氯代挥发性有机物（VOCs）氯同位素测试技术及其在地下水污染中的应用研究进展

在有机氯污染的研究中,氯同位素（³⁷Cl）的应用能够在原子水平上识别污染源并研究污染机理,为更加有效地研究地下水的有机污染提供了有利的工具。综述了8种氯代VOCs氯同位素的测试方法与技术,论述了氯代VOCs氯同位素在识别地下水污染源、监测有机污染物的降解过程、检验防治措施的修复效果、鉴别氯代VOCs的生产厂商、示踪氯代VOCs在土壤和水体中的迁移和混合过程等方面的应用,认为应尽快在国内研制先进的测试流程,开展有机氯同位素分馏机理的研究,加强应用C和Cl同位素技术对氯代VOCs污染和检测修复效果的研究。     

某石油化工场地土层挥发性有机物的污染特征

在调查华北平原一个污染年限超过35年的石油化工场地时,采用便携式仪器土层测气方法,快速、准确地测定了场地内40多个钻孔不同深度土层中挥发性有机物(VOCs)的浓度。基于对场地地质水文地质条件的认识,以及通过对大量数据的分析对比和应用空间变异分析方法,得出了对场地土层介质中VOCs污染特征的如下认识:(1)土层VOCs浓度的垂向变化可概括为污染源淋滤型、包气带扩散污染型、地下水波动带污染型和混合污染型四种污染类型;(2)在包气带砂土层和粉土层中,VOCs的扩散规律可近似用指数模型描述;(3)包气带土层中VOCs优先积聚在渗透性强的砂性土层中,砂土层中VOCs浓度是粉土层中VOCs浓度的1.5～12倍,平均3.76倍;(4)土层VOCs浓度的水平变异性表现为包气带土层的变异性要比地下水波动带土层大,且水平变异性能在25m尺度内得到充分显示;而土层VOCs浓度的垂向变异性随地而异,变化复杂,很难用统一的一个量化尺度来表征。本文对这一典型污染场地的剖析,有助于从事污染场地调查人员认识我国华北平原石油化工类场地的污染特征,并为调查与治理类似污染场地提供技术依据。     

化学氧化技术异位处理地下水非水相有机污染物中试研究

选取某农药厂旧厂区为试验场地,考察化学氧化技术异位处理地下水非水相有机污染物的运行效果。基于小试研究,确定高锰酸钾、高铁酸钾、芬顿试剂以及次氯酸钠4种氧化剂在中试试验中的适宜投加量。中试结果表明,当进水流量为1.0 m^3/h时,不同氧化剂对于常规水质指标及特征有机污染物的去除效果存在差异性。总体而言,四种氧化剂对于中长链石油烃类污染物(C10-C36)的去除率可达20%~70%,但对氯代烷烃类污染物的去除效果低于20%;高铁酸钾和次氯酸钠分别对于苯酚类和多环芳烃类污染物的去除效果较好(70%~100%);芬顿试剂对各类污染物均有显著氧化效果,其中对于短链石油烃(C6-C9,去除率20%~40%)、苯系物(去除率40%~90%)的去除效果高于其他三种氧化剂。研究不同氧化剂对于多组分有机污染地下水的处理效果,为将化学氧化技术应用于此类污染场地提供了理论和技术支持。     

某废弃煤矿有机污染场地地下水修复治理中试研究

某废弃煤矿竖井经倾倒有机废液,导致环境污染事件,造成巷道及采空区内地下水污染。本文结合场地实际情况,选取倾倒竖井(事故井)及周边区域为中试区域,采用“抽出处理+原位氧化循环”两阶段联合修复技术对污染场地开展中试研究。本文介绍了场地污染概况、地下水修复中试方案设计和实施,以及对修复效果进行评价。结果表明,中试处理后地下水中COD和二氯甲烷最高去除率分别为97.88%和99.74%。中试试验表明, “抽出处理+原位氧化循环”两阶段修复技术,对处理矿区内巷道及采空区等复杂地层结构下深层地下水中有机污染物具有较好的去除效果,可以结合现场实际情形对整个污染场区进行规模应用。     

