Dynamics of trace metals in organisms and ecosystems: prediction of metal bioconcentration in different organisms and estimation of exposure risks

Metal ions interact with biological materials and their decomposition products by ligation (coordination complex-formation with certain moieties containing O, N, S, etc.). The extent of this interaction depends on the identities of both ligand and metal ion and can be described by some equation derived from perturbation theory. Uptake of metal ions - including highly toxic ones - from soils is controlled by a competition between root exudate components and soil organic matter (SOM) for the ions. SOM consists of a variety of potential ligands which evolve during humification towards more efficient binding (retention) of metals such as Cu, Ni, Cr but also of toxicants like U, Cd. The actual way of interaction can be inferred from stoichiometry of the involved compounds and the C/N ratio in the soil, providing predictions as to which metals will be most efficiently shuttled into green plants or fungi, respectively. The latter, selective process is crucial for closing nutrient cycles and sensitively depends on C/N ratio and the extent of "forcing" by onfalling leaf or needle litter. Therefore, analytical data on the soil can be used to predict possible risks of exposition to toxic metals also for human consumption of plant parts.     

Waterborne and sediment toxicity of fluoxetine to select organisms

Ecological risk assessments of pharmaceuticals are currently difficult because little-to-no aquatic hazard and exposure information exists in the peer-reviewed literature for most therapeutics. Recently several studies have identified fluoxetine, a widely prescribed antidepressant, in municipal effluents. To evaluate the potential aquatic toxicity of fluoxetine, single species laboratory toxicity tests were performed to assess hazard to aquatic biota. Average LC(50) values for Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas were 0.756 (234 microg/l), 2.65 (820 microg/l), and 2.28 microM (705 microg/l), respectively. Pseudokirchneriella subcapitata growth and C. dubia fecundity were decreased by 0.044 (14 microg/l) and 0.72 microM (223 microg/l) fluoxetine treatments, respectively. Oryias latipes survival was not affected by fluoxteine exposure up to a concentration of 28.9 microM (8.9 mg/l). An LC(50) of 15.2 mg/kg was estimated for Chironomus tentans. Hyalella azteca survival was not affected up to 43 mg/kg fluoxetine sediment exposure. Growth lowest observed effect concentrations for C. tentans and H. azteca were 1.3 and 5.6 mg/kg, respectively. Our findings indicate that lowest measured fluoxetine effect levels are an order of magnitude higher than highest reported municipal effluent concentrations.     

Solid phase microextraction as a tool to predict internal concentrations of soil contaminants in terrestrial organisms after exposure to a laboratory standard soil

Uptake and accumulation of three chlorobenzenes was studied in both biota (Enchytraeus crypticus) and 30 mum polydimethylsiloxane (PDMS) solid phase microextraction (SPME) fibers after exposure to spiked OECD soil. The OECD soil was spiked with three different concentrations of all contaminants. Uptake of all three chlorobenzenes in E. crypticus was fast and steady state levels were reached within 2-4 days. Also in the PDMS-SPME fibers uptake was very fast for all three compounds, with steady state levels reached after 1 day. Comparison of steady state levels in biota and in the PDMS-SPME fibers showed a relationship which was consistent over the range of concentrations of chlorobenzenes in soil and the difference in logKow. This shows that measuring the concentrations of hydrophobic chemicals in a hydrophobic phase such as PDMS can be used as a simple tool to estimate internal concentrations of these chemicals in biota exposed to complex matrices such as soil.     

Experimental approaches and analytical techniques for determining organic compound bound residues in soil and sediment

Research has shown that many chemicals form persistent and permanently bound residues in soils and sediments that play an important role in soil and sediment detoxification processes, long-term compound partitioning behaviour and compound bioavailability and toxicity in soil and sediment. This article reviews the methodological approaches that have been applied to determine the nature of bound residues in soil and sediment, the application of specific analytical techniques, the type of information they generate, and their relative advantages and disadvantages. It begins by defining bound residues and discussing soil-compound interactions. The application of model compound studies for elucidating specific binding interactions is reviewed along with long-term laboratory and field soil incubation experiments. The use of radiolabelled compounds, isotopically labelled compounds and combinations of both in these experiments are outlined by examples from the literature, along with sequential extraction schemes for releasing bound residues from soil, sediment and humic materials. The importance of spectroscopic methods, and particularly nuclear magnetic resonance techniques for characterising the structure of bound residues in soil and sedimentary humic substances is discussed and illustrated by examples from the literature on the subject. The process of bound residue formation is highly complex and requires further research to establish the mechanisms of bound residue formation and their subsequent environmental and toxicological fate. Much of the uncertainty regarding the elucidation of bound residue formation arises from our poor understanding of the structure of soil and sedimentary organic matter. Significant advances in our understanding of the formation and fate of bound residues will be made when we develop a deeper insight into the complex and heterogeneous structure of soil and sedimentary organic matter.     

