DGT use in contaminated site characterization. The importance of heavy metal site specific behaviour

The objective of this study is to provide an insight into the techniques for measuring the lability of heavy metals in solid-phase pool of soils in order to assess the environmental risk arising from pollution. The technique of diffusive gradients in thin films (DGT) and a sequential extraction procedure were used to quantify the labile pools of Cu, Fe, Mn and Ni. These results were compared to metal concentrations in groundwater, measured directly using the in situ piezometers, and to the total concentration of metal in the soils. High concentrations of metal in the directly analysed soil solution compared to DGT measurement were attributed to the presence of colloidal metal. The use of DGT allowed only to calculate leaching parameters of the free ions and labile fractions of the metals. For this reason DGT technique needs preliminary investigation on metal speciation in soil solution before its application as a good tool in the characterization procedure of contaminated sites.     

Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.     

典型污染场地中滴滴涕浓度空间变异性研究

利用经典统计学和地统计学相结合的方法,以某滴滴涕(DDT)粉剂生产企业为例,对污染场地中表层和地下5m处土样DDT浓度的空间变异性进行了研究。结果表明:表层和地下5m处土样DDT浓度经过对数转化后均通过了柯尔莫哥洛夫-斯蜜诺夫检验(K-S检验),能够很好地服从正态分布;表层和地下5m处土样DDT浓度的半变异函数拟合符合高斯模型,决定系数分别为0.8973和0.9348,由空间自相关引起的空间变异性分别占系统总变异性的99.11%和83.12%;用克里格插值法制出的DDT浓度等值线图能直观地反映表层和地下5m处土样DDT浓度的空间分布特征,DDT浓度呈现以原粉生产车间为中心向四周扩散的趋势,地下5m处土样DDT浓度空间分布与表层基本一致。     

六氯苯在中国典型持久性有机污染物污染场地中空间分布研究

在多年六氯苯生产车间及周围布设采样点,采取不同深度的土壤进行分析,研究持久性有机污染物(POPs)污染场地中六氯苯的空间分布规律.结果表明,生产车间附近污染严重,六氯苯的最高质量浓度为25 911.95 mg/kg,平均为4 944.07 mg/kg,在风力作用下六氯苯浓度向东南方向扩散;-3 m土层(以表土层为基准,表土层以下的土层深度为负值)中六氯苯最高质量浓度为369.63 mg/kg.平均为54.77 mg/kg,六氯苯浓度较表土层迅速下降,六氯苯污染中心位置与表土层对应;-5 m土层由于土壤类型为黏土或淤泥质黏土,六氯苯浓度相对于- m土层反而升高.平均质量浓度为92.13 mg/kg.纵观整个污染场地六氯苯的污染分布情况,污染中心位置向南移动,且六氯苯在垂直方向的迁移和浓度与土壤有机质含量相关.     

典型氯碱污染场地环境风险评价

以广东某氯碱化工污染场地为研究区域,采集了场地22个土壤及地下水样品,分析了25项污染物在不同区域的分布特征及其来源。监测结果表明,煤炭堆场与锅炉房区土壤受重金属铅、镍污染。六六六、四氯化碳、三氯甲烷、六氯苯、苯是场地的特征污染物,主要分布在危险品仓库、漂洗车间与四氯化碳车间。根据监测结果开展了不同暴露途径致癌风险值及非致癌危害商的计算。结果表明,部分样品表层土壤中上述有机污染物的基于人体健康致癌风险指数均超过10-6,最高达到1.65×10-2,表明风险水平高;非致癌危害在各暴露途径下也超过可接受值1,最高达5.59×104,表明风险水平高。说明对于存在高风险的区域必须进行采取合适的措施进行修复,减缓场地再利用后对人群健康的影响。     

Perchlorate in fish from a contaminated site in east-central Texas

Perchlorate, a known thyroid endocrine disruptor, contaminates surface waters near military instillations where solid fuel rocket motors are manufactured or assembled. To assess potential perchlorate exposure to fish and the human population which may feed on them, fish were collected around the Naval Weapons Industrial Reserve Plant in McLennan County, TX, and analyzed for the presence of the perchlorate anion. The sampling sites included Lake Waco and Belton Lake, and several streams and rivers within their watersheds. The general tendency was that perchlorate was only found in a few species sampled, and perchlorate was not detected in every individual within these species. When detected in the fish, perchlorate tissue concentrations were greater than that in the water. This may be due to highly variable perchlorate concentrations in the water coupled with individual-level variation in elimination from the body, or to routes of exposure other than water.     

Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.     