某石化污染场地含水层自然降解BTEX能力评估

地下水污染问题是国家关注的重要环境问题之一,监测与评估含水层自然降解污染物能力是防治地下水污染的基本手段,也是国外地下水中修复技术研究热点课题。以华北平原某石油化工类场地为案例,通过调查场地水文地质条件、土壤及地下水污染现状,监测场地地下水中苯系物(BTEX)浓度及相关化学参数变化,运用微生物水文地球化学方法和水文地质方法,估算了该场地含水层自然降解苯系物量。这一研究成果为评估我国石油类场地地下水污染的自然修复能力提供了实证和基础数据。     

甲苯在土壤地下水中迁移规律研究

石油泄漏导致甲苯等有机污染物污染土壤地下水,并且甲苯等石油类有机污染物对土壤地下水污染具有隐蔽性强、难以逆转等特点,污染治理难度大。因此,研究甲苯有机污染物在土壤地下水中运移规律是治理的关键。该文以某污染场地为研究区,以甲苯有机污染物为研究对象,考虑了淋滤、吸附的影响,采用模型计算方法,分析了甲苯在污染场地土壤地下水中迁移规律。结果表明：甲苯在土壤地下水中迁移过程中,淋滤作用对甲苯浓度变化影响显著;吸附影响下扩散作用及地下水位变化对甲苯迁移产生的影响均受到抑制。该文获得的甲苯在土壤地下水中迁移规律可为甲苯有机污染物污染场地修复提供依据。     

地下水污染场地污染的控制与修复

我国存在大量的地下水污染场地,给地下水资源的使用带来了严重威胁。将地下水污染场地划分为4大类,15个亚类,为制定不同地下水污染场地的管理、控制和修复规定提供了依据;对地下水污染防治规划的内容和方法技术进行了论述。提出了建立地下水污染的预警系统,为污染的预防奠定基础;介绍了地下水污染的控制与修复技术,并对地下水污染防控和治理的基本原则进行了探讨。     

脱卤杆菌介导的厌氧微生物富集菌群对1,2,4-三氯苯的降解特性

1,2,4-三氯苯是我国工业污染场地土壤和地下水中典型的有机污染物,具有持久性、生物蓄积性和高毒性特点,对生态环境和人体健康危害巨大。1,2,4-三氯苯密度比水大,容易迁移至深部厌氧区域,因此,开展1,2,4-三氯苯厌氧微生物降解与修复研究具有重要实际应用价值。本文通过长期富集培养,获得一份可以稳定地将1,2,4-三氯苯还原脱氯至1,4-二氯苯,再进一步还原脱氯至氯苯的厌氧菌液。通过16S rRNA基因扩增子测序及引物特异性的定量PCR实验,证明厚壁菌门的脱卤杆菌属细菌(Dehalobacter species)是1,2,4-三氯苯和1,4-二氯苯厌氧还原脱卤的功能菌株,其生长率为(1.68±0.8)×10⁶ copies·μmol^-1(释放的氯离子)。通过PCR扩增,获得Dehalobacter菌株的16S rRNA基因序列,构建了系统发育树。本研究可为1,2,4-三氯苯污染场地开展原位厌氧微生物修复提供菌株资源和理论指导。     

冻结技术在水土重金属污染净化与修复中的应用及进展

随着工业化进程的加快,水土重金属污染事件逐渐增多,对其治理与修复成为当前的迫切工作。冻结技术在治理修复污染水土时,其修复过程只向地层输入“冷量”,属于绿色修复技术,无二次污染风险,受到越来越多的关注。详细总结了冻结技术的修复机理,及其在污水、污泥、重金属污染土壤治理修复中的应用现状和最新研究进展。冻结修复机理是通过冰的自净作用和固-液相平衡原理来实现污染物的定向驱赶和富集,而黏性土壤颗粒的吸附和阻滞作用使单一技术对重金属污染土壤的修复难度增大,其他修复手段与冻结技术联合处理成为一种新的思路。利用冻结土体的低渗透性,还可有效降低污染物的迁移速度,封闭不同种类污染物,形成阻隔污染物扩散的冻结屏障。冻结修复技术在水土重金属污染净化及修复领域具有良好的应用前景。     