Bioavailability and biodegradation of prosulfocarb in soil

Active microbial degraders of the herbicide prosulfocarb (PSC) were isolated to evaluate their performance in soil with a view to their use for bioremediation. The isolated cultures (a microbial consortium and a Pseudomonas sp. strain) were active when tested in mineral medium with PSC as the only carbon source, but had an adverse effect on the soil indigenous microflora. Biodegradation in the inoculated soils was thus lower than in the uninoculated soil when only the indigenous microflora was present. Further tests showed that the strong affinity of PSC for soil organic matter affected its bioavailability and hence its biodegradation by the inocula. Bioremediation of PSC contaminated soils could thus be undertaken by biostimulation of indigenous microflora.     

土壤/沉积物中重金属生物有效性和生物可利用性的研究进展

土壤/沉积物中重金属的污染问题越来越引起重视,而重金属在环境中的生态风险与其生物可利用性和生物有效性密切相关。在总结国内外研究的基础上,明确了重金属生物有效性和生物可利用性的定义;概述了用于研究土壤/沉积物中重金属生物有效性的生物模型(小鼠、猪、兔子等);总结了用于研究土壤/沉积物中重金属生物可利用性的几种体外方法,包括模拟人类肠胃消化(PBET、SBRC、UBM等)和底栖生物消化;分析了土壤/沉积物中重金属生物有效性和生物可利用性的关键影响因素(土壤/沉积物理化性质和分析方法)。提出了未来土壤/沉积物中重金属生物有效性和生物可利用性的研究方向,以期为重金属生态风险的评价和控制提供参考。     

Bioavailability of polychlorinated dibenzo-p-dioxins and dibenzofurans from contaminated Wisconsin River sediment to carp

The bioavailability of 2,3,7,8-TCDD from sediment to freshwater fish was studied in laboratory exposures. Carp (10g) exposed to Wisconsin River sediment (39 pg/g) for 55 days accumulated 7.5 pg/g. Maintaining exposured fish in clean water for an additional 205 days resulted in depuration of 32–34% TCDD. These values compare to field data where sediments ranged from 30–200 pg/g and 1.5 kg carp (70 pg/g) depurated 55% in 325 days. Analysis of sediment, laboratory exposed fish, and Wisconsin River fish for other PCDDs and PCDFs showed residues of 2,3,7 and 8 substituted congeners selectively enriched.     

Behavior of Chlorpyrifos-methyl in soil and sediment

This research was carried out with the aim of obtaining information regarding the possible environmental impact of Chlorpyrifos-methyl, an organophosphoric insecticide used in agriculture for its phytoiatric action against Hemiptera, Lepidoptera, Coleoptera, and Diptera. Studies relating to the degradation kinetics of the insecticide in two soils and one sediment have shown a rapid degradation process in all three. The prevalent form of degradation would appear to be the chemical type, because the degradation kinetics in a sterile soil have not demonstrated that micro-organisms play a significant part. The adsorption isotherms showed that the insecticide has a greater affinity for the sediment (Kf=143) as opposed to the soils (Kf=65) and that the adsorption process is practically irreversible. Moreover, hydrolysis tests in buffered solutions at pH 4, 7, and 9 revealed that the molecule is particularly unstable with a basic pH.     

生物沥滤去除污泥、土壤和底泥中3种重金属比较研究

以硫酸亚铁为底物,对城市污泥、土壤和河流底泥进行生物沥滤实验,探讨了污泥、底泥和土壤在沥滤过程中重金属的去除效果和化学形态转化规律,了解当地土壤在酸化条件下重金属的释放过程,并对三者的研究结果进行比较分析。结果表明,污泥生物沥滤对重金属（Zn、Cu和Pb）的沥滤的沥滤效果较佳（去除率75.45%、63.12%和40.96%）。沥滤过程中,重金属Cu在生物沥滤中期（3~5 d）沥出效果较好,而Zn和Pb则在沥滤后期（5~9 d）。同一重金属在不同沥滤体系中的形态变化过程差异较大,沥滤后的污泥、土壤和底泥中的重金属大部分呈现稳定状态。     

Avoidance test with Enchytraeus albidus (Enchytraeidae): effects of different exposure time and soil properties

