Uncertainties in the Environmental Risk Assessment of Metals

As life has evolved in the presence of metals, the assessment of the potential adverse effects of metals on ecosystems requires a different approach than those presently used for man-made organic substances. This article provides a brief review of applications and limitations of current techniques and presents, based on recent research results, suggestions for improving the scientific relevance and accuracy of environmental risk assessments of metals. The importance of the following factors responsible for major uncertainties in current environmental risk assessments of metals are discussed: factors affecting metal bioavailability and toxicity, the potential importance of deficiency effects (for essential metals), and field extrapolation of laboratory toxicity data. Possible (regulatory) consequences of inaccurately assessing the natural background concentrations of metals and acclimatization/adaptation potential of laboratory organisms and resident communities are illustrated using examples of recent research, hypothesis development, and a probabilistic environmental risk assessment.     

Issues in Ecological Risk Assessment of Inorganic Metals and Metalloids

Ecological risk assessment (ERA) is a process that evaluates the potential for adverse ecological effects occurring as a result of exposure to contaminants or other stressors. ERA begins with hazard identification/problem formulation, progresses to effects and exposure assessment, and finishes with risk characterization (an estimate of the incidence and severity of any adverse effects likely to occur). Risk management initially sets the boundaries of the ERA and then uses its results for decision-making. Key information required for an ERA includes: the emissions, pathways and rates of movement of contaminants in the environment; and, information on the relationship between contaminant concentrations and the incidence and (or) severity of adverse effects. Because of specific properties and characteristics of metals in general and of certain metals in particular, a generalized ERA process applicable to organic substances is inappropriate for metals. First, metals are naturally occurring and can arise, sometimes in very high concentrations, from non-anthropogenic sources; organisms can and do adapt to a wide range of metal concentrations. Second, certain metals (e.g., copper, zinc) are essential for biotic health, which means there is an effect threshold for both deficiency and excess, and that standard body burden indices such as bioaccumulation factors (BCFs) can be misleading. Third, metals can occur in the environment in a variety of forms that are more or less available to biota but adverse biological effects can only occur if metals are or may become bioavailable. Fourth, whereas the bioavailability and hence the possibility of toxicity of persistent organic substances are mainly dependent on their intrinsic properties (i.e., lipophilicity), those of metals are generally controlled by external environmental conditions. Examples include pH and ligands, which affect the metal speciation and coexisting cations (e.g., H⁺, Ca²⁺) which compete with the metal ions. ERAs involving metals must include the above four major considerations; other considerations vary depending on whether the ERA is for a site, a region, or is global in scope.     

Conducting Ecological Risk Assessments of Inorganic Metals and Metalloids: Current Status

Ecological risk assessment (ERA) of inorganic metals and metalloids (metals) must be specific to these substances and cannot be generic because most metals are naturally occurring, some are essential, speciation affects bioavailability, and bioavailability is determined by both external environmental conditions and organism physiological/biological characteristics. Key information required for ERA of metals includes: emissions, pathways, and movements in the environment (Do metals accumulate in biota above background concentrations?); the relationship between internal dose and/or external concentration (Are these metals bioreactive?); and the incidence and severity of any effects (Are bioreactive metals likely to result in adverse or, in the case of essential metals, beneficial effects?) — ground-truthed in contaminated areas by field observations. Specific requirements for metals ERA are delineated for each ERA component (Hazard Identification, Exposure Analysis, Effects Analysis, Risk Characterization), updating Chapman and Wang (2000). In addition, key specific information required for ERA is delineated by major information category (conceptual diagrams, bioavailability, predicted environmental concentration [PEC], predicted no effect concentration [PNEC], tolerance, application [uncertainty] factors, risk characterization) relative to three different tiered, iterative levels of ERA: Problem Formulation, Screening Level ERA (SLERA), and Detailed Level ERA (DLERA). Although data gaps remain, a great deal of progress has been made in the last three years, forming the basis for substantial improvements to ERA for metals.     

