Terrestrial Metals Bioavailability: A Comprehensive Review and Literature-Derived Decision Rule for Ecological Risk Assessment

Interstudy variation among bioavailability studies is a primary deterrent to a universal methodology to assess metals bioavailability to soil-dwelling organisms and is largely the result of specific experimental conditions unique to independent studies. Accordingly, two datasets were established from relevant literature; one includes data from studies related to bioaccumulation (total obs = 520), while the other contains data from studies related to toxicity (total obs = 1264). Experimental factors that affected toxicity and bioaccumulation independent of the effect of soil chemical/physical properties were statistically apportioned from the variation attributed to soil chemical/physical properties for both datasets using a linear mixed model. Residual bioaccumulation data were then used to develop a non-parametric regression tree whereby bootstrap and cross-validation techniques were used to internally validate the resulting decision rule. A similar approach was employed with the toxicity dataset as an independent external validation. A validated decision rule is presented as a quantitative assessment tool that characterizes typical aerobic soils in terms of their potential to sequester common divalent cationic metal contaminants and mitigate their bioavailability to soil-dwelling biota.     

Health Risk Assessment of Heavy Metals in Urban Soil of Karachi,Pakistan

The potential health risk due to lifetime exposure to copper, lead, chromium, zinc, and iron in urban soil of Karachi, Pakistan, was evaluated. Mean concentrations of Cu, Pb, Cr, Zn, and Fe in topsoil samples were 33.3 ± 12.8, 42.1 ± 55.8, 9.6 ± 4.2, 99.5 ± 37.3, and 908.4 ± 57.8 mg kg^?1, respectively. A U.S. Environmental Protection Agency model was adopted for the carcinogenic and non-carcinogenic risk assessment from different exposure pathways. Risk assessment indicated that the overall results for the carcinogenic risk were insignificant. However, the carcinogenic risk from Pb due to oral ingestion of soil exceeded the value of 1 × 10^?6, in some areas of the city. It indicates that the exposure to Pb-contaminated soil may cause adverse health effects in humans, especially in children. The Hazard Quotient (HQ) for different metals through ingestion and dermal pathways was also found to be less than 1. The combined Hazard Index (HI) for children through different routes of exposure was 8.9 times greater than for adults. It indicates that the children are more susceptible to non-carcinogenic health effects of trace metals compared to adults. Particularly, non-carcinogenic risk of Pb to children via oral ingestion needs special attention.     

Incorporating Information on Bioavailability of Soil-Borne Chemicals into Human Health Risk Assessments

Definition of the term bioavailability varies in the environmental sciences. In human health risk assessment, bioavailability is defined as the fraction of the dose of chemical delivered that is absorbed into the systemic circulation. Bioavailability can be expressed as either absolute or relative bioavailability, and both are important in calculating risks from contaminants in soils. Bioavailability of chemicals is addressed in all risk assessments, although not always in a transparent manner. Because data on bioavailability are limited, approximations and assumptions regarding chemical uptake are extensively used. The risk assessment process could benefit from new information on the bioavailability of chemicals, but there are important questions about the best means to develop this information and how it should be used. To foster discussion on these issues, three articles are presented in this issue of the journal offering different perspectives on bioavailability method development, validation, and use.     

Bioavailability of Soil-borne Chemicals: A Regulatory Perspective

U.S. Environmental Protection Agency (USEPA) risk assessment guidance documents dating back to 1989 have articulated the principles for incorporating information on bioavailability into the risk assessment process. However, in the interim period both the methods for obtaining media or route specific measures of bioavailability and the corresponding guidance to incorporate these data have languished. Presently, USEPA is developing guidance to address both of these concerns. This article outlines the broad framework for systematically evaluating the role of bioavailability in site-specific risk assessment from a regulatory perspective. At the same time, in appreciation of the vast horizon of uncharted territory ahead, the focus of USEPA's draft guidance, and consequently this report, is on bioavailability adjustments for soil-borne metals. The article describes a two-stage process. The first stage outlines a paradigm for screening sites to determine if generating site-specific data on the bioavailability of a metal in soil is of technical utility and economically justifiable. The second stage focuses on the collection, analysis, and incorporation of these data into the risk assessment for decision-making purposes.     