Enchytraeids are ecologically relevant soil species and are commonly used in standardized toxicity tests. Their rapid reaction to a chemical exposure can be used as a toxicological measurement endpoint that assesses the avoidance behavior. The objectives of this investigation were to determine the effects of soil properties on the avoidance behavior of Enchytraeus albidus and to optimize the duration of avoidance test. The avoidance tests included (1) exposures in OECD artificial soil with standard or modified properties (pH, clay or peat content), and (2) exposures to copper chloride, cadmium chloride, and to the organic pesticides dimethoate and phenmedipham for different time periods. Results showed that alteration of OECD soil constituents significantly affected the avoidance behavior of enchytraeids, and that the 48-h exposure was the optimal duration of the test. Consideration of soil properties is important for selecting appropriate experimental design and interpreting the results of the enchytraeid avoidance test.     

Phosphorus and copper leaching from dredged sediment applied on a sandy loam soil: column study

In this paper, downward movement of phosphorus and copper as dredged sediment applied on sandy loam soil was studied by column leaching experiments. Three sediment application rate, (i.e., 1, 2 and 5-cm depth of sediments) were applied to the top of the soil columns. Two and a half months leaching experiments were conducted, which include a 15-day un-watered period. Concentrations of phosphorus and copper in the leachate and the vertical distribution of Olsen-P and diethylenetriaminepentaacetic acid (DTPA) extractable Cu in the soil columns were determined. The results showed that, un-watered period could increase the downward movements of phosphorus and copper. Sediment application significantly increased Olsen-P concentration in the top 15 cm of the soil columns, but has not significantly affected that in the deeper soil layer. The 1-cm depth sediment treatment did not increase the DTPA extractable Cu concentration in the whole soil column. The 5-cm depth sediment treatment, however, significant increased the DTPA extractable Cu in the deeper soil layers. This study suggested that the application of dredged sediment laden with P and Cu on sandy loam soil might cause the significant downward movement of phosphorus and copper.     

Surface metal adsorption on zooplankton carapaces: implications for exposure and effects in consumer organisms

The current study aimed to determine the potential of two important aquatic invertebrate crustacean species, Daphnia magna and Ceriodaphnia dubia, to adsorb cadmium on to their carapaces from aqueous solution. Using the Langmuir equation to model data outputs, it was shown that cadmium readily became associated with the carapace surfaces of both species, with uptake being dependent on exposure time and concentration. Maximum carapace-adsorption potential was found to be directly related to surface area, so that at predicted carapace saturation, D. magna neonates bound approximately five times more cadmium than the smaller C. dubia neonates. However, adsorption per unit surface area was found to be similar under the same exposure conditions. Results of surface metal adsorption studies in C. dubia suggested that short term exposures to high concentrations of aqueous cadmium would lead to similar levels of adsorption as obtained with long-term exposures to low concentrations. The study illustrates that contaminants adsorbed to prey surfaces may be an important mechanism of exposure to predators, and highlights some potential problems of feeding organisms during long-term toxicity tests.     

Modeling time-dependent toxicity to aquatic organisms from pulsed exposure of PAHs in urban road runoff

Understanding of the magnitude of urban runoff toxicity to aquatic organisms is important for effective management of runoff quality. In this paper, the aquatic toxicity of polycyclic aromatic hydrocarbons (PAHs) in urban road runoff was evaluated through a damage assessment model. Mortality probability of the organisms representative in aquatic environment was calculated using the monitored PAHs concentration in road runoff. The result showed that the toxicity of runoff in spring was higher than those in summer. Analysis of the time-dependent toxicity of series of runoff water samples illustrated that the toxicity of runoff water in the final phase of a runoff event may be as high as those in the initial phase. Therefore, the storm runoff treatment systems or strategies designed for capture and treatment of the initial portion of runoff may be inappropriate for control of runoff toxicity.     

Effects of low dissolved oxygen on organisms used in freshwater sediment toxicity tests

Minimum dissolved oxygen requirements are part of standard guidelines for toxicity testing of freshwater sediments with several benthic invertebrates, but the data underlying these requirements are somewhat sparse. We exposed three common test organisms to ranges of dissolved oxygen concentrations to determine their responses in 10-d exposures, relative to published guidelines for sediment toxicity tests. The oligochaete, Lumbriculus variegatus, showed 100% survival in all exposures down to the lowest concentration tested, 0.7 mg O(2)l(-1). Midge (Chironomus dilutus) larva showed a more pronounced response; while survival was less than 90% only below 1.0mg O(2)l(-1), the biomass endpoint showed EC(50), EC(20), and EC(10) values of 1.00 (0.91-1.10), 1.41 (1.16-1.71), and 1.67 (1.25-2.24) mg O(2)l(-1). The amphipod, Hyalella azteca, showed no adverse effects at concentrations as low as 2.12 mg O(2)l(-1). The combination of these data with other literature data suggest that DO minima in current North American 10-d sediment test guidelines are reasonable.     