Probabilistic Risk Assessment and Risk Mapping of Sediment Metals in Sydney Harbour Embayments

Sediment metal concentrations in embayments of Sydney Harbour, acquired from the literature and from samples collected for this study, were used to generate contaminant probability density distributions using AQUARISK. The sediment metal concentrations often exceeded Australia's interim sediment quality guidelines. Similarly, estuarine spiked sediment toxicity test literature provided adverse biotic effects concentration data to generate species sensitivity distributions using AQUARISK. Although the harbor is subject to other inorganic and organic contamination, we have used sediment metals to demonstrate an approach for ecological risk mapping and environmental management prioritization. Sufficient spiked sediment toxicity test data were found for only three metals—Cd, Cu, and Zn—and some tests were likely to overestimate toxicity. The estimates of the hazardous concentration to 5% of species (the 50th percentile of the 95% species protection level) were 5, 12, and 40 mg/kg DW of total sediment metal for Cd, Cu, and Zn, respectively. These values were generally low when compared with the interim sediment quality guidelines due to the overestimation of toxic effects in the literature data. The parameters for the species sensitivity distributions have been combined with the measured sediment metal concentrations in Homebush Bay to generate risk maps of the estimated species impact for each metal as well as for all three metals collectively assuming proportional additivity. This has demonstrated the utility of comparing contaminants on a consistent scale—ecological risk.     

Heavy metal sorption by microalgae

Viable microalgae are known to be able to accumulate heavy metals (bioaccumulation). Against a background of the increasing environmental risks caused by heavy metals, the microalgae Chlorella vulgaris and Spirulina platensis and their potential for the biological removal of heavy metals from aqueous solutions were taken as an example for investigation. Small-scale cultivation tests (50 1) with Cd-resistant cells of Chlorella vulgaris have shown that approx. 40% of the added 10 mg Cd/l was removed from the solution within seven days. At this heavy metal concentration sensitive cells died. Non-viable microalgae are able to eliminate heavy metal ions in a short time by biosorption in uncomplicated systems, without any toxicity problems. Compared with original biomasses, the sorption capacity of microalgal by-products changes only insignificantly. Their low price makes them economical.     

Effects of Chronic Waterborne and Dietary Metal Exposures on Gill Metal-Binding: Implications for the Biotic Ligand Model

The biotic ligand modeling (BLM) approach has gained recent widespread interest among the scientific and regulatory communities because of its potential for developing ambient water quality criteria (AWQC), which are site-specific, and in performing aquatic risk assessment for metals. Currently, BLMs are used for predicting acute toxicity (96?h LC50 for fish) in any defined water chemistry. The conceptual framework of the BLM has a strong physiological basis because it considers that toxicity of metals occurs due to the binding of free metal ions at the physiologically active sites of action (biotic ligand, e.g., fish gill) on the aquatic organism, which can be characterized by conditional binding constants (log K) and densities (B_max). At present, these models assume that only water chemistry variables such as competing cations (e.g., Na⁺, Ca²⁺, Mg²⁺, and H⁺), inorganic ligands (e.g., hydroxides, chlorides, carbonates), and organic ligands (dissolved organic matter) can influence the bioavailability of free metal ions and thereby the acute toxicity of metals. Current BLMs do not consider the effects of chronic history of the fish in modifying gill-metal binding characteristics and acute toxicity. Here, for Cu, Cd, and Zn, we review a number of recent studies on the rainbow trout that describe significant modifying effects of chronic acclimation to waterborne factors (hardness and chronic metal exposure) and dietary composition (metal and essential ion content) on gill metalbinding characteristics (on both log K and B_max) and on acute toxicity. We conclude that the properties of gill-metal interaction and toxicological sensitivity appear to be dynamic rather than fixed, with important implications for further development of both acute and chronic BLMs. Now that the initial framework of the BLM has been established, future research needs a more integrative approach with additional emphasis on the dynamic properties of the biotic ligand to make it a successful tool for ecological risk assessment of metals in the natural environment.     

