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.     

Fractionation,Source Identification and Risk Assessments for Heavy Metals in Soils near a Small-Scale Industrial Area (Çanakkale-Turkey)

Contamination of soils by heavy metals due to urbanization increases various environmental concerns. The objective of this research was to determine the potential sources of heavy metals in agricultural soils in the vicinity of a small-scale industrial area and to assess their environmental impacts. Soil samples were obtained from 15 different locations near a small industrial area in the Çanakkale province of Turkey. Heavy metal (Cd, Co, Cu, Ni, Pb, Zn) contents of soil samples were determined with four different geochemical fractions via a sequential extraction procedure. The results revealed that pseudo-total heavy metal concentrations were ordered in decreasing order as Zn > Pb > Cu > Ni > Co > Cd. Considering the results, Cd (1.95 ± 0.12 µg/g), Pb (39.21 ± 2.14 µg/g) and Zn (64.99 ± 8.16 µg/g) values were above the normal values specified for agricultural lands. The findings obtained from sequential extraction procedure showed that Cd (78%) and Pb (65%) existed mostly in mobile phases. Such mobile phases originated mostly from anthropogenic sources. These findings were also supported by chemometric analyses. Risk assessments pointed out that while Pb and Zn have moderate risks on the environment, Cd creates high risks.     

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.     

Distribution and Risk Assessment of Heavy Metals in the Xinzhuangzi Reclamation Soil from the Huainan Coal Mining Area,China

The contamination of coal-mine soil by heavy metals is a widespread problem. This study analyzes the heavy metals (Cu, Zn, Ni, Pb, Cr, Cd, and Hg) found in 33 surface soil samples from Xinzhuangzi, China restored coal-mining land used as cultivated land. The results show that the selected elements were cumulative, especially for Cd. An index of geo-accumulation indicates that the soil was practically uncontaminated by Cu, Zn, Ni, and Hg, uncontaminated to moderately contaminated by Pb and Cr, and moderately to heavily contaminated by Cd. Based on the U.S. Environmental Protection Agency's ecological soil screening levels (Eco-SSLs) for Cu, Zn, Ni, Pb, and Cd and the Dutch Target and Intervention Values for Cr and Hg, the plants and soil invertebrates were not likely greatly influenced by the selected metals. Although the Cd concentration was found to have no significant effect on plants and soil invertebrates, it is the only metal with a concentration significantly above that required by Chinese standards (HJ/T 332–2006) for edible agricultural products, indicating that Cd is the predominant factor that determines the use of the reclaimed coal-mining area for farmland. Thus, employing the reclaimed land as farmland may not be a good option.     

Plan for an Integrated Human and Environmental Risk Assessment in the S. Domingos Mine Area (Portugal)

The need for the integration of the assessment of human and ecological risks in contaminated areas, such as derelict mines, widely increases. The risk assessment process is becoming a powerful tool to provide sound scientific bases for decision-making processes. In Portugal, the risk assessment process is in its early years and the lack of multidisciplinary teams of experts is frequently mentioned as the main obstacle to its implementation. Therefore, the majority of the reclamation actions are based on impact assessment studies that usually are characterized by few biological and toxicological considerations. In order to account for some of these constraints, the ecological