Bioavailability assessment and environmental fate of polycyclic aromatic hydrocarbons in biostimulated creosote-contaminated soil

When hydrocarbon-contaminated soil is subjected to bioremediation technology, hydrocarbon depletion is typically marked by an initially rapid reduction rate. This rate decreases over time and frequently a residual concentration remains in the soil. This kinetic has been attributed primarily to the enrichment of more recalcitrant fractions, as well as to the lack of resting hydrocarbon bioavailability. Thus, at the end of the bioremediation process, a part of the residual hydrocarbon soil concentration represents the non-bioavailable fraction, which is difficult to degrade by microbial populations and which poses a minor hazard. Therefore, determination of the bioavailable fraction in a bioremediation project represents both an estimation of the maximum level of achievable biodegradation, as well as an additional indication of the environmental health hazard. In the present study, aged creosote-contaminated soil was subjected to biostimulation processes, and the bioavailable fraction for several target polycyclic aromatic hydrocarbons (PAHs) was calculated using a mild extraction with cyclodextrines. The amount of PAH extracted corresponded to the desorbing fraction and can be regarded as the bioavailable fraction. The non-desorbing fraction data obtained from this procedure were compared to the remaining PAH concentrations following bioremediation treatment of soil microcosms. These results permitted the establishment of a theoretical biodegradation limit based on the desorbing fraction. In addition, neither accumulation of intermediate metabolites, nor the formation of bound-residues or reduced acute toxicity was observed.     

Bioavailability of selenium to forage crops in a sandy loam soil amended with Se-rich plant materials

Greenhouse experiments were conducted to study the bioavailability of selenium (Se) to sorghum (Sorghum bicolor L.), maize (Zea mays L.) and berseem (Trifolium alexandrinum L.) fodders in a sandy loam soil amended with different levels of Se-rich wheat (Triticum aestivum L.) and raya (Brassica juncea L. Czern) straw containing 53.3 and 136.7microg Seg(-1), respectively. Each of the fodder crops was grown after incorporation of Se-rich materials either individually or in a sequence - sorghum-maize-berseem by incorporating Se-rich straws only to the first crop. Application of Se-rich straws to each crop, even at the greatest rate of 1%, did not have any detrimental effect on dry matter yield of different crops. With increase in the level of wheat straw from 0% to 1%, Se content in sorghum and maize plants increased to greatest level of 1.3 and 1.5microg g(-1), respectively, at 0.3% of applied straw and thereafter it decreased consistently. In case of raya straw, the greatest Se content in sorghum (2.3microg g(-1)) and maize (3.0microg g(-1)) was recorded at 0.3% and 0.4% of the applied straw, respectively. Unlike sorghum and maize fodders, Se content in all the four cuts of berseem continued to increase with increase in the level of applied straws and for different cuts of berseem it varied from 1.6 to 2.3 and 3.4 to 4.3microg g(-1) in case of wheat and raya straw, respectively. Similar variations in Se content of different fodder crops were recorded when these were grown in the sequence - sorghum-maize-berseem; but Se content was 2-4 times lower than when each crop was grown with fresh application of Se-rich straw. None of the fodders absorbed Se in levels toxic for animal consumption (>5microg g(-1)) even at the greatest level of applied straw. Of the total Se added through Se-rich straws, utilization of Se was not more than 2% in case of sorghum and maize crops and up to 5% in case of berseem. At the time of sowing of sorghum, hot water soluble Se (HWS-Se) in soils treated with different levels of Se-rich wheat and raya straw, respectively, varied from 18 to 36 and 18 to 79microg kg(-1). Whereas in case of berseem, it varied from 33 to 101 and 33 to 154microg kg(-1), respectively. HWS-Se present at the sowing time of berseem was significantly correlated with Se content of all the four cuts in the soil treated with Se-rich straws; the coefficients of correlation 'r' varied between 0.79 (p0.05) and 0.99 (p0.001). Selenium-rich materials supplied significant amounts of S, P and micronutrients to the growing fodder crops. These investigations suggest that Se-rich raya and wheat straw may be disposed off safely in soils used for growing fodders.     