土壤重金属生物毒性研究进展

世界范围内土壤重金属污染不断加重,由污染所带来的问题以及如何治理污染已经受到人们越来越多的关注.土壤重金属将对土壤生物产生影响,而土壤生物在重金属的胁迫下也会产生不同的响应.综述了国内外近年来土壤重金属生物毒性的研究进展,介绍了土壤重金属污染对陆地生态系统中植物、动物和微生物生长的影响;土壤重金属生物毒性的影响因素;土壤重金属生物毒性的研究方法;土壤重金属生物毒性的预测模型,最后提出了问题和展望.     

Toxicity of cadmium and zinc to Diplostomum spathaceum (Trematoda: Diplostomidae) cercarial survival

The toxicity of cadmium and zinc at concentrations ranging from 0.1 to 10000 microg/l was investigated with cercariae of Diplostomum spathaceum at three temperatures (12, 20, 25 degrees C) and three levels of water hardness (distilled water, soft water, hard water). Under most environmental conditions survival of cercariae was reduced by increasing metal concentration. Increasing water hardness and decreasing water temperature caused an increase in the survival of both control and metal exposed cercariae. However, with decreasing temperature increased survival of metal-exposed cercariae above the control occurred at a number of low metal concentrations. Differences in the relative toxicity of cadmium and zinc to cercariae was dependent on the environmental conditions of exposure. The two heavy metals demonstrated little toxicity to cercariae during the period of maximum cercarial infectivity (0-5 h).The mechanisms of metal toxicity and their effects on cercarial survival are discussed.     

Scientific and societal considerations in selecting assessment endpoints for environmental decision making

It is sometimes argued that, from an ecological point of view, population-, community-, and ecosystem-level endpoints are more relevant than individual-level endpoints for assessing the risks posed by human activities to the sustainability of natural resources. Yet society values amenities provided by natural resources that are not necessarily evaluated or protected by assessment tools that focus on higher levels of biological organization. For example, human-caused stressors can adversely affect recreational opportunities that are valued by society even in the absence of detectable population-level reductions in biota. If protective measures are not initiated until effects at higher levels of biological organization are apparent, natural resources that are ecologically important or highly valued by the public may not be adequately protected. Thus, environmental decision makers should consider both scientific and societal factors in selecting endpoints for ecological risk assessments. At the same time, it is important to clearly distinguish the role of scientists, which is to evaluate ecological effects, from the role of policy makers, which is to determine how to address the uncertainty in scientific assessment in making environmental decisions and to judge what effects are adverse based on societal values and policy goals.     

Human Health Risk of Metals in Drinking-Water Source Areas from a Forest Zone after Long-Term Excessive Deforestation

The concentrations of 10 metals (As, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Se, Zn) were determined in drinking water in Khingan, China, a forest zone after long-term excessive deforestation. These metals’ concentrations in water exceeded background values of metals in some other regions of the world, indicating that there were other metal sources contributing to such high levels of metals in Khingan. Arsenic was the only metal whose concentration exceeded the maximum levels allowed in drinking water. Principal component analysis showed that As, Cd, Cu, and Se originated from anthropogenic sources and exhibited significantly high concentrations in north Khingan, while Fe and Mn derived from natural formation and showed significantly high concentrations in central Khingan. Health risks from metals were evaluated by a model recommended by the U.S. Environmental Protection Agency. Ingestion was the predominant pathway of exposure to metals in water for local residents. Arsenic was also the only metal causing both noncarcinogenic hazard and carcinogenic risk in Khingan. The high risks occurred mainly in north Khingan and are associated with coal combustion. This study indicates that long-term excessive deforestation may increase As concentration considerably in drinking water and then pose health risks to local residents.     

Chemical speciation of some heavy metals and human health risk assessment in soil around two municipal dumpsites in Sagamu,Ogun state,Nigeria

