Heavy Metal Contamination in the Brownfield Soils of Cleveland

The results esults of a survey of heavy metal contamination at Cleveland area brownfields and public spaces are presented. Soils were analyzed using a 24?h, 1N HCl extraction procedure. The study was conducted to seek brownfield soils that manifest properties of “old” sequestered contamination and to develop a better understanding of the nature and extent of heavy metal burdens at brownfield sites in the Greater Cleveland area. The results indicated that Cleveland brownfields commonly yield soil burdens well above remediation triggers for residential soils and often yield values above industrial remediation triggers. It was also discovered that public areas in the vicinity of brownfields commonly have heavy metal contamination significantly above background levels and occasionally above residential remediation triggers. These results indicate that brownfields redevelopment initiatives should proceed with caution. The appropriate remediation goals or restrictions must be imposed to control urban exposure to heavy metal contamination.     

Risk-Based Corrective Action of Hydrocarbon Contamination at a Former Major Urban Petroleum Storage Site in the U.K.

The former site of a major petroleum storage facility adjacent to a major urban watercourse was found to have potentially significant concentrations of hydrocarbons in soil and groundwater that needed to be addressed prior to redevelopment. A series of intrusive investigations were undertaken to collect physical and chemical data for a Quantitative Risk Assessment (QRA) of potential impacts on human health and the wider environment, in order to derive a remedial strategy for redevelopment of the site for light industrial use. A site-specific QRA methodology was devel oped using both U.K. and U.S. guidance to produce Risk-Based Clean-up Levels (RBCLs) for benzene, and other petroleum hydrocarbons. The U.K. has no nationally based guidance on risk assessment and studies are designed by the consultant for submission to the U.K. Environment Agency (EA) for their approval. It is the EA's role to determine whether the work has been undertaken satisfactorily. To achieve these RBCLs, ex situ bioremediation was identified as the best practicable remedial option. This was carried out in windrows using mechanical aeration (to achieve oxygenation with ammonia nitrate granule and woodchip addition) for a total of approximately 5291?m³ of soil. The bioremediation process was successful in achieving the site specific RBCLs for benzene and for other hydrocarbons within an average of 5 to 6 weeks. This article describes the successful implementation of Risk-Based Corrective Action (RBCA) at this petroleum release site as a demonstration of how risk-based remedial standards for contaminated sites can be achieved with regulatory approval.     

A Spatially Explicit Model to Predict Radiocesium Body Burdens of White-Tailed Deer on the U.S. Department of Energy's Savannah River Site

We developed a spatially explicit exposure model to interpolate and predict radiocesium (¹³⁷Cs) body burdens found in white-tailed deer (Odocoileus virginianus) on the U.S. Department of Energy's (USDOE) Savannah River Site (SRS) to gain insight into and differentiate between the main contributing sources of this radionuclide for use in harvest management strategies that focus on minimizing human risk. Hunting has been allowed from permanent stands as a mechanism to manage the deer herd since 1965. All animals are monitored in the field for gross beta and gamma activity levels, providing a spatially explicit dataset. The models described here use the relative locations of the hunt-stands to predict ¹³⁷Cs exposure distributions. We used kriging to create an interpolation surface using average white-tailed deer body burdens. Cross-validations of the kriged surfaces differentiated between sources of ¹³⁷Cs and where deer reside on the SRS. The kriged surfaces, coupled with additional regression analyses, provide a comprehensive assessment of deer's ¹³⁷Cs body burdens with predictive capability that quantifies the scale at which such investigations can be conducted. Although the models are local in scale, the methods presented here can be used as a template for other large areas that are being monitored for radioactive fallout.     