Assessing sediment hazard through a weight of evidence approach with bioindicator organisms: a practical model to elaborate data from sediment chemistry, bioavailability, biomarkers and ecotoxicological bioassays

Quality assessments are crucial to all activities related to removal and management of sediments. Following a multidisciplinary, weight of evidence approach, a new model is presented here for comprehensive assessment of hazards associated to polluted sediments. The lines of evidence considered were sediment chemistry, assessment of bioavailability, sub-lethal effects on biomarkers, and ecotoxicological bioassays. A conceptual and software-assisted model was developed with logical flow-charts elaborating results from each line of evidence on the basis of several chemical and biological parameters, normative guidelines or scientific evidence; the data are thus summarized into four specific synthetic indices, before their integration into an overall sediment hazard evaluation. This model was validated using European eels (Anguilla anguilla) as the bioindicator species, exposed under laboratory conditions to sediments from an industrial site, and caged under field conditions in two harbour areas. The concentrations of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and trace metals were much higher in the industrial compared to harbour sediments, and accordingly the bioaccumulation in liver and gills of exposed eels showed marked differences between conditions seen. Among biomarkers, significant variations were observed for cytochrome P450-related responses, oxidative stress biomarkers, lysosomal stability and genotoxic effects; the overall elaboration of these data, as those of standard ecotoxicological bioassays with bacteria, algae and copepods, confirmed a higher level of biological hazard for industrial sediments. Based on comparisons with expert judgment, the model presented efficiently discriminates between the various conditions, both as individual modules and as an integrated final evaluation, and it appears to be a powerful tool to support more complex processes of environmental risk assessment.     

Bioavailability of PCDD/F from contaminated soil in young Goettingen minipigs

For the general population the intake of food of animal origin is the main route of human exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). Besides this the ingestion of contaminated soil might be an important exposure path for small children. For risk assessment the knowledge of the bioavailable fraction of soil bound contaminants is important. In a balance study with young Goettingen minipigs the oral bioavailability of PCDD/F from contaminated soil was estimated by determination of the retention of PCDD/F from soil in different organs and tissues. Relative bioavailability was estimated by comparing the retention from soil to the retention of PCDD/F in organs and tissues after oral administration of a PCDD/F mixture extracted from the same soil by solvent. The soil had a PCDD/F-contamination of 5.3 microg I-TEq/kg and originated from a former arable land that had been treated with sludge from the port of Hamburg some years ago. Two groups of each four animals were exposed daily for 28 days via their diet either to 0.5 g soil per kg body weight and day (2.63 ng I-TEq/(kg(bw).d)) or to a daily dose of 1.58 ng I-TEq/(kg(bw).d) given to the diet by solvent. Five unexposed animals were used as a control group. Liver, adipose tissue, muscle, brain and blood were analyzed for their PCDD/F content. Accumulation of PCDD/F from soil or solvent in comparison to control animals was only observed for congeners with 2378-chlorosubstitution and predominantly took place in the liver. Bioavailability of 2378-chlorosubstituted congeners was in the range of 0.64%-21.9% (mean: 10.1%) from soil and 2.8%-59.8% (mean: 31.5%) when administered by solvent. The soil matrix reduced the bioavailability by about 70%. Expressed as I-TEq only 13.8% of the PCDD/F contamination were bioavailable from soil. The relative bioavailability of 2378-chlorosubstituted congeners from soil in relation to administration by solvent was in the range of 2%-42.2% (mean: 28.4%). When not considering the bioavailability, the risk by oral uptake of PCDD/F contaminated soil might be overestimated.     

Hydrocarbon pollution fixed to combined sewer sediment: a case study in Paris

Over a period of two years (2000-2001), sediment samples were extracted from 40 silt traps (STs) spread through the combined sewer system of Paris. All sediment samples were analysed for physico-chemical parameters (pH, organic matter content, grain size distribution), with total hydrocarbons (THs) and 16 polycyclic aromatic hydrocarbons (PAHs) selected from the priority list of the US-EPA. The two main objectives of the study were (1) to determine the hydrocarbon contamination levels in the sediments of the Paris combined sewer system and (2) to investigate the PAH fingerprints in order to assess their spatial variability and to elucidate the PAH origins. The results show that there is some important inter-site and intra-site variations in hydrocarbon contents. Despite this variability, TH and PAH contamination levels (50th percentile) in the Parisian sewer sediment are estimated at 530 and 18 microg g(-1), respectively. The investigation of the aromatic compound distributions in all of the 40 STs has underlined that there is, at the Paris sewer system scale, a homogeneous PAH background pollution. Moreover, the study of the PAH fingerprints, using specific ratios, suggests the predominance of a pyrolytic origin for those PAHs fixed to the sewer sediment.