Bioavailability of hydrophobic organic contaminants in soils: fundamental concepts and techniques for analysis

Soils represent a major sink for organic xenobiotic contaminants in the environment. The degree to which organic chemicals are retained within the soil is controlled by soil properties, such as organic matter, and the physico‐chemical properties of the contaminant. Chemicals which display hydrophobic and lipophilic characteristics, as well as a recalcitrant chemical structure, will be retained within the soil, and depending on the ‘strength’ of the association may persist for long periods of time. This review describes the behaviour of hydrophobic organic contaminants in soils, focusing on the mechanisms controlling interactions between soil and contaminants. The bioavailability of contaminants in soil is also discussed, particularly in relation to contact time with the soil. It considers the degradation of organic contaminants in soil and the mechanisms microbes use to access contaminants. Finally, the review discusses the ‘pros’ and ‘cons’ of chemical and biological techniques available for assessing bioavailability of hydrophobic organic chemicals in soils, highlighting the need to quantify bioavailability by chemical techniques. It concludes by highlighting the need for understanding the interactions between the soil, contaminants and biota which is crucial to understanding the bioavailability of contaminants in soils.     

The use of a microbial contact toxicity test for evaluating cadmium bioavailability in soil

Background, Aims and Scope

Bioavailability of toxic compounds in soil can be defined as the fraction able to come into contact with biota and to cause toxic effects. The contact toxicity tests may detect the total toxic response of all bioavailable contaminants present in a sample. The objectives of this study were to evaluate the use of microbial contact toxicity tests for cadmium bioavailability assessment and to evaluate the relationship between sorption, soil characteristics and cadmium bioavailability.

Methods

A test soil bacterium,Bacillus cereus, was put in direct contact with the solid sample. Four unpolluted soils were selected to provide solid samples with a variety of physicochemical characteristics. The toxicity and sorption behaviour of cadmium spiked to the soil samples were determined.

Results, Discussion and Conclusions

A significant correlation between contact toxicity test results and partitioning of cadmium in the soil samples (r²= 0.79, p <0.05; n = 26) was found. The results confirm that the bioavailability of cadmium in soil depends on its sorption behaviour. Cadmium sorbed to the cation exchange sites associated with fulvic acids is non-bioavailable in the toxicity test employed in this study. It is concluded that the microbial contact toxicity test is a suitable tool for detecting cadmium bioavailablity in the soils used in this study.

Outlook

The application of microbial contact toxicity tests for bioavailability assessment can be very useful for the risk identification and remediation of soil-associated contaminants.     

土壤中有机污染物的老化及其环境意义

持久性有机污染物随着在土壤中时间的延长,其生物有效性和毒性会逐渐下降的现象被称为老化。老化对有机污染物的有效性和行为归趋有着重要的影响。本文对国外有关老化对有机污染物生物有效性和可浸提性的影响,老化的机理和影响因素,以及老化后有机污染物生物有效性评价方法的研究作了概述。指出老化作为土壤对有机污染物修复的一种自然修复过程,可降低有机污染物的潜在环境风险,具有重要的环境意义。     

生物质炭修复重金属及有机物污染土壤的研究进展

生物质炭是生物质原料在完全或部分缺氧条件下高温热解后的固体产物,它具有丰富的孔隙结构和较高的碳含量。该物质具有巨大的表面积和较强的阳离子交换能力等特殊性质,对受污染土壤中的重金属和有机物都具有很强的吸附能力,有效地降低这些污染物的生物有效性和在环境中的迁移,对改善土壤环境具有重大意义。近年来我国土壤污染严重,利用生物质炭修复受污染土壤的技术得到了广泛的关注。本文简述了生物质炭修复土壤污染的基本原理,探讨了与其他修复方法相比存在的优势,阐述了国内外近年来利用生物质炭修复污染土壤的研究进展,最后展望了今后需要进一步研究的领域。     

