional tank under different hydrodynamic conditions. An image analysis procedure was used to determine the distribution of DNAPL saturation and the morphology of the contaminated region. Experimental observations revealed a dependence of mass transfer rate on the aqueous phase velocity under high flow regimes, whereas the mass transfer rate was controlled mainly by morphometric indexes under low velocity flow conditions. Experimental results indicate that higher mass reduction and contaminant fluxes are obtained at low saturation values. The mass flux emanating from an elongated source aligned perpendicularly to the direction of water flow is greater due to a higher DNAPL?Cwater contact surface in comparison to a lower mass flux from horizontal pools with high saturation. These aspects should be considered in an inverse modeling technique for locating the source zone and also in all remediation approaches based on an increase in water circulation through a contaminated zone (i.e., pump and treat).     

Risks due to groundwater contamination at a plutonium processing facility

The specter of contaminated groundwater looms over industrialized, suburban, and rural areas. The sources of groundwater contamination are many and the contaminants numerous. Historical waste disposal practices pose the greatest threat to groundwater in the United States. Common solvents such as trichloroethylene, tetrachloroethane, benzene, and carbon tetrachloride have been found in widespread areas. For this study, a risk assessment is performed using a multimedia environmental transport model to estimate public risk from a contaminated groundwater plume. From 1955 to 1973, a crib above the groundwater plume was used for the disposal of plutonium processing waste. The plume contains chemical and radioactive wastes that could pose a health threat to people living in the vicinity of the site. Remedial designs are selected for remediating the different contaminants in the groundwater plume through a multiple phase treatment process. This study evaluates: baseline health risks to the public, health risk reduction to the public as a result of the remedial activities, health risk to the workers directly involved in cleaning up the site, and costs associated with each remedial activity.     

Simulation of chromium transport in the unsaturated zone for predicting contaminant entries into the groundwater

Heavy metal contaminations in the top‐soil layers can impose serious threats to groundwater quality. A seepage water prognosis of probable future contaminant entries at the groundwater surface has to take into account the emission characteristics of the source zone and the reactive transport of the contaminated leachate through the unsaturated zone. Here, a possible approach is presented, exemplarily for a site contaminated with chromium, encompassing batch elution experiments, unsaturated soil column leaching experiments with flow interruption, soil monolith lysimeter experiments, and numerical modeling of non‐equilibrium solute transport. The prognosis provides a long‐term prediction of Cr concentrations at the groundwater surface. It must be emphasized, that the modeling results are uncertain, because several of the parameters in the simulations can be determined only with significant errors. Additionally, the approach is not applicable routinely for every hazardous waste site. Our study reveals, however, that reactive contaminants can possibly reach the groundwater at hazardous concentrations within very short time.     

An integrative method to quantify contaminant fluxes in the groundwater of urban areas

Background, Aims, and Scope  Groundwater in urban areas is often contaminated and emission sources can be located close to groundwater wells. The delineation of contaminant plumes is difficult because of the various potential emission sources. Thus, detection, quantification and remediation of contaminated sites in a city need more integrative approaches. Methods  A method has been developed which allows quantification of mass fluxes of contaminants in groundwater between control planes. Budget zones along the flow path are defined to calculate a contaminant balance and to quantitatively reveal input areas. Concentrations and water budgets are used to calculate mass balances for each contaminant. The city of Darmstadt (Germany) was chosen to evaluate the method. Results  The groundwater monitoring wells (GMWs) upstream of the city showed anthropogenically superposed background values for all naturally occurring inorganic species. The contaminant concentrations increased in the city (probably influenced by road traffic, gas stations, leaking sewers, etc.). Downstream from the city, concentrations usually decreased. Organic compounds typical for urban environments, such as polycyclic aromatic hydrocarbons (PAH), locally exceeded drinking water regulations. In GMWs with high concentrations of organic contaminants in the city or downstream from industrial areas, a significant increase in Fe²⁺ and Mn²⁺ could be observed, in some cases coinciding with a decrease in NO₃, SO₄ and an increase in NH₄. Discussion  For typical urban contaminants, a positive budget was calculated in several zones, which shows that emissions from urban sources are reaching the groundwater. Negative budgets can be mainly explained with diving plumes and degradation. The input calculated from the individual budget zones is usually higher than the input estimated from urban emissions. Differences between the calculated and the estimated input can be explained with additional sources or (bio)degradation processes. Conclusions  It was confirmed that high concentrations of contaminants do not necessarily correlate with high fluxes. Integrative approaches can reveal areas of high contaminant mass input. The results obtained with the new method are plausible compared to the land use and the estimated urban input. The concentration pattern of Fe²⁺, Mn²⁺, SO₄ and NO₃ is partly due to natural processes, triggered by the degradation of organic matter and organic contaminants. Recommendations  Since this method includes mass balances and flux calculations, avoiding an overestimation of single point contaminant concentration, it is recommended to use this approach to quantify groundwater contamination in cities. Further research is focusing on the role of urban soils as natural reservoirs for the input of contaminants.     

Behaviour and assessment of bioavailability of organic contaminants in soil: relevance for risk assessment and remediation

Abstract. Soils contaminated with organic chemicals are now widespread in industrialized and developing countries, and the risk assessment and remediation of such contaminated sites is a priority. However, containment and remediation strategies are complicated in many cases by the range of contaminants present and the historical nature of the contamination. Research has increased our understanding of the behaviour of organic contaminants in soil and the factors that control their behaviour. There is a fundamental need to understand and, where possible, quantify the bioavailable fraction as well as the total concentration of contaminant present in soil: the bioavailable fraction is key to toxicity or biodegradation. To quantify these fractions, a large number of techniques have been employed, ranging from organic and aqueous based solvent extractions to the use of biota. Many studies have been carried out investigating the use of chemical techniques to describe bioavailability, which could be used in the assessment and remediation of contaminated land. The aim of this review is to consider the behaviour of organic contaminants in soil, highlighting issues of bioavailability, and then to discuss the relevance of the various methods for assessing risk and potential remediation of organic contaminants in soil.     

利用表面活性剂强化去除土壤中NAPLs的研究进展

该文评述了近年来国内外利用表面活性剂去除土-水系统中非水相流体(NAPLs)的研究进展，重点讨论了其作用机理和主要影响因素。大量研究表明，表面活性剂能促进NAPLs从土壤颗粒中解吸，并通过增溶和增流作用改善NAPLs在土壤中的溶解和迁移能力，进而提高抽出处理法的去除效率。同时，表面活性剂对NAPLs的生物降解也有一定影响。表面活性剂对NAPLs去除效率与其种类和投加浓度、土壤异质性、电解质和温度等因素有关。     

基于AHP筛选的有机污染土联合修复技术案例研究

为了研究联合修复技术在有机物污染场地中的筛选方法以及修复效果，以山西某搬迁遗留场地土壤修复工程为案例，本文提出了采用层次分析法（AHP）对常用的物理、化学、生物修复技术方法进行优选，最终确定“常温解吸+异位热脱附+填埋场覆土利用+水泥窑协同处置”的新联合修复模式，并且研究了该联合修复模式的处理效果及其对环境造成的影响。结果表明，AHP可用于有机污染场地修复最佳方案的筛选；采用该联合修复模式费用低、效果良好且未对周围环境造成影响。可见该联合修复模式能够有效地处理此类型场地污染土体。该修复模式的成功实施为类似污染场地土壤修复项目提供了借鉴和参考价值，并在一定程度上控制了土壤资源的流失。