Instances of Soil and Crop Heavy Metal Contamination in China

Both general and specific investigations of soil and crop heavy metal contamination were carried out across China. The former was focused mainly on Cd, Hg, As, Pb, and Cr in soils and vegetables in suburbs of four large cities; the latter investigated Cd levels in both soils and rice or wheat in contaminated areas throughout 15 provinces of the country. The results indicated that levels of Cd, Hg, and Pb in soils and some in crops were greater than the Governmental Standards (Chinese government limits for soil and crop heavy metal contents). Soil Cd ranged from 0.46 to 1.04?mg kg^?1, on average, in the four cities and was as high as 145?mg kg^?1 in soil and 7?mg kg^?1 in rice in the wide area of the country. Among different species, tuberous vegetables seemed to accumulate a larger portion of heavy metals than leafy and fruit vegetables, except celery. For both rice and wheat, two staple food crops, the latter seemed to have much higher concentrations of Cd and Pb than the former grown in the same area. Furthermore, the endosperm of both wheat and rice crops had the highest portion of Cd and Cr. Rice endosperm and wheat chaff accumulated the highest Pb, although the concentrations of all three metals were variable in different parts of the grains. For example, 8.3, 6.9, 1.4, and 0.6?mg kg^?1 of Pb were found in chaff, cortex, embryo, and endosperm of wheat compared with 0.11, 0.65, 0.71, and 0.19?mg kg^?1 in the same parts of rice, respectively. Untreated sewage water irrigation was the major cause of increasing soil and crop metals. Short periods of the sewage water irrigation increased individual metals in soils by 2 to 80% and increased metals in crops by 14 to 209%. Atmospheric deposition, industrial or municipal wastes, sewage sludge improperly used as fertilizers, and metal-containing phosphate fertilizers played an important role as well in some specific areas.     

重金属污染土壤修复技术中有关淋洗剂的研究进展

淋洗法是修复污染土壤的一种很有效的方法 ,是对污染土壤生物修复的一种补充 ,使污染土壤修复的系统化成为可能。淋洗法就是使用淋洗剂来清洗土壤 ,使土壤中污染物随淋洗液流出 ,然后对淋洗液及土壤进行后续处理 ,从而达到修复污染土壤的目的。而淋洗剂的选择是影响这一技术效率高低的主要因素之一。本文对目前淋洗剂的应用情况 ,作用机制进行了总结和评价。探讨了天然有机酸、生物表面活性剂等对环境影响小的淋洗液的应用前景。并根据“以废治污”的指导思想提出并分析了以柠檬酸废水和味精废水作为淋洗剂修复重金属污染土壤的可行性。     

Metal(loid)-Contaminated Soils as a Source of Culturable Heterotrophic Aerobic Bacteria for Remediation Applications

Heavy metal–contaminated soils are a serious environmental problem. Herein, the culturable heterotrophic bacterial community present on two metal(loid)-contaminated sites in the Northern Portugal was investigated. The bacterial counts ranged from 5.96 to 7.69 and 7.04 to 7.51 (log CFU g^?1 soil) in Sites 1 and 3, respectively. The bacterial population was predominantly composed of Firmicutes, Proteobacteria, and Actinobacteria on both sites. The most represented genera in Site 1 were Bacillus (41%) and Pseudomonas (27%), whereas Arthrobacter (21%) and Pseudomonas (13%) were the most represented genera in Site 3. Several bacterial isolates showed tolerance to high concentrations of metal(loid)s, suggesting that both contaminated sites are a valuable source of metal(loid)-tolerant bacteria, which may be further used in bioremediation and/or phytoremediation processes.     

Assessment of Health Protectiveness of the Risk-Based Soil Remediation Standards of the Midwestern States

In the last decade, risk-based remediation following a framework similar to risk-based correction action (RBCA) has gained acceptance across the country and generic/Tier 1 Risk-Based Action Limits (RBALs) for hundreds of chemicals have been tabulated. However, there have been only a few studies that focused on understanding the causes of discrepancy among cleanup standards and policies of the hazardous waste programs among the states. This study aims to fill this critical need by examining the basis of generic (i.e., Tier 1) residential RBALs developed by the states, which are within the regulatory domain of U.S. Environmental Protection Agency's Region 5. Specifically, we seek to investigate the approaches/methodologies and the policy/technical rationale used in establishing RBALs, along with degree of inconsistency, and the causes and implications of inconsistencies. In addition, we developed RBALs for a case study site using both deterministic and probabilistic risk assessment approaches and compared these against RBALs developed by the states to infer about public health-protectiveness of the state-specific RBALs. We found three- and four-order-of magnitude difference among state RBALs for PAHs and VOCs, respectively. The degree of clean up deemed appropriate under Tier 1 evaluation by the midwestern states significantly differ from one another, which has both public health and economic implications.     