Extractability and Bioavailability of Mercury from a Mercury Sulfide Contaminated Soil in Oak Ridge, Tennessee, USA

Historically as part of its national security mission, the U.S. Department of Energy’s Y-12 National Security Facility in Oak Ridge, TN acquired a significant fraction of the world’s supply of elemental mercury. During the 1950s and 1960s, a large amount of elemental mercury escaped confinement and is still present in the watershed surrounding the Y-12 facility. A series of remediation efforts have been deployed in the watersheds around the Oak Ridge site. However, most recently, concentration of total mercury in fish and water of the lower East Fork Poplar Creek (EFPC) of Oak Ridge has increased although majority of the mercury contamination in the local soils is present in the form of mercury sulfide. We have studied the extractability, solubility, and bioavailability of mercury sulfide in Oak Ridge soils. Dynamics of the dissolution of mercury sulfide by various extractants, including acids and a chelating agent, have been investigated. After three seasons of planting, soil mercury sulfide is more easily dissolved by both 4 M and 12 M nitric acid than is pure mercury sulfide reagent as indicated by their dissolution kinetics. Mercury release by EDTA from HgS-contaminated soil increased with time of reaction and soil mercury level. This chelating chemical increases the solubility of mercury in HgS-contaminated Oak Ridge soil. The results also show that mercury sulfide in contaminated Oak Ridge soils was still to some extent bioavailable to plants. The increase of bioavailability of soil mercury sulfide after three seasons of planting may contribute to the recent increase of mercury levels in water of the Lower East Fork Popular Creek (LEFPC) of Oak Ridge.     

Availability of polycyclic aromatic hydrocarbons in aging soils

Purpose  

The soil contamination by hydrophobic organic contaminants (HOCs), such as polycyclic aromatic hydrocarbons (PAHs), poses great threats to human health and ecological security and attracts worldwide concerns. The total HOC concentrations overestimate its available fraction to the soil biota. Increased understanding of the availabilities of PAHs in soil environment will have considerable benefits for their risk assessment and be very instructive to food safety and remediation strategies in contaminated sites. However, the availability of PAHs in aging soils and particularly the correlations of the availabilities with their forms in soils have yet to be elucidated. In this work, the availabilities of PAHs in aging soils were evaluated using a sequential mild extraction technique.     

大范围土壤监测方案的一般问题: 综述

Numerous scientific challenges arise when designing a soil monitoring network (SMN), especially when assessing large areas and several properties that are driven by numerous controlling factors of various origins and scales. Different broad approaches to the establishment of SMNs are distinguished. It is essential to establish an adequate sampling protocol that can be applied rigorously at each sampling location and time. We make recommendations regarding the within-site sampling of soil. Different statistical methods should be associated with the different types of sampling design. We review new statistical methods that account for different sources of uncertainty. Except for those parameters for which a consensus exists, the question of testing method harmonisation remains a very difficult issue. The establishment of benchmark sites devoted to harmonisation and inter-calibration is advocated as a technical solution. However, to our present knowledge, no study has addressed crucial scientific issues such as how many calibration sites are necessary and how to locate them.     

Properties of an aged phenanthrene-contaminated soil and its response to bioremediation processes

Purpose  

Persistent organic compounds exhibit declining extractability and bioavailability to microorganisms and other soil organisms with increasing contact time or ageing. Among the possible mechanisms are the association of organic compounds with natural organic matter. Ageing can reduce the negative effects that an organic pollutant may have on the biological, biochemical properties and phytotoxicity of the contaminated soil. The aim of the present work was to evaluate, under laboratory conditions, the response of an agricultural soil contaminated with phenanthrene (Phe) and subjected to 2-year ageing and the effects and potential remediation capabilities of compost and an effective Phe-degrading bacterial culture.     