Assessment of Human Health Risk for an Area Impacted by a Large-Scale Metallurgical Refinery Complex in Hunan,China

Due to accelerated urbanization and reform of industrial structure in China, polluting industries in major cities have been closed or relocated. Consequently, large numbers of industrial sites were generated and the contaminated soils on and around these sites may pose risks to humans. This case study presents an estimation of human health risks for an area that is mainly impacted through air dispersion and deposition from a large-scale metallurgical refinery complex in Zhuzhou city, Hunan Province, China. Carcinogenic and non-carcinogenic risks posed by the contaminants were estimated under future industrial and residential land use scenarios. The result shows that adverse health effects may occur primarily through ingestion of soils contaminated with As, Cd, and Pb. The total carcinogenic risks of multiple contaminants for a large area exceed the acceptable risk level of 1 × 10^?5, and several localized hotspots, where the total hazard index exceeds 1 were identified. Soils in the Tongda site pose the highest carcinogenic risks and non-carcinogenic hazards. It is concluded that potential human health risks exist under the proposed redevelopment scenarios, and development of risk-based remediation strategies is recommended.     

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.     

Aquatic Risk Assessment of Metals in Sediment from South Florida Canals

A major watershed restoration effort is underway in south Florida, yet there are significant gaps in scientific information on exposure and risks of contaminants to its natural resources. We conducted a two-tier aquatic screening-level ecological risk assessment for metals that were monitored in sediment at 32 sampling sites in south Florida freshwater canals from 1990–2002. For tier 1, the chemicals (or metals) of potential ecological concern (COPECs) were identified as arsenic, cadmium, chromium, copper, lead, nickel and zinc based on their exceedences of Florida sediment quality guidelines at 10 sites. For tier 2, we used a probabilistic risk assessment method to compare distributions of predicted pore water exposure concentrations of seven metal COPECs with distributions of species response data from laboratory toxicity tests to quantify the likelihood of risk. The overlap of pore water concentrations (90th centile for exposure) for metal COPECs and the effects distributions for arthropods (10th centile of LC50s) and all species (10th centile of chronic NOECs) were used as a measure of potential acute and chronic risks, respectively. Arsenic (25%) in the Holey Land tracts, in Broward County north of Everglades National Park (ENP), and chromium (25%) in the C-111 freshwater system, at the east boundary of ENP, were the most frequently detected COPECs in sediment. Antimony (6%), zinc (6%) and lead (5%) were the least frequently detected COPECs in sediment. The 90th centile concentrations for bulk sediment were highest for zinc (at S-178) and lead (at S-176) in the C-111system. The 90th centile concentration for pore water exposure was highest for arsenic in the Holey Land tracts and lowest for cadmium and chromium. The estimated acute 10th centile concentration for effects was lowest for copper and arthropods. The probabilities of pore water exposures of copper exceeding the estimated acute 10th centile concentration from the species sensitivity distributions (SSD) of acute toxicity data (for arthropods) were 57 and 100% for copper at S-177 and S-178 in the C-111 system, respectively. The probability of pore water exposures of copper exceeding the estimated NOEC 10th centile concentration from the SSD of chronic toxicity data (for all species) was 93 and 100% for copper at S-177 and S-178, respectively. Uncertainties in exposure and effects analysis and risk characterization are identified and discussed. The study presents a straightforward approach to estimate exposure and potential risks of metals detected in sediment from south Florida canals.     