Microwave-Assisted Process (MAPTM) for the Extraction of Contaminants from Soil

Laboratory-scale tests were performed to evaluate the use of Environment Canada's patented Microwave-Assisted Process (MAP_TM) for the extraction of petroleum hydrocarbons from contaminated soil. The purpose of these tests was to determine the potential for using the process for large-scale processing of contaminated soil. Tests were performed using three soil types: a certified sediment and certified soil, both contaminated with polycyclic aromatic hydrocarbons (PAHs), and spiked peat soil contaminated with long-chain petroleum hydrocarbons. The test methods used were based on existing MAP techniques that have been proven for the sample preparation of contaminated soils for analytical purposes. The parameters evaluated concentrated on those that are amenable to a continuous large-scale process running at atmospheric pressures. This meant using solvents that are inexpensive and readily available in large volumes, low solvent to material ratios, and optimized energy inputs. In general, it was found that microwaves could be used to enhance the solvent extraction of the contaminants from the soil and that the properties of the soil greatly affected the extent to which the contaminants were removed.     

Arsenic Pollution of a Loam Soil: Retention Form and Decontamination

A study was conducted to assess the retention form of arsenic in soil and to evaluate the use of phosphate for releasing it from the soil. In this study, a loam soil was artificially polluted with arsenate at pH 5.5, which is one of the pH values at which maximum arsenic adsorption occurred. The soil was kept for 2.5 months under wet conditions to allow for stabilization. The soil was maintained under aerobic condition and losses of arsenic by volatilization were determined to be minimal. The soil was then sequentially extracted with a series of chemicals to identify the soil fractions in which the arsenic was bound. The percentage of arsenic found in the Fe bound-exchangeable, reducible-residual, Al bound exchangeable, residual, calcium bound exchangeable, and easily exchangeable forms was 31.6, 27.3, 25.2, 5.5, 4.9, and 4.7%, respectively. A batch experiment showed that at 20°C, 80% of the bound arsenic was removed by phosphate in the pH range of 5 to 7. A power function model was found to fit the data with a desorption rate constant of 402?mg/kg As h^?1.     

Impact of Oil-Spill Contamination on a Soil Bacterial Community: A 40-Year History of Rehabilitation in the Arava Valley

The present study evaluated the effect of crude oil contamination on a microbial community in hyper-arid soils. The Evrona Nature Reserve of Israel, situated in the Arava, was exposed twice in the last 40 years to petroleum-hydrocarbon-spill pollution. The first pollution event took place 40 years ago and was never treated, presenting a unique future time-point perspective to the second (2014) contamination event. Soil samples were collected after the second spill, and abiotic properties and bacterial diversity in the sampled soil were analyzed. The results showed that there is a significant decrease over time in the number of observed bacterial species in the contaminated samples, coupled together with bacterial species replacement toward species capable of using source oil as the sole carbon and energy source. The presence of petroleum in soil significantly changed the composition and functional diversity of a microbial community, and the Evrona Nature Reserve is still in the middle of a bioremediation process even 40 years after the crude oil contamination.     