Environmental and health risk posed by heavy metals from municipal landfill cannot be over emphasized. However, the toxicity and fate of metal in the soil is dependent on its chemical form and therefore quantification of the different forms of metal is more meaningful than the estimation of its total concentration. This study investigated the chemical form and potential hazards of heavy metal pollution at two municipal landfills in Sagamu, Ogun state, Nigeria. Soil samples were collected around the landfills and chemical form of Cu, Zn, Cd, Pb, and Fe were studied, using the Tessier Five-step sequential chemical extraction procedure. The results showed that Cu and Fe were speciated into residual fractions with averages of 23.9 and 31.3% respectively, while Cd and Zn were associated with Carbonate fractions with respective averages of 20.3 and 20.6%. The order of mobility and bioavailability of these metals are: Cd > Pb > Cu > Zn > Fe. A comparison of the result of total extractible metals with standard set by USEPA reveals that Cd and Cu level in the dumpsite soils are far above the critical permissible limit of 3.0 and 250 mg kg^?1, respectively which potent a health risk. Assessment of soil pollution level using geoaccumulation index (I_geo) revealed that the landfill was extremely polluted by Cd (I_geo > 5). Pearson correlation and principal component analysis showed that there were no significant correlations (p < 0.05) among all the metals, suggesting that they are all from different anthropogenic sources. The cancer risk ranged from 1.36E?01 to 2.18E?04 and 5.82E?01 to 9.35E?04 for Children and Adult respectively. The level of cancer risk falls above the threshold values (10^?4–10^?6) which US Environmental Protection Agency considered as unacceptable risk. Based on the above findings, it was suggested that environmental management policy should be implemented to decrease the environmental risks.     

Structural diversity of microorganisms in chemically perturbed soil assessed by molecular and cytochemical approaches

Until recently, our understanding of microbial community development in soil ecosystems exposed to different inorganic and organic pollutants has been limited to culturable microorganisms because of the techniques available. The discovery that most soil microorganisms are non-culturable but potentially viable and metabolically active accelerated the application of different culture-independent methods for structural diversity assessments of the microbial community. This review examines the results of recent studies on the impact of heavy metals and organic pollutants on the diversity of the microflora obtained with methods based on analyses of signature biomarkers such as nucleic acids and fatty acids. The application of these techniques allowed researchers to pinpoint reduction of microbial diversity in contaminated soil, and significant shifts in the community structure, leading to the dominance of only a few populations (species) and the disappearance of others, some of which were never isolated by conventional methods (e.g. an increase in Acidobacterium or a decrease in terrestrial non-thermophilic Crenarchaeota). Although the new techniques are not free from limitations, they allow the monitoring of the virtual impact of stressors on soil microorganisms and the direction of resuscitation of the microbial community during natural or induced bioremediation, especially when using combined approaches.     

EDTA-Enhanced Phytoremediation of Heavy Metals: A Review

The increase in heavy metal terrestrial ecosystems’ contamination through anthropogenic activities is a widespread and serious global problem due to their various environmental and human implications. For these reasons, several techniques, including phytoremediation of heavy metals, have been extensively studied. In spite of significant recent advancement, ethylene diamine tetraacetic acid (EDTA)-enhanced heavy metal phytoextraction as well as related ecological risks are still topical and remain an important area of research. In fact, EDTA favors the solubilization of metals and metalloids in soils, and was therefore extensively studied during the last two decades in order to improve phytoextraction efficiency and reduce treatment duration. This review highlights the recent findings (2010–2012) and mechanisms behind EDTA-enhanced (1) solubilization of heavy metals in soil, (2) mobilization/transport of soluble metals towards plant root zone, and (3) metal absorption by plant roots and translocation towards aerial parts. The review also presents potential risks associated with EDTA-enhanced phytoextraction: (1) environmental persistence of EDTA and/or metal-EDTA complex; (2) potential toxicity of EDTA and/or metal-EDTA complex to plants; and (3) leaching and contamination of groundwater. Moreover, field-scale cost of EDTA-enhanced remediation and the role of EDTA in time required for heavy metal remediation is discussed.     