Effects-based Assays in the Earthworm Aporrectodea caliginosa: Their Utilisation for Evaluation of Contaminated Sites before and after Remediation (8 pp)

Goal, Scope and Background   In a preliminary ecological risk assessment, potential adverse effects of contaminants are often evaluated by measuring chemical residues and comparing these with regulatory guidelines. However limitations with this approach with regards to establishing actual effects have resulted in the increasing usage of sublethal effects-based assays, including biomarkers, to evaluate the hazard posed by contaminants in the environment. In this study a number of effects-based endpoints in the earthworm Aporrectodea caliginosa were evaluated to determine their comparative sensitivity for assessment of adverse effects of soil contaminated with petroleum hydrocarbons. Methods   Adult and juvenile earthworms were exposed for 4 weeks to sublethal concentrations of soil collected before and after remediation of a petroleum-contaminated site. A suite of endpoints were measured in these earthworms, including mortality, fecundity, growth, and juvenile maturation, and two less traditional endpoints, the biomarker, the neutral red retention assay (NRRA) and an avoidance behaviour test. Results and Discussion   Cocoon viability in this species is not a reliable parameter to measure, due to low viability in controls and a high coefficient of variation. Growth in adult earthworms was a more sensitive parameter than cocoon production. Maturation and growth of juveniles have been proposed as more sensitive endpoints than adult cocoon production and growth respectively. This was not apparent in the growth parameters, but maturation of juveniles did appear to be more sensitive than cocoon production by adults. The NRRA was a more sensitive parameter than cocoon production, and the NRRA and growth were both affected at the lowest concentration tested. The NRRA response appeared to be more sensitive than growth, but NRRT was only evaluated in one soil only, while the other parameters were assessed in two soils. However, the NRRA has previously been found to be more sensitive than growth after exposure to a number of contaminants. The avoidance behaviour assay exhibited similar sensitivity to growth and fecundity and could therefore be useful as a simple pre-screening test. Conclusion   The chronic endpoints, growth, cocoon production, and juvenile maturation parameters, were all sensitive endpoints for detecting exposure to the petroleum-hydrocarbon-contaminated soil. The NRRA was the most sensitive of the endpoints assessed and could be used as an early-warning indicator to predict adverse impacts. Avoidance behaviour could be used as a simple pre-screening test to evaluate contaminated soils prior to more extensive and invasive testing. Recommendations and Perspective   Measuring chemical concentrations in environmental samples is not always useful, as the toxicological impacts of exposure to these concentrations are not always discernible. However, the use of effects-based endpoints, either in situ or in the laboratory using laboratory-reared earthworms, can account for the bioavailability of chemicals in the soil, and can therefore provide information on the toxicological impacts of exposure. The assays tested in this research were sensitive indicators of exposure, and therefore can be used to determine potential ecological risks at contaminated sites and to monitor the progress of remediation at these sites.     

Organoclays reduce arsenic bioavailability and bioaccessibility in contaminated soils

Purpose  

Naturally occurring layer silicate clay minerals can be value added by modifying their surface properties to enhance their efficacy in the remediation of environmental contaminants. Silicate clay minerals modified by the introduction of organic molecules into the mineral structure are known as organoclays and show much promise for environmental remediation applications. The present study assesses the extent of decrease in bioavailable and bioaccessible arsenic (As) via enhanced adsorption by soil treated with organoclays.     

土壤中有机复合污染物微生物组转化机制与调控原理：进展与展望

实际污染土壤中有机污染物通常以复合污染状态存在,有机复合污染物的微生物降解过程及其作用机制显得更为复杂。土壤微生物类群多样,具有丰富的功能多样性。而有机复合污染物的降解通常由微生物组操控,通过微生物群落代谢网络完成污染物的去除。近年来,研究者逐渐关注有机复合污染土壤中微生物群落适应机制-微生物组转化过程-合成微生物组设计-原位微生物组修复等方面的研究,对认知污染土壤治理和修复具有重要的科学意义。本文以具有代谢协同性及功能互补性的微生物组为切入点,系统阐述土壤中有机复合污染物的微生物组转化机制与调控原理等,探讨微生物组在复合污染土壤绿色可持续原位生物修复中的发展前景。     