Risk Assessment of the Abandoned Jukjeon Metal Mine in South Korea Following the Korean Guidelines

Toxic metal contamination in the vicinity of Korean abandoned metal mines has been reported. A risk assessment for these metals was performed for the inhabitants in the area of the abandoned Jukjeon metal mine. Soil, groundwater, and crop samples were collected around the mine. After pretreatment of these samples, metal concentrations were measured and then a risk assessment was performed using the Korean soil-contamination risk assessment guidelines. Phytoaccumulation of metals in crops was observed in soybeans (As and Zn), red peppers (Zn), sweet potatoes (As and Zn), and cabbage (Cu), which had higher metal concentrations than soils in the area. The metal intake rate was highest for inhalation of soil. Cancer risk was highest from ingestion of As-contaminated crops. The sum of carcinogenic risks was 6.29 × 10^–3. The non-carcinogenic risk was highest for ingestion of As-contaminated crops (8.17). Most of the risks were attributable to As, Pb, and Hg contamination, therefore these three metals must be considered as the principal metals toxic to human health in the sampled area. In particular, the inhalation of metal-contaminated soil should be considered for risk assessment along with ingestion of water and crops in abandoned mine areas.     

Human Health Risk Assessment for Environmental Exposure to Metals in the Catalan Stretch of the Ebro River,Spain

The aim of this study was to investigate the environmental impact and the human health risks associated with metals exposure in the Catalan stretch of the Ebro River, Spain. The concentrations of the following elements were determined in soils and tap water: As, Cd, Cr, Cu, Hg, Mn, Ni, and Pb. Carcinogenic and non-carcinogenic risks were separately assessed for adults and children. Relatively low metal concentrations in tap water were found. It indicates that water intake is not a relevant source of metals for human health impact in the area under evaluation. In turn, the levels of metals in soils were similar or less than those found in a number of recent worldwide surveys. The presence of industrial facilities located upstream the Ebro River, including a chloralkali plant, should not mean additional non-carcinogenic risks for the population living in the area. The results of the current study allow us to establish that the concentrations of most carcinogenic elements (with the exception of As) should not mean potential health risks for the local population. However, because of the relatively high levels of geological origin found for As, a continued monitoring of these elements would be desirable.     

Heavy Metal Contamination in Urban Surface Soil of Klang District (Malaysia)

This study aimed to determine bioavailability of heavy metal concentrations (Al, Fe, Zn, Cu, Co, Cd, Pb and Cr) in 76 urban surface soil samples of Klang district (Malaysia). This study also aimed to determine health risks posed by bioavailability of heavy metals in urban soil on adults and children. For bioavailability of heavy metal concentrations, a physiologically bioavailability extraction test in vitro digestion model was used. Mean values of bioavailability heavy metal concentrations for this study were found to be the highest in Al (25.44 mg/kg) and lowest in Cr (0.10 mg/kg). Results of Spearman correlation coefficient (r) values showed significant correlations were observed for Al-Fe (r = 0.681), Cd-Co (r = 0.495), Cu-Zn (r = 0.232), Fe-Pb (r = 0.260), Fe-Zn (r = 0.239). For cluster analysis, output showed that these heavy metals could be classified into four clusters: Cluster 1 consisted of Cd, Cr, Co, and Pb; Cluster 2 consisted of Zn and Cu; Cluster 3 consisted of Fe; and Cluster 4 consisted of Al. For Clusters 1 and 2, anthropogenic sources were believed to be the sources, while for Clusters 3 and 4 the heavy metals originated from natural sources. Health risks were determined in adults and children through health risk assessment. For adults, Hazard Quotient (HQ) value was <1, indicating no non-carcinogenic risk, while for children, the HQ value was >1, indicating a non-carcinogenic risk. Meanwhile, for carcinogenic risk, heavy metal contamination in the Klang district might not pose a carcinogenic risk to adults while it may pose a carcinogenic risk to children because TR values in this study were >1.0E-04 for children. Output has identified the general health risk in the Klang district. Moreover, this study's findings will contribute to fill in the gap of knowledge on heavy metals' impacts on human health and urban development in the Klang District.     