Importance of Clean Techniques and Speciation in Assessing Water Quality for Metals

Trace metals in aquatic and soil systems exist in a number of different soluble and particulate forms that impact the effect of the metals on these ecosystems. Appropriate methods of sampling and analysis are required to accurately determine the low concentrations present. Although assessment of metals in many regulatory programs is based on data for total metal concentrations, such values rarely correlate with effects. Consequently, other means are needed for the prediction of risk. Bioavailability of metals depends on their speciation, whose importance was first established for copper in aquatic systems where the toxicity of metals is related to the activity of the free metal ion. Small concentrations of natural organic matter strongly complex metals ameliorating toxicity. Several electroanalytical techniques are available that allow the assessment of metal species. Recently, a modeling approach, the Biotic Ligand Model (BLM), has been applied to the prediction of acute toxicity. The model accounts for the effects of natural organic matter, pH, and hardness and is able to predict toxicity over several orders of magnitude of soluble metal concentration using only easily determined site parameters. Total metal concentrations in sediment cover several orders of magnitude with no distinction of sediments that cause effects and those that do not except at low total metal concentrations. Relating the metal concentration to the concentrations of sulfide and organic matter binding sites enables the sediments containing higher concentrations of metals to be divided into those that do and those that do not have adverse effects. It is essential that metal speciation be considered to realistically evaluate the potential of metals to pose risk.     

Heat shock protein genes in the green alga Tetraselmis suecica and their role against redox and non-redox active metals

Microalgae are capable of tolerating variations in water temperature and sudden exposures to toxic substances, and cellular heat shock proteins (HSPs) help to protect cells from such stress. Here, we determined the complete open reading frames (ORF) of small TsHSP20 and large TsHSP70 and 100 in the chlorophyte Tetraselmis suecica, and examined the expression levels of these genes after exposure to thermal stressors, redox-active metals, and non-redox-active metals. Putative TsHSP20, TsHSP70, and TsHSP100 proteins had conserved HSP-family motifs with different C-terminus motifs. Phylogenetic analyses of individual HSPs showed that T. suecica clustered well with other chlorophytes. Real-time PCR analysis showed that thermal stress did not significantly change the expression of all the tested TsHSPs. In addition, TsHSP20 showed little gene expression after being exposed to copper, whereas TsHSP70 and 100 genes greatly responded to the redox-active metals in CuSO₄ followed by CuCl₂, but not to the non-redox active metals. Redox-active metals strongly affected the physiology of the cells, as judged by cell counting, reactive oxygen species imaging and photosynthetic efficiency. These findings suggest that small and large HSPs are differentially involved in the response against environmental stressors. Moreover, metal toxicity may be specifically controlled by the anions in the metal compounds.     

An Ecological Risk Assessment of Air Emissions of Trace Metals from Copper and Zinc Production Facilities

Trace metals are components of releases to air emitted by copper and zinc production facilities in Canada. Six metals (copper, zinc, nickel, lead, cadmium, and arsenic) are examined as part of an overall environmental assessment of these releases. Estimates of metal deposition rates to soils and surface waters were derived from monitoring data in the vicinity of the production facilities and also through dispersion modelling studies. Fate and transport modelling of the metals deposited allowed an estimation of critical loads. Estimated annual deposition rates were compared with 25^th-percentile critical loads typically representative of effects on sensitive organisms under 25% of conditions in sandy soils or circumneutral to acidic lake waters. The results of the comparison suggest that there is a potential for adverse effects on aquatic and/or soil-dwelling organisms from exposure to steadystate concentrations of metals in the vicinity of copper and zinc production facilities. Approaches of particular significance in these assessments include probabilistic estimation of critical loads for metals, allowance for the speciation of metals defining the bioavailable fraction and limiting critical effect levels to the high end of natural background metal concentrations.     

Selenium detoxification of heavy metals: a possible mechanism for the blood plasma

Among the activities of the essential trace element selenium is the ability to reduce the toxicity of heavy metal ions like cadmium(II) and mercury(II). Detoxification often depends on the metabolic reduction of selenium to hydrogen selenide; the mechanism generally advanced to explain such selenium/metal interactions is that selenide combines with heavy metal ions to give a metal selenide which is metabolically inert. However, this hypothesis does not consider circumstances where selenide is quickly removed by other reactions. Given the ease with which selenide is oxidized, such conditions are likely to occur in the blood plasma, an environmental rich in oxidizing agents and a site for many selenium/metal interactions. Using polarography to monitor both selenide and cadmium, we have found that selenide reacts rapidly in vitro with the disulfide bonds present in bovine serum albumin in preference to forming cadmium selenide. We hypothesize that a similar reaction occurs in the blood plasma with the disulfide bonds of plasma proteins to generate thiol groups on the protein involved, and that these newly formed thiols are responsible for the observed reduction of metal toxicity through the ability to chelate heavy metal ions.     