Effect of the initial soil water saturation on the behaviour of a mixed LNAPL and heavy metal contaminated glaciofluvial deposit

Soil contamination by mixtures of petroleum hydrocarbons and heavy metals is common in urban and industrial localities. Interactions between these contaminants have an impact on the mobility and the management of contamination. We have characterized the modifications to the transport of heavy metals (Cd, Cu, Pb, Zn) in soil induced by residual light non‐aqueous phase liquid (LNAPL) for two conditions of trapping. Experiments on the elution of tracers and heavy metals in columns of soil were performed with a glaciofluvial material as the soil. Tracer experiments were modelled with the mobile–immobile (MIM) system of partial differential equations. The experiments were designed to compare water flow and metal transport in LNAPL‐contaminated soil with a control set. Residual LNAPL was trapped in water‐saturated and dry soil to ensure preferential wettability of soil surfaces, namely either water‐wet or LNAPL‐wet. In water‐wet soil columns, LNAPL decreased water flow by two orders of magnitude and increased the fraction of immobile water. Solute residence times (SRTs) suggested that heavy metals resided mainly in mobile water where the reaction time was sufficient to reach steady‐state retention. The SRTs also indicated that a fraction of the heavy metal flux diffused to the immobile water where its retention was limited by diffusion. Retention of heavy metals was significantly greater than in the control columns. In LNAPL‐wet soil columns, the obstruction of small pores and surface coating by residual LNAPL significantly decreased the attenuation capacity of the soil by decreasing the diffusion of heavy metals to immobile water and surface sites. Evidently, the individual behaviour of heavy metals can be significantly modified by non‐miscible organic contaminants. These modifications can have important implications for risk evaluation, contamination management and in situ remediation of soil that is contaminated by mixtures of petroleum hydrocarbons and heavy metals.     

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。     

土壤中氯苯类化合物的归趋过程及潜在修复策略研究进展

Chlorobenzenes (CBs) are a group of organic pollutants that pose a high environmental risk due to their toxicity,persistence and possible transfer in the food chain.Available data in literature show that CBs are detected in different environmental compartments such as soil,water,air and sediment.The widespread presence of CBs in the environment is related to their former extensive use in agriculture and industry.Some CBs are ranked in the list of priority pollutants by the Stockholm Convention,and their reduction or elimination from the environment is therefore of high importance.Environmental risk assessment of CBs requires knowledge on the role and importance of the main environmental fate processes,especially in soil.Furthermore,development of remediation strategies for reduction or elimination of CBs from the environment is related to the enhancement of fate processes that increase their dissipation in various environmental compartments.The main objectives of the current review were to present up-to-date data on fate processes of CBs in the soil environment and to explore possible remediation strategies for soils contaminated with CBs.Dechlorination of highly-chlorinated benzenes is the main degradation pathway under anaerobic conditions,leading to the formation of lower-chlorinated benzenes.Biodegradation of lower-chlorinated benzenes is well documented,especially by strains of adapted or specialized microorganisms.Development of techniques that combine dechlorination of highly-chlorinated benzenes with biodegradation or biomineralization of lower-chlorinated benzenes can result in useful tools for remediation of soils contaminated with CBs.In addition,immobilization of CBs in soil by use of different amendments is a useful method for reducing the environmental risk of CBs.     