某岩溶矿坑场地污染特征及潜在风险分析

某灰岩矿坑场地受到了有机污染,对当地脆弱的岩溶地下水环境构成威胁。在查明场地周边岩溶发育特征的基础上,结合区域水化学、水动力场调查结果,分析了场地及周边地下水污染特征和污染场地的潜在风险。结果表明：场地内水体受到了萘、氯乙烯、苯酚、邻苯二甲酸二丁酯、PCB52等多种有机物的污染,其中以4-氯-3-甲基苯酚、2,4-二硝基苯酚等酚类化合物含量最高;场地内水体水质兼具地下水特征,水化学类型为Cl·SO4-Na·Ca型,与其相邻的2个矿坑水质已受到影响,水体水化学类型往污染场地水体类型演化;场地周边地下水水质总体较好,仅场地西侧1个地下水井水质受到了污染矿坑的影响。目前,该矿坑场地仍处于水位漏斗恢复期,污染物并无向外迅速扩散的水动力条件,但当矿坑场地流场恢复至天然状态后,矿坑内污染物可通过场地周边的3条岩溶裂隙带-60 m标高以浅的地层向周边迁移,对环境造成了巨大威胁,应采取降低矿坑水位、定期监测矿坑水和地下水水质、实施帷幕灌浆工程等措施防控场地的潜在污染风险。     

Technical Challenges to In-situ Remediation of Polluted Sites

Throughout the world, subsurface contamination has become a widespread and pervasive problem. Toxic chemicals such as heavy metals and organic compounds are commonly used in a myriad of industries. However, largely through inadvertent or accidental release, these chemicals are presently polluting sites across the United States. In order to protect public health and the environment, further pollution must be prevented and sites with existing contamination urgently need remediation. Unfortunately, remediating subsurface contamination has proved to be a daunting task. Heavy metals and organic compounds often coexist and their distribution within the subsurface is highly dependent on particle and macro-scale heterogeneities. Vast resources have been invested to develop efficient remediation technologies, yet very few of these technologies have been successful. In-situ remediation is often preferred due to minimal site disturbance, safety, simplicity, and cost-effectiveness. The effectiveness of in-situ remediation technologies depends largely on the contaminant chemistry and subsurface heterogeneities (including particle-scale heterogeneities such as fine-grained soils, soils with reactive minerals, and/or soils rich in organic matter as well as macro-scale heterogeneities such as irregular soil layers and/or lenses). Under such heterogeneous conditions, integrated electrokinetic remediation technology has great potential. As a safe and economical remedial option for so many contaminated sites, the application of integrated electrokinetic remediation offers enormous public health, environmental, and financial benefits.     

Co-contamination of water with chlorinated hydrocarbons and heavy metals: challenges and current bioremediation strategies

Chlorinated hydrocarbons can cause serious environmental and human health problems as a result of their bioaccumulation, persistence and toxicity. Improper disposal practices or accidental spills of these compounds have made them common contaminants of soil and groundwater. Bioremediation is a promising technology for remediation of sites contaminated with chlorinated hydrocarbons. However, sites co-contaminated with heavy metal pollutants can be a problem since heavy metals can adversely affect potentially important biodegradation processes of the microorganisms. These effects include extended acclimation periods, reduced biodegradation rates, and failure of target compound biodegradation. Remediation of sites co-contaminated with chlorinated organic compounds and toxic metals is challenging, as the two components often must be treated differently. Recent approaches to increasing biodegradation of organic compounds in the presence of heavy metals include the use of dual bioaugmentation; involving the utilization of heavy metal-resistant bacteria in conjunction with an organic-degrading bacterium. The use of zero-valent irons as a novel reductant, cyclodextrin as a complexing agent, renewable agricultural biosorbents as adsorbents, biosurfactants that act as chelators of the co-contaminants and phytoremediation approaches that utilize plants for the remediation of organic and inorganic compounds have also been reported. This review provides an overview of the problems associated with co-contamination of sites with chlorinated organics and heavy metals, the current strategies being employed to remediate such sites and the challenges involved.     