Development and validation of an experimental life support system for assessing the effects of global climate change and environmental contamination on estuarine and coastal marine benthic communities

An experimental life support system (ELSS) was constructed to study the interactive effects of multiple stressors on coastal and estuarine benthic communities, specifically perturbations driven by global climate change and anthropogenic environmental contamination. The ELSS allows researchers to control salinity, pH, temperature, ultraviolet radiation (UVR), tidal rhythms and exposure to selected contaminants. Unlike most microcosms previously described, our system enables true independent replication (including randomization). In addition to this, it can be assembled using commercially available materials and equipment, thereby facilitating the replication of identical experimental setups in different geographical locations. Here, we validate the reproducibility and environmental quality of the system by comparing chemical and biological parameters recorded in our ELSS with those prevalent in the natural environment. Water, sediment microbial community and ragworm (the polychaete Hediste diversicolor) samples were obtained from four microcosms after 57 days of operation. In general, average concentrations of dissolved inorganic nutrients (NO₃^?; NH₄⁺ and PO₄^?3) in the water column of the ELSS experimental control units were within the range of concentrations recorded in the natural environment. While some shifts in bacterial community composition were observed between in situ and ELSS sediment samples, the relative abundance of most metabolically active bacterial taxa appeared to be stable. In addition, ELSS operation did not significantly affect survival, oxidative stress and neurological biomarkers of the model organism Hediste diversicolor. The validation data indicate that this system can be used to assess independent or interactive effects of climate change and environmental contamination on benthic communities. Researchers will be able to simulate the effects of these stressors on processes driven by microbial communities, sediment and seawater chemistry and to evaluate potential consequences to sediment toxicity using model organisms such as Hediste diversicolor.     

The environmental risks of pollution in the Scheldt estuary

The ecotoxicological effects of pollution in the Scheldt estuary is evaluated for several routes of exposure by comparing observed concentrations of micro-contaminants in water and tissues of biota with toxicity data in literature. Ecological risks are estimated for dissolved trace metals according to the method of VAN STRAALEN (1990) using published data on NOECs from aquatic toxicity tests concerning reproduction, mortality and growth for cold blooded marine and estuarine organisms. Of eight investigated trace metals, zinc and nickel cause the highest risks, both affecting up to 4% of the aquatic species. The occurrence of bioaccumulation of PCBs and cadmium is investigated in several trophic levels. High concentrations of PCBs are observed in tissues of biota and may indicate adverse effects on top predators (seals, terns), especially in the brackish zone. Environmental risks of other organic micro-contaminants have not been indicated due to the limited number of data on toxicity or environmental concentrations. The effects of a mixture of pollutants in sediments from the Scheldt estuary were investigated with an oyster larvae bioassay showing an increased toxicity in upstream direction. Moreover, in the upper part of the estuary, preconditions regarding the oxygen concentration are not met and overshadow the toxic effects of pollution with micro-contaminants. Especially in the less contaminated part of the estuary more ecotoxicolgical research is required to perform an integral risk evaluation. At present, still little is known about effects that may occur in the field.     

Nutritional factors in relation to heavy metal toxicants.

An increased environmental exposure to various toxic heavy metals such as lead, cadmium, or mercury seems to be a fact of 20th-century life. But relatively little attention has been paid to the possible implications of sucy exposure for the nutritional status of humans and animals. This review summarizes the information available concerning the effect of various nutritional factors in resistance to metal toxicants and the effect of heavy metal toxicity on nutritional status. In particular, the following questions are considered: 1) Are there any examples of heavy metal toxicity that are potentiated by a nutritional deficiency? 2) Is there any evidence that nutritional deficiency can be caused by heavy metal toxicity? 3) Is there any proof that heavy metal toxicity can be decreased by an excess intake of nutrients: 4) Is there any proof that heavy metal toxicity can be increased by an excess intake of nutrients? The discussion is focused primarily on studies with animal models but, wherever possible, implications for human health are pointed out.