Bioavailability and toxicity of copper in soils: Integrating chemical approaches with responses of microbial biosensors

Copper (Cu) is a trace element essential for the healthy functioning of soil biological systems. However, at elevated concentrations Cu can be a potential toxicant. Consequently, an understanding of Cu availability and toxicity to soil biota is essential for effective ecological assessment of metal impacts in soil. The present study measured the response of a constitutive and Cu specific luminescence marked Pseudomonas fluorescens to Cu analytically determined in five soils.Conditioned Cu amended and historically contaminated soils were used. The free ion, soil pore water and solid-phase Cu were defined analytically by standard techniques frequently used to assess environmental availability of metals in soils, i.e. exchange resin, single and sequential metal extractions. The response of the constitutively expressed biosensor (i.e. a decrease in bioluminescence in the presence of Cu) assessed directly the toxicity of soil pore water Cu. The expression of bioluminescence by the bioreporter (i.e. an induction of bioluminescence by the presence of Cu) enabled quantification of Cu bioavailability in soil pore waters. Analytically determined Cu²⁺ concentrations strongly linked Cu toxicity to the biosensor responses and thus supported the conventional view of free metal ion toxicity in soil solutions. However, in two soils, other forms of Cu than free ion caused a response of the bioreporter, hence were bioavailable. Relationships between biological responses and analytically defined solid-phase Cu fractions identified pools of labile, potentially bioavailable Cu. As no single chemical method could be used to quantify bioavailable fraction of solid-phase Cu in all soils, the bioreporter provided analytical techniques with inherent biological relevance.This study demonstrates that Cu in soils with aged amendments of inorganic salts is more chemically available than in soils treated with sludge containing Cu. These differences are due to the concentration and form of Cu in the aqueous phase and the corresponding extractability of Cu in the soil solid phase. Bioreporter and biosensor validate the performance of rigorous analytical soil chemistry approaches. Their value in soil pollution should be considered a complementary technique rather than an alternative as their performance in complex environmental matrixes is yet to be validated.     

油葵和苦荬菜根际土壤中镉和锌的活化机制及修复潜力比较

  目的  研究油葵和苦荬菜根际土壤固、液相对镉（Cd）和锌（Zn）的活化机制,比较两种植物在轻、中度复合污染农田的修复潜力。  方法  通过大田试验种油葵和苦荬菜,测定成熟期土壤的pH值、有机酸、重金属总量及其生物有效性;测定土壤溶液中的溶解性有机质（DOM）、主要离子、水溶态重金属及其形态分布;测定植物各部位中重金属的浓度及形态,通过计算重金属在植物中的富集系数（BCF）和转运系数（TF）,比较两种植物对土壤重金属污染的修复潜力。  结果  油葵和苦荬菜根系分泌的低分子有机酸均使根际土壤pH值下降明显,显著低于非根际土壤（P < 0.05）;苦荬菜根际土中低分子有机酸及DOM的浓度显著高于油葵根际土（P < 0.05）。两种植物根际土壤溶液中的Cd以离子态和DOM结合态为主,Zn以离子态为主;两种植物根际土壤中有效态的Cd差异不显著,油葵根际有效态Zn显著高于苦荬菜;两种植物根际土壤的Zn和Cd有效态与土壤溶液中Cd-DOM和Zn-DOM呈显著相关。苦荬菜根对重金属的富集能力较强,但油葵地上部分能吸收转运更多的Cd和Zn,并在叶中以毒性较低的不溶性磷酸盐结合态和草酸结合态富集。  结论  两种植物根际分泌的有机酸可以增加根际土壤中的Cd-DOM和Zn-DOM的浓度,提高土壤中的Cd和Zn的有效性,苦荬菜根际对重金属有较强的活化能力,但油葵地上部分对Cd和Zn的吸收转运能力更强。两种植物都具有较强的土壤重金属修复潜力,但从经济角度出发,油葵更适合现阶段我国农田重金属污染的修复。     