土壤类型及组分对热活化过硫酸盐氧化降解土壤中挥发性氯代烃的影响

为了探究高级氧化技术对土壤中有机氯代烃的氧化降解作用,为ISCO（in situ chemical oxidation）技术体系提供重要的理论依据和数据支撑,考察了热活化过硫酸盐（persulfate,PS）氧化降解不同类型土壤（砂类土壤、黏土类土壤）中挥发性氯代烃污染物（三氯乙烯（TCE）、三氯乙烷（TCA）、顺式-1,2-二氯乙烯（cis-1,2-DCE）、1,2-二氯乙烷（1,2-DCA））的效能;同时,通过硫酸盐与土壤相互作用过程研究,探究了不同土壤介质中有机质和无机组分在过硫酸盐消耗中所占比例。结果表明：在50℃时,热活化过硫酸盐可有效降解土壤中1,2-DCA、cis-1,2-DCE、TCA和TCE,砂类土壤介质中4种氯代烃降解效果依次为25%、89%、5%和61%,黏土类土壤介质中4种氯代烃降解效果依次为35%、86%、8%和63%;4种氯代烃的降解效果从高到低顺序依次为cis-1,2-DCE、TCE、1,2-DCA、TCA,砂类土壤中的氯代烃总体降解效果优于黏土类土壤中氯代烃的降解效果。另外,土壤中过硫酸盐氧化降解氯代烃反应研究发现,砂类和黏土类土壤介质组分中有机质消耗率分别为81.3%和72.6%,铁元素消耗率分别为80.5%和38.6%,表明土壤介质组分与过硫酸盐发生了氧化还原反应,从而导致过硫酸盐自身的大量消耗。由此可知,土壤介质中的有机质、铁元素等矿物质均参与过硫酸盐的消耗过程,且土壤有机质、铁元素与氯代烃之间在消耗过硫酸盐反应上存在竞争关系,土壤组分过多地消耗了过硫酸盐,导致了氯代烃的氧化降解效率较低。因此,针对实际有机氯代烃污染场地,采用过硫酸盐氧化技术进行修复时,过硫酸盐的实际投加量要远高于化学计量值,需充分考虑到土壤组分对过硫酸盐自身的消耗作用。     

浅层地下水氯代烃污染天然衰减速率的估算

天然衰减恢复技术是恢复和控制浅层地下水氯代烃污染的技术之一,如何简便获取可靠的氯代烃衰减速率常数是该技术应用的一个关键。趋势线分析方法是一种简便有效的方法,在污染羽状体稳定的条件下,通过地下水流向上至少3口监测井的资料,能够比较准确地估算出污染物的天然衰减速率常数和生物降解速率常数。某氯代烃污染典型区的应用实例研究表明,该区四氯乙烯(PCE)的天然衰减速率常数和生物降解速率常数分别为0·000925d-1和0·000537d-1,证实该区浅层地下水中的PCE存在天然生物降解,但降解速率比较缓慢。忽略吸附作用的天然衰减容量计算所得出的天然衰减速率常数明显小于实际结果,说明尽管典型区包气带及含水层介质的有机碳含量很少,但它们对PCE的吸附作用不容忽视。     

The effects of aquifer heterogeneity on the 3D numerical simulation of soil and groundwater contamination at a chlor-alkali site in China

The simulation of groundwater flow and solute transport at contaminated sites often neglects the important influence that aquifer heterogeneity can have on the sub-surface distribution of contaminants. In this paper, the method of transition probability for geological statistics (T-PROGS) included in the Groundwater Model System (GMS) was applied to a chlor-alkali-contaminated site that was sampled with 68 soil borings and 15 groundwater monitoring wells. A 3-D groundwater numerical model and solute transport model was developed that was constrained by soil and groundwater data from the site. The spatial distribution of chloroethylene concentrations was simulated for a number of times using the levels measured in the field as a baseline. The results of these simulations showed that shapes and distribution of contaminant plumes are irregular both vertically and horizontally. The solute-transport simulations indicated that much of the contamination will preferentially move in groundwater through silt and fine-sands whereas flow is largely blocked in clays. Consequently, fine sand and silts become the most seriously polluted zones at the site, whereas, areas underlain by clays are largely uncontaminated. Heterogeneous lithologies beneath a site increase the complexity of coupling simulations of soil and groundwater.     

Organic Contamination of Soil and Goundwater in the Piedimont Plain of the Taihang Mountains

The risk of groundwater contamination following the infiltration of waste surface water, is of great interest, particularly in areas experiencing water shortage. In this study, the distribution characteristics of contaminants along the Cihe River, in the piedimont plain of the Taihang Mountains, China, was investigated by measuring the soil and water samples. The main organic contaminants detected in different media include hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, and pesticides. The main contaminants found in different media are mostly derived from the river water, which can be seen from the results of waste water from the river and groundwater, from the soil samples from different depth and distance of the profiles along the river. The distribution characteristics showed that there has been a natural attenuation of the contaminants from the river during their transportation through the soils and groundwater. The sorption of organic compounds to soil organic matter is thought to be a main mechanism of natural attenuation.     