Flux-based assessment at a manufacturing site contaminated with trichloroethylene

Groundwater and contaminant fluxes were measured, using the passive flux meter (PFM) technique, in wells along a longitudinal transect passing approximately through the centerline of a trichloroethylene (TCE) plume at a former manufacturing plant located in the Midwestern US. Two distinct zones of hydraulic conductivity were identified from the measured groundwater fluxes; a 6-m-thick upper zone ( approximately 7 m to 13 m below the ground surface or bgs) with a geometric mean Darcy flux (q(0)) of 2 cm/day, and a lower zone ( approximately 13 m to 16.5m bgs) with a q(0) approximately 15 cm/day; this important hydrogeologic feature significantly impacts any remediation technology used at the site. The flux-averaged TCE concentrations estimated from the PFM results compared well with existing groundwater monitoring data. It was estimated that at least 800 kg of TCE was present in the source zone. The TCE mass discharge across the source control plane (85 m x 38 m) was used to estimate the "source strength" ( approximately 365 g/day), while mass discharges across multiple down-gradient control planes were used to estimate the plume-averaged, TCE degradation rate constant (0.52 year(-1)). This is close to the rate estimated using the conventional centerline approach (0.78 year(-1)). The mass discharge approach provides a more robust and representative estimate than the centerline approach since the latter uses only data from wells along the plume centerline while the former uses all wells in the plume.     

基于风险的中国污染场地管理体系研究

在分析借鉴国外污染场地管理框架体系的基础上,结合中国近几年在污染场地法律法规及标准建设方面的经验以及各地的管理实践,提出了建立基于风险的中国污染场地管理模式、管理技术程序、层次化的风险评估方法,以及相应的标准体系构想。     

Serum profiles of PCDDs and PCDFs, in individuals near the Escambia Wood Treating Company Superfund site in Pensacola, FL

The Escambia Wood Treating Company (ETC) Superfund site, Pensacola, FL, is contaminated with polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F), benzo(a)pyrene, lead and arsenic from pentachlorophenol (PCP), creosote, and other compounds used to treat utility poles and foundation pilings. Although ETC's operations ceased in 1982, soils in the areas surrounding the facility continue to exhibit elevated levels of contaminants attributable to ETC operations. In July 2000, individuals who may have been affected by contamination from the ETC site, including current and former residents and former workers and their household members were invited to participate in a study, which included a health and exposure history and routine blood analysis. We also conducted a toxicological health evaluation of a subset of these eligible workers/residents by analyzing serum levels of 17 PCDD/F congeners. Members of the ETC cohort exhibited elevated serum PCDD/F relative to the general population, and congener profiles in members of the cohort reflected patterns commonly observed in persons exposed to PCP. Hypertension prevalence in the cohort was found to correlate with PCDD/F levels, although no other significant relationships were identified with monitored health indices.     

Metal availability in a highly contaminated, dredged-sediment disposal site: Field measurements and geochemical modeling

Two complementary approaches were used to characterize arsenic and metal mobilizations from a dredged-sediment disposal site: a detailed field study combined with hydrogeochemical modeling. Contaminants in sediments were found to be mainly present as sulfides subject to oxidation. Secondary phases (carbonates, sulfates, (hydr)oxides) were also observed. Oxidative processes occurred at different rates depending on physicochemical conditions and contaminant contents in the sediment. Two distinct areas were identified on the site, each corresponding to a specific contaminant mobility behavior. In a reducing area, Fe and As were highly soluble and illustrated anoxic behavior. In well-oxygenated material, groundwater was highly contaminated in Zn, Cd and Pb. A third zone in which sediments and groundwater were less contaminated was also characterized. This study enabled us to prioritize remediation work, which should aim to limit infiltration and long-term environmental impact.     

Estimating risk at a Superfund site using passive sampling devices as biological surrogates in human health risk models

Passive sampling devices (PSDs) sequester the freely dissolved fraction of lipophilic contaminants, mimicking passive chemical uptake and accumulation by biomembranes and lipid tissues. Public Health Assessments that inform the public about health risks from exposure to contaminants through consumption of resident fish are generally based on tissue data, which can be difficult to obtain and requires destructive sampling. The purpose of this study is to apply PSD data in a Public Health Assessment to demonstrate that PSDs can be used as a biological surrogate to evaluate potential human health risks and elucidate spatio-temporal variations in risk. PSDs were used to measure polycyclic aromatic hydrocarbons (PAHs) in the Willamette River; upriver, downriver and within the Portland Harbor Superfund megasite for 3 years during wet and dry seasons. Based on an existing Public Health Assessment for this area, concentrations of PAHs in PSDs were substituted for fish tissue concentrations. PSD measured PAH concentrations captured the magnitude, range and variability of PAH concentrations reported for fish/shellfish from Portland Harbor. Using PSD results in place of fish data revealed an unacceptable risk level for cancer in all seasons but no unacceptable risk for non-cancer endpoints. Estimated cancer risk varied by several orders of magnitude based on season and location. Sites near coal tar contamination demonstrated the highest risk, particularly during the dry season and remediation activities. Incorporating PSD data into Public Health Assessments provides specific spatial and temporal contaminant exposure information that can assist public health professionals in evaluating human health risks.     