Effects of a Combined Amendment on Pb,Cd, and As Availability and Accumulation in Rice Planted in Contaminated Paddy Soil

The objectives of the present study were to investigate the mitigation of lead (Pb), cadmium (Cd), and arsenic (As) in a multi-metal contaminated soil and their accumulation in rice plants (Oryza sativa L., cv II You 93) using a combined amendment (CMF, calcium carbonate + metakaolin + fused calcium–magnesium phosphate fertilizer). The results showed that application of CMF was effective in reducing the acid-extractable concentrations of soil Pb and Cd. The exchangeable concentrations of soil As showed an initial decrease followed by a gradual increase. The application of 0.2% CMF notably reduced the concentrations of Pb, Cd, and As in brown rice by 46.5%, 43.6%, and 32.0%, respectively. The concentration of As in brown rice was 0.179 mg kg^?1 at 0.2% CMF, which met the maximum levels of contaminants in foods of China (MLs) (the ML of Pb, Cd, and As is 0.2 mg kg^?1 according to the China national standard GB 2762-2012). At 1.6% CMF, the concentrations of Pb and Cd in brown rice were 0.002 and 0.185 mg kg^?1, respectively, i.e., reductions of 99.6% and 74.1%, and these values also fell within the MLs.     

The Detoxification of Heavy Metals in the Phosphate Tailing-contaminated Soil through Sequential Microbial Pretreatment and Electrokinetic Remediation

In this paper, the heavy metals (HMs) in the phosphate tailing-contaminated soil were detoxified using the microbial pretreatment in combination with electrokinetic remediation (EKR).. This study provides compelling evidence that the sequential usage of the bioleaching and electrokinetics is superior to the individual method for the detoxification of Pb, Cu, Zn, Cd, and As from the contaminated soil. In the sequential system, the detoxification efficiency of Zn was the highest and that of As was the lowest. Except the element As, the detoxification efficiencies of HMs in the sequential system were generally higher than that using the single biological treatment and EKR technique. Bioleaching, generation of the passivation, and migration direction of the ions are concluded as the factors attributable to the final results; and, the initial increase in the inoculation doping of Thiobacillus ferrooxidans considered has no obvious impact on improving the final detoxification efficiency rates.     

Developing a Remediation Strategy for Phosphorus Immobilization: Effect of Co-blending,Al-residual and Ca-Mg Amendments in a Manure-Impacted Spodosol

A remediation strategy called “co-blending” was developed for rapid phosphorus (P) immobilization. Immobilization was achieved through the combination of an Al-based water treatment residual (Al-WTR) with Ca-Mg-based materials (Slag and magnesium oxide) for use in incubation and leaching experiments. Al-WTR was co-blended with Slag and MgO as “Al-WTR+Slag” and “Al-WTR+MgO,” respectively. Sequential extraction was used to delineate P species into operationally defined fractions: soluble or exchangeable, Al-Fe, and Ca-Mg-bound pools. Results from soils used in the incubation experiment showed that Al-amended material tended to sequester P bound (～26%) to the Al-Fe pool. On the other hand, Ca-Mg-based materials tended to sorb (～70%) of P greatly associated to the Ca-Mg pool. Amendments were applied at 2% or 20 g kg^?1 as Al-WTR, MgO, and Slag and at 1%+1% or 10 g kg^?1+10 g kg^?1 as co-blended Al-WTR+MgO and Al-WTR+Slag, respectively, on mass basis. Results from leaching data suggest that treatment effects on pH are significant at (p < 0.0001) and also significant (p < 0.01) with weeks of leaching. A similar significant (p < 0.0001) trend was observed for effects of treatment on redox potential (Eh). However, treatment effects on weeks of leaching were not significant. Cumulative soluble P (mg) of leachate showed linear reduction (96%) from the control (without amendments) using a regression model. Potential co-blended material selected was Al-WTR+Slag (1%+1%) due to less P in leachates, moderate effect on pH, and fewer amounts of Al-WTR and Slag used compared with 2% Al-WTR and Slag, respectively. In addition, the RMSE of Al-WTR+Slag data fitted to a regression model was the least. Results suggested that the metal cations Al, Ca, and Mg tended to bind different forms of total P at any given pH. Through co-blending, less soluble P may be lost to the environment than using sorption materials independently.     