An Integrated Geostatistical Approach for Contaminated Site and Soil Characterisation

For several years, abandoned or stopped industrial sites increasingly arouse the interest of politics and investors. Having a high social and economic estate value, these sites generally reveal contaminated soils that must be remediated first before receiving any new use. Due to financial, environmental or human health stakes, heuristic methods appear inappropriate because they do not provide reliable estimations of contaminated soil volumes and ignore spatial uncertainties. Problems at hand may be very complex, involving multiple correlated contaminants for which spatially varying pollutant grades are to be estimated and confronted to various regulatory thresholds, depending on redevelopment target areas. In such conditions, geostatistics provides effective methods to quantify local and global uncertainties about soil contamination and contaminated soil volumes. By quantifying uncertainties, geostatistical models are useful as support for decision-making about redevelopment scenarios or remediation techniques. Specific approaches are required, however, to overcome particular modelling issues as related to the skewness of pollutant grade distributions or change of support. Making use of our practical experience, such an integrated geostatistical approach is proposed for modelling contaminated sites. It is illustrated by application to a recent actual case study.     

Risk Assessment on Organic Contamination of Shallow Groundwater of an Oilfield in Northeast China

With the oil contaminated site of an oil field in northeast as the research area, based on the site geological and hydrogeological conditions, and by virtue of the methods of assessment on current situation of organic contamination and environmental impact assessment as well as leaching mobility assessment on organics, the internal and external risk assessments on organic contamination of shallow groundwater in the research area are conducted respectively. According to the results, about 30 kinds of organic components, including chlorinated hydrocarbons, mononuclear aromatics, heteroaromatic compound, polycyclic aromatic hydrocarbon and n-alkanes, are detected in the shallow groundwater in the research area. The current situation contamination of dichloromethane is the most serious, and all well points are of contamination at medium or above level. Compared with dichloromethane, contamination of trichloromethane and benzene is lighter, but several seriously contaminated well points occur in these two groups. The leaching mobility of dichloromethane, trichloromethane and benzene is extremely high, posing the greatest contamination risks against groundwater.     

Soil contamination near non-ferrous metal smelters: A review

This review summarizes over 160 studies focused on soil contamination near non-ferrous metal smelters. The methods of these investigations were examined with an emphasis on the combinations of traditional (geo)chemical approaches with various mineralogical and metal isotope techniques that are particularly helpful for depicting the fate of smelter-derived contamination in the soil. Differences in the distributions and binding of metal(loid)s in smelter-affected soils from temperate and (sub)tropical climatic zones indicate the greater vulnerability of the latter. Prevailing wind direction is a key factor affecting the dispersion of smelter emissions and their subsequent deposition into the soils, with greater importance found especially in arid areas. Whereas the greatest contamination is generally observed in the surface soil layers, downward migration of metal(loid)s in the soil profiles has been documented at numerous sites. Contamination of smelter soils significantly affects both plants and soil organisms, but suitable remediation techniques (such as chemical stabilization of soils by amendments) can be used for reducing the bioavailability of contaminants.     

Carcinogenic risk evaluation for human health risk assessment from soils contaminated with heavy metals

Human activities have progressively increased in recent years. Consequently, significant environment deterioration resulted. Soils have a particularly varied vulnerability to heavy metal pollution, especially in the vicinity of industrial areas. Heavy metal contamination of soil may induce risks and hazards to humans and the ecosystem, while toxic metals in soil can severely inhibit the biodegradation of organic contaminants. This paper is focused on human health risk assessment from extremely contaminated soil with heavy metals, mainly with carcinogenic elements. The study refers to an agricultural area in the vicinity of an old metallurgical processing industrial facility. The contaminants evaluated in the present paper are beryllium (Be), cadmium (Cd), chromium (Cr), nickel (Ni) and lead (Pb). Contamination level is pointed out through laboratory analysis results of soil samples taken from 0–0.2 m, 0.2–0.4 m soil layers and up to 2.1 m soil depth. Some heavy metal concentrations (Cd, Cr and Pb) exceed the intervention thresholds for sensitive areas, as they are stipulated in the national regulation in Romania. The identified average concentration levels of Cd, Cr^VI and Pb in the first layer of the investigated land are 23.83, 7.71 and 704.22 mg/kg_d.w, respectively. The results show that the potential risk of human health is relevant (higher than the acceptable one after World Health Organization) and a possible solution for the remediation should become a major concern for the investigated area.