Health Risk Assessment of Heavy Metals in Soils and Vegetables from a Typical Greenhouse Vegetable Production System in China

There is growing concern about food safety and environmental contamination due to potential health risks to consumers. The aims of this study are to elucidate the accumulation status, influencing factors, and potential risk of selected heavy metals in soils and vegetables from a typical greenhouse vegetable production system in China. The potential health risks of heavy metals through soil contact and vegetable consumption were evaluated for greenhouse and corresponding open field production. The results indicated that the mean concentrations of Hg, Pb, Cu, and Zn in greenhouse vegetable soils were greater than those in open field soils. Leaf vegetables had relatively higher concentrations and transfer factors of heavy metals than root and fruit vegetables, especially for Cd. The target hazard quotient of heavy metals through vegetable consumption was greater than 1 for leaf vegetables, and was also higher for greenhouse vegetables than those from open field. The risk of exposure to heavy metals through direct contact with soil and vegetable consumption was higher for children than for adults and seniors. Planting patterns with different vegetable types and soil properties can affect bioavailability and crop accumulation of heavy metals.     

Assessing the Bioavailability and Risk from Metal-Contaminated Soils and Dusts

Exposure to contaminated soil and dust is an important pathway in human health risk assessment. Physical and chemical characteristics and biological factors determine the bioaccessibility/bioavailability of soil and dust contaminants. Within a single sample, contamination may arise from multiple sources of toxic elements that may exist as different species that impact bioavailability. In turn, the bioaccessibility/bioavailability of soil and dust contaminants directly impacts human health risk. Research efforts focusing on development and application of in vitro and in vivo methods to measure the bioaccessibility/bioavailability of metal-contaminated soils have advanced in recent years. The objective of this workshop was to focus on developments in assessing the bioaccessibility/bioavailability of arsenic-contaminated soils, metals’ contamination in urban Canadian residences and potential children's exposures to toxic elements in house dust, an urban community-based study (i.e., West Oakland Residential Lead Assessment), bioavailability studies of soil cadmium, chromium, nickel, and mercury and human exposures to contaminated Brownfield soils. These presentations covered issues related to human health and bioavailability along with the most recent studies on community participation in assessing metals’ contamination, studies of exposures to residential contamination, and in vitro and in vivo methods development for assessing the bioaccessibility/bioavailability of metals in soils and dusts.     

Assessment of Human Health and Ecological Risks Posed by the Uses of Steel-Industry Slags in the Environment

Steel-industry slag, a co-product of iron and steel production, is produced and sold for use in a wide range of applications. A comprehensive study of the potential human health risks associated with the environmental applications (e.g., fill, roadbase, landscaping) of iron- and steel-making slag was performed using characterization data for 73 samples of slag collected from blast furnaces, basic oxygen furnaces, and electric arc furnaces. Characterization data were compared to regulatory health-based “screening” benchmarks to determine constituents of interest. Antimony, beryllium, cadmium, trivalent and hexavalent chromium, manganese, thallium, and vanadium were measured above screening levels and were assessed in an application-specific exposure assessment using standard U.S. Environmental Protection Agency risk assessment methods. A stochastic analysis was conducted to evaluate the variability and uncertainty in the inhalation exposure and risk estimates, and the oral bioaccessibility of certain metals in the slag was quantified. The risk assessment found no significant hazards to human health as a result of the environmental applications of steel-industry slag. However, site-specific ecological risk assessment may be required for slag applications in and around small water bodies with limited dilution volume, because high pH and aluminum were found to leach at levels that may be harmful to aquatic life     