Biodegradation combined with ozone for the remediation of contaminated soils

The effectiveness of the SS-SBR (Soil Slurry – Sequencing Batch Reactor) process for the remediation of soils contaminated by several organic pollutants has been evaluated. Experimental tests have been performed on two different soils, a spiked one and an industrial aged soil. The spiked soil, artificially contaminated, has been prepared trying to simulate the pollution of an industrial aged soil in terms of number and kind of contaminants. PAHs (Polycyclic Aromatic Hydrocarbons) and phenols degradation has been particularly investigated because they are considered persistent and recalcitrant. Concerning the spiked soil, removal efficiencies higher than 95% in 6 to 9 weeks have been found for all the pollutants, except for five-rings PAHs; however, these compounds were partly removed in 11 to 13 weeks. Good results have been achieved also for the industrial aged soil with a maximum removal of about 80% in 7–8 weeks. To enhance the pollutants degradation, trying to obtain a faster remediation, the biological treatment has been combined with a chemical oxidation with ozone. The best degradation effectiveness of the combined process has been obtained applying the ozonation after few days of the biological treatment. Therefore, a combined biological and chemical treatment allowed to markedly improve the remediation of contaminated soils.     

Influence of Water Content and Plants on the Dissipation of Chlorinated Volatile Organic Compounds in Soil

To devise effective procedures for the remediation of soil contaminated by VOCs, an improved understanding of their fate and transport mechanisms in soil is essential. To show the effect of plants on the dissipation of 1,1,1-trichloroethane (TCA), trichloroethylene (TCE) and tetrachloroethylene (PCE), two types of experiments, vial and column, were conducted. The results suggested that keeping the soil moisture content at field capacity is desirable for VOCs dissipation. All VOCs were dissipated quickly in unplanted columns than planted conditions in early periods of the experiment because more volatilization occurred in unplanted conditions. The plants could take up and retard volatile contaminants, and prevent contamination of ambient air. Although the time for acclimation for microbial communities to contaminants for enhanced biodegradation should be considered, phytoremediation is potentially a cost-effective remediation technique for soils contaminated by volatile organic compounds (VOCs).     

Effects of Grasses on the Fate of VOCs in Contaminated Soil and Air

Plant toxicity and chemical removal tests were conducted to investigate the remediation ability of grasses with respect to volatile organic contaminants (VOCs) in contaminated soil and air. Eastern gamagrass (Tripsacum dactyloides) and annual ryegrass (Lolium rigidum) were exposed to artificially contaminated soil or air containing a mixture of 1,1,1-trichloroethane (TCA), trichloroethylene (TCE), and tetrachloroethylene (PCE) under controlled laboratory conditions. The results showed that the grasses are more severely affected in hydroponics than potted soil contaminated with a mixture of these contaminants. It was observed from the results that more contaminants were detected in the shoot and root of plants grown in a closed system with contaminated air than in an open system with contaminated soil. It is suggested from the results that grasses can be used for purification of VOCs from contaminated air especially in a closed system, but the purification effects are likely to be low. The results also suggested that the concentration level of VOCs in shoot, root, and soil could be used as contamination indicator at contaminated sites.     

Bioavailability as a Factor in Risk Assessment of Metal-Contaminated Soil

To accurately assess the risks of metal contaminants in soil, the bioavailability of the metals need to be considered. The bioavailable concentrations determined from homogenized, dried soils are not necessarily representative of in situ conditions of undisturbed field soils. In this study, we investigated the accumulation of metals in wheat (Triticum aestivum) grown in undisturbed contaminated (Pb, Zn, Cu, and Cd) soil cores, in relation to total soil, leachate, and diffusive gradients in thin films (DGT)-labile metal concentrations. Despite the fact that many of the samples contained metal concentrations above guideline values, no significant effects were observed on wheat growth. The bioavailability of metals in the most contaminated samples was estimated to be medium to low, possibly explaining why few effects were observed in the bioassay. For Cu, Zn, and especially for Pb, leachate and DGT-labile concentrations were better predictors of uptake by wheat than total concentrations based on correlations. It is suggested that DGT and leachate concentrations in combination with bioassays in undisturbed soil cores can be used to account for metal bioavailability in soil. These tests could be used during the ecological risk screening stage, in conjunction with total concentrations and guideline values to better estimate receptor exposure.