MIP系统在某挥发性氯代烃污染地块调查中的应用

针对我国挥发性有机污染地块调查评估中存在的采样缺失、成本高及周期长等问题,选择华北地区某挥发性氯代烃污染地块为研究对象,采用现行调查方法与基于膜界面探针(MIP)系统快速调查技术联合使用的方式,现场完成场地钻探调查点位4个(土壤样品36个),MIP系统调查点位11个(验证点位4个),以研究MIP验证点位检测电信号值与其对应场地钻探点位的地层信息、实验室检测数据之间的相关性,以及使用MIP电信号值模拟地块地层和污染空间的分布特征。结果表明,MIP系统检测的土壤电导率电信号值(EC)能够更为详尽地表征地块的地层结构信息;在地块范围内的同一种土质中,MIP系统的专用卤素检测器电信号值(XSD)与实验室检测数据拟合度相对较高(R²>0.99);MIP系统快速调查技术与现行调查方法联合使用能够快速且高效表征调查地块内VCHs的污染空间分布特征。本研究结果可为MIP系统快速调查技术在挥发性有机污染地块调查评估中的应用提供参考。     

碱活化过硫酸盐在某氯代烃污染场地地下水修复中的应用

碱活化过硫酸盐适用于降解污染土壤及地下水中的氯代烃。以典型氯代烃类污染场地为研究对象,开展了碱活化过硫酸盐降解地下水中氯代烃的小试实验研究及中试规模工程应用。结果表明：污染物去除率与污染物初始浓度、氧化剂投加比相关;污染物初始浓度越高,去除率越低;氧化剂投加量越大,去除率越高,用于该场地地下水修复的最佳氧化剂投加比为1%~3%。中试药剂原位注入采用高压旋喷注射工艺,按最佳氧化剂投加比将药剂注入至污染含水层,跟踪监测结果表明：经注药修复8个月后,地下水中氯代烃污染物浓度明显下降,大部分区域的污染物浓度已达到修复目标,局部初始浓度偏高区域的污染物浓度接近修复目标。同时,对氧化剂产物残留$ {\rm{S}}{{\rm{O}}^{2 - }_4}$浓度进行监测发现：$ {\rm{S}}{{\rm{O}}^{2 - }_4}$浓度随修复后时间延长逐渐降低,通过趋势分析预测的残留$ {\rm{S}}{{\rm{O}}^{2 - }_4}$浓度将逐步下降直至恢复正常水平或满足相关标准。     

Overview and Update of the Superfund Innovative Technology Evaluation (site) Demonstration Program

The Superfund Innovative Technology Evaluation (SITE) Program is now in its sixth year of demonstrating technologies applicable to Superfund sites. The SITE Program, conducted by the U.S. Environmental Protection Agency’s Risk Reduction Engineering Laboratory, is intended to accelerate the use of new and innovative treatment processes as well as evaluate innovative measurement and monitoring techniques. Within the SITE Program, the Demonstration Program and the Emerging Technologies Program are responsible for innovative/ alternative waste treatment technology development. Separate and parallel activities are progressing for development and evaluation of measuring and monitoring technologies as well as technology transfer operations.     

地下水监测在污染场地管理中的重要作用、存在问题与对策建议

我国污染场地修复行业长期存在“重土轻水”的现象。然而,由于土壤与地下水共同构成了有机统一的地下环境,污染物在土壤和地下水之间存在密切的物质交换,因此,充分掌握目标场地的地下水污染状况对于场地环境管理及修复后地块的安全利用起着举足轻重的作用。对地下水监测在整个污染场地环境管理工作中的四方面作用进行了剖析,阐明了我国污染场地地下水监测中存在的问题,并针对性地提出了解决思路和政策建议,以期为我国的污染场地管理提供参考。     

场地地下水中氯代甲烷烃自然衰减机制

自然衰减监控技术在农药污染场地的实践应用较少,作用机制尚不明确.为此,以农药污染场地监控自然衰减实际工程案例为基础,对地下水中氯代甲烷烃的自然衰减能力、作用机制及降解时间进行了分析.Mann-Kendall趋势检验结果表明,作为污染源的MW1-17点位地下水中的四氯化碳和氯仿随时间呈现下降趋势,在4 a内降解率分别在9...