Soil Heavy Metal Pollution Assessment Near the Largest Landfill of China

To assess the extent and potential hazards of heavy metal pollution at Shanghai Laogang Landfill, the largest landfill in China, surface soil samples were collected near the landfill and concentrations of Cu, Zn, Cd, Pb, and Cr were determined. The results revealed that the concentrations of heavy metals, except Pb, were higher in the surface soil near the landfill than in the background soil. Principal component analysis and hierarchical cluster analysis suggested that the enrichment of Cu in soil was probably related to agricultural activities and Cd and Pb to landfill leachates, whereas Zn and Cr concentrations were probably controlled by soil matrix characteristics. The pollution indices (PIs) of the metals were: Cd > Cu > Cr > Zn > Pb. Among the five measured metals, Cd showed the largest toxic response and might cause higher ecological hazards than other metals. The integrated potential eco-risk index (RI) of the five metals ranged from 26.0 to 104.9, suggesting a low-level eco-risk potential. This study indicated the accumulations of Cu, Zn, Cd, Pb, and Cr did not reach high pollution levels, and therefore posed a low eco-risk potential in surface soil near the landfill.     

Metals in Northern Forest Ecosystems: Role of Vegetation in Sequestration and Cycling,and Implications for Ecological Risk Assessment

Mass estimates of phytoaccumulated trace metal contaminants and transfers to soils are necessary to properly evaluate the impact of historic and continued anthropogenic metal deposition to northern forest ecosystems. An investigation of Cu, Ni, Pb, and Zn mass balances in plant communities subject to metal contamination from smelter emissions in Canada, found that accumulation of metals differed significantly among plant vegetation compartments (foliage, fine roots, bark, trunk, and branches). Analysis of plant community biological accumulation factors (BAFs), calculated using total soil metal and free soil metal ion (Me²⁺) found that free soil metal BAFs were more similar among locations than total soil metal BAFs, but that disparity still existed. Fine roots were found to dominate annual vegetation transfer of Cu, Ni, and Pb to soils, relative to foliage; fine root mortality played a smaller role than foliage for Zn plant-soil transfer. Plant-associated metal inputs were found to rival or exceed current estimates of atmospheric metal deposition, suggesting that potential benefits of future reductions in emissions to forests need to be evaluated within the context of phytocycling of metals already present.     

Identifying Metals Contamination in Soil: A Geochemical Approach

The geochemical evaluation methodology described in this paper is used to distinguish contaminated samples from those that contain only naturally occurring levels of inorganic constituents. Site-to-background comparisons of trace elements in soil based solely on statistical techniques are prone to high false positive indications. Trace element distributions in soil tend to span a wide range of concentrations and are highly right-skewed, approximating lognormal distributions, and background data sets are typically too small to capture this range. Geochemical correlations of trace versus major elements are predicated on the natural elemental associations in soil. Linear trends with positive slopes are expected for scatter plots of specific trace versus major elements in uncontaminated samples. Individual samples that may contain a component of contamination are identified by their positions off the trend formed by uncontaminated samples. In addition to pinpointing which samples may be contaminated, this technique provides mechanistic explanations for naturally elevated element concentrations, information that a purely statistical approach cannot provide. These geochemical evaluations have been successfully performed at numerous facilities across the United States. Removing naturally occurring constituents from consideration early in a site investigation reduces or eliminates unnecessary investigation and risk assessment, and focuses remediation efforts.     

Framework for Human Health Risk Assessment

The views expressed in this paper are those of the authors and do not necessarily reflect the views or policies of the USEPA. The U.S. Government has the right to retain a nonexclusive royalty-free license in and to any copyright covering this article. The U.S. Environmental Protection Agency has recognized the need to develop a framework for human health risk assessment that puts a perspective on the approaches in practice throughout the Agency. In response, the USEPA's Risk Assessment Forum has begun the process of developing a framework for human health risk assessment. This paper provides some additional background to the previous review of the framework efforts and notes the Agency's extramural efforts to begin the process of integrating and harmonizing risk assessment approaches for all human health endpoints.     

Assessment of Pollution-Induced Microbial Community Tolerance to Heavy Metals in Soil Using Ammonia-Oxidizing Bacteria and Biolog Assay

This study attempted to investigate if the tolerance of soil bacterial communities in general, and autotrophic ammonia-oxidizing bacteria (AOB) in particular, evolved as a result of prolonged exposure to metals, and could be used as an indigenous bioindicator for soil metal pollution. A soil contaminated with copper, chromium, and arsenic (CCA) was mixed with an uncontaminated garden soil (GS3) to make five test soils with different metal concentrations. A modified potential ammonium oxidation assay was used to determine the metal tolerance of the AOB community. Tolerance to Cr, Cu, and As was tested at the beginning and after up to 13 months of incubation. Compared with the reference GS3 soil, the five CCA soils showed significantly higher tolerance to Cr no matter which form of Cr (Cr³⁺, CrO₄ ^2?, or Cr₂O₇ ^2?) was tested, and the Cr tolerance correlated with the total soil Cr concentration. However, the tolerance to Cu²⁺, As³⁺, and As⁵⁺ did not differ significantly between the GS3 soil and the five CCA soils. Community level physiological profiles using Biolog microtiter plates were also used to examine the chromate tolerance of the bacterial communities extracted after six months of exposure. Our results showed that the bacterial community tolerance was altered and increased as the soil Cr concentration was increased, indicating that the culturable microbial community and the AOB community responded in a similar manner.     

Environmental Risks of Inorganic Metals and Metalloids: A Continuing,Evolving Scientific Odyssey

Ecological risk assessment (ERA) of metals, metalloids, and inorganic metal substances (collectively referred to as metals) no longer focuses solely on persistence and bioaccumulation, but rather on solubility, toxicity, natural occurrence (concentrations above/added to background), essentiality (deficiency as well as excess), speciation, and bioavailability. Tolerance (both acclimation and adaptation) and possible resultant energetic costs are being considered, and realism is being increased in laboratory toxicity tests by the use of organisms pre-acclimated to natural levels of metals. The present status of ERAs for inorganic metals is summarized in terms of four key questions: (1) Do metals accumulate in biota above background levels? (2) Are these metals metabolically active? (3) If so, are they likely to result in adverse effects to individuals either alone or in combination with other stressors? (4) If so, are they likely to result in adverse impacts to populations? The most pragmatically useful future research will be that focused on the interactive risks of both complex chemical mixtures (metals and non-metals) and non-chemical stressors (both biotic and abiotic). Ideally this should occur in the context of continued metal loadings to terrestrial and aquatic ecosystems assessed holistically, including trophic food web relationships, metal transfer, and genetic diversity. Relationships between environmental concentrations and internal, metabolically active doses are the key to understanding and predicting environmental risks without excessive reliance on safety factors.     

Non-Carcinogenic Risk Assessment of Heavy Metals and Fluoride in Some Water Wells in the Al-Baha Region,Saudi Arabia

On a global scale, pathogenic contamination of drinking water poses the most significant health risk to humans. However, significant risks to human health may also result from exposure to nonpathogenic, toxic contaminants that are often ubiquitous in waters. The purpose of this study is to determine the levels of heavy metal and fluoride contaminants in water wells used in the Al-Baha region, Saudi Arabia, to evaluate if the levels of metals will have non-carcinogenic effects. Samples were collected from private wells in the area and were analyzed for chemical contamination using approved methods of collection and analysis. Chromium, manganese, zinc, iron, and fluoride were detected in all samples, and were selected for toxicological evaluation. Exposure through ingestion and dermal contact were the scenarios proposed in this study. Chronic daily intakes (CDIs) were estimated for both routes and then compared with health guideline values. The non-cancer risk estimations show that manganese, chromium, and zinc individually have oral Hazard Quotient (HQ) values less than a value of one. Iron and fluoride were found to have oral HQ values greater than 1 in some samples. Also, on considering the additive effect of the contaminants we found that some samples have Hazard Index (HI) values greater than 1, which indicates that there is a concern for chronic non-cancer adverse health effects in case of oral and dermal routes of exposure to water from these wells.