Use of the IEUBK Model for Determination of Exposure Routes in View of Site Remediation

The Integrated Exposure Uptake Biokinetic (IEUBK) model is frequently used to estimate blood lead concentrations of children exposed to lead. Simulations with the IEUBK model were run to estimate the blood lead concentration in children living in the vicinity of a non-ferrous plant, situated in Hoboken, Belgium. Concentrations in soil ranged from 59–2425 mg Pb/kg dm, average concentrations in house dust ranged from 234–73394 mg Pb/kg dm. Measured blood lead concentrations in children aged 2–7 years were between 3 and 35 μ g/dl. Exposure sources were indoor dust in the house and the school, outdoor dust and soil in the home surrounding and at the school's playground, and suspended dust in the air. Soil ingestion values and lead exposure from food were changed to Flemish values. The model was able to predict the measured blood lead concentrations adequately except for the lowest exposure group. Predictions showed a systematic overestimation. Analysis of the data revealed that the neighbourhood's school is an important source of exposure to lead; indoor house dust dominates exposure for children going to school outside the area, because of the high concentrations of lead in indoor dust (3 to 5 times higher than in outdoor soil).     

An Application of Delaware's Risk-Based Corrective Action Program: To a Site with MTBE Contamination

MTBE is a gasoline additive addressed in Delaware's Risk-Based Corrective Action Program. Due to inconclusive toxicological data, MTBE is difficult to address in a risk-based fashion pertaining to actual cancer risk. MTBE action levels in Delaware's Risk-Based Corrective Action Program (DERBCAP) are based on the low end of the aesthetic range of the contaminant (10 ppb), not a health-based number. Addressing MTBE in this manner can make it very amenable to risk-based decision making. When MTBE concentrations exceed Tier 1 RBSL values, the site must be remediated to those values or modeled in Tier 2 to calculate Site Specific Target Levels (SSTLs) and demonstrate a stable and shrinking plume. A case study is provided to evaluate the applicability of MTBE in DERBCAP at a site where several shallow, private supply wells were contaminated with MTBE following a gasoline release several hundred feet up-gradient. Following well replacement and site characterization, Tier 2 modeling was performed to establish clean-up goals (RBCA Toolkit). By using initial concentrations at the POC wells and forward calculating concentrations down-gradient, clean up goals were established for the 180 and 230 m POCs at 500 and 1100 ppb, respectively. These clean up goals will be protective of the 10 ppb maximum exposure limit (MEL) established at the down-gradient point of exposure (POE). Modflow (WHI) and MT3D (Zheng 1990) were used to determine if the pump and treat remediation schedule set forth by the consultant was sufficient to remediate to the calculated clean up levels. Transient simulations showed that pumping from wells on the leading and trailing edge of the plume “core” for 1 week each month for 2 years resulted in a drop in POE and source concentrations of 40 to 60%. Although the drop is significant, the down-gradient POE would still be in jeopardy of exceeding the MEL. This suggests that additional and/or more frequent remediation may be necessary.     

In situ bioremediation of hydrocarbon in soil

Laboratory and field experiments were carried out for bioremediation of soils contaminated by fuel oil and motor oil. Bioventing was combined with the application of selected bacteria and dissolved nutrients. In the field experiments, soil gas was evacuated by air pumps from the permeable boreholes. The process was followed by both soil and gas analysis. Biodegradation of oil contamination and the microbial activity was measured by the oil and cell concentration in the soil. In 2 months, the oil content decreased considerably, and the cell number increased by one order of magnitude or more. The evacuated gas was tested for CO₂, O₂ and volatilized hydrocarbon content. The CO₂ level proves the presence of biodegradation: a permanent high value about ten times higher than normal, could be measured for 2 months, followed by a slow decrease in the third month. Volatilized hydrocarbon content was the highest in the first 2 d. After a continuous decrease, it dropped under the threshold of measurability for the third month. Selective biodegradation of hydrocarbon mixtures (oily wastes) was investigated as well: gas Chromatographic oil analysis showed the changes in the oil composition. The appropriate microflora was working in an ideal commensalism, and as a result, all of the hydrocarbon components were degraded nearly to the same extent.     

基于神经网络模型和地统计学方法的土壤养分空间分布预测

采用径向基函数神经网络模型与普通克里格法相结合的方法,预测川中丘陵区县域尺度土壤养分(有机质和全氮)的空间分布,并与普通克里格法和回归克里格法进行比较.结果表明：各方法对研究区土壤养分的预测结果相似.与多元回归模型相比,神经网络模型对验证样点土壤有机质和全氮的预测值与样点实测值的相关系数分别提高了12.3%和16.5%,表明神经网络模型能更准确地捕捉土壤养分与定量环境因子间的复杂关系.对469个验证样点预测结果的误差分析表明,神经网络模型与普通克里格法相结合的方法对土壤有机质和全氮预测结果的平均绝对误差、平均相对误差、均方根误差较普通克里格法分别降低了6.9%、7.4%、5.1%和4.9%、6.1%、4.6%,降低幅度达到极显著水平(P<0.01);与回归克里格法相比则分别降低了2.4%、2.6%、1.8%和2.1%、2.8%、2.2%,降低幅度达显著水平(P<0.05).     

Bioaccessibility of Mercury in Soils

The initial risk assessment for the East Fork Poplar Creek (EFPC) floodplain in Oak Ridge, Tennessee, a superfund site heavily contaminated with mercury, was based on a reference dose for mercuric chloride. Mercuric chloride, however, is a soluble mercury compound not expected to be present in the floodplain, which is frequently saturated with water. Previous investigations had suggested mercury in the EFPC floodplain was less soluble and therefore potentially less bioavailable than mercuric chloride, possibly making the results of the risk assessment unduly conservative. A bioaccessibility study, designed to measure the amount of mercury available for absorption in a child's digestive tract (the most critical risk pathway endpoint), was performed on 20 soils from the EFPC floodplain. The average bioac-cessible mercury for the 20 soils was 5.3%, compared with 100% of the mercuric chloride subjected to the same conditions. The alteration of the procedure to more closely mimic conditions in the digestive tract did not significantly change the results. Therefore, the use of a reference dose for mercuric chloride at EFPC, and potentially at other mercury-contaminated sites, without incorporating a corresponding bioavailability adjustment factor may overestimate the risk posed by the site.     

Study of Heavy Metal Distribution in Soils Impacted with Crude Oil in Southern Nigeria

The study presents the levels and enrichment factors of heavy metals in soils of southern Nigeria that have received significant impact of crude oil spillage. The results revealed that the concentrations of heavy metals in the examined soils fitted into levels found in agricultural soils except for cadmium. Heavily impacted sites showed elevated levels of heavy metals compared to less impacted sites and background levels. The mean enrichment factors for Cd, Cu, Cr, Pb, Mn, Ni, and Zn were 37.3, 2.8, 14.4, 14.0, 0.77, 5.4, and 1.27 for topsoil and 37.5, 1.30, 7.81, 1.59, 4.12, and 1.28 for subsoil, respectively. This clearly indicates that there is gradual build-up of heavy metals in these soils as a result of the oil spillage and related anthropogenic activities in this area.     

Fenton's Reagent-Based In Situ Chemical Oxidation Treatment of Saturated and Unsaturated Soils at a Historic Railroad Site

A targeted treatment program utilizing in situ chemical oxidation was used to remediate diesel fuel-derived petroleum compounds in unsaturated and saturated soils at a historic railroad facility. This program consisted of multiple injections at varying depths within temporary Geoprobe® injection points. The actual treatment time was less than 3 months. Overall concentrations of volatile and semivolatile organic petroleum compounds were reduced by approximately 70%, while the total petroleum hydrocarbon concentration was reduced by nearly 50%. Treatment efficiency in unsaturated soil was similar to that in saturated soil. The results of the remedial program indicate that the effect of grain size of the subsurface materials on treatment efficacy is significant. The project has shown that the use of this technology can be as effective as other in situ treatment technologies used for treating subsurface diesel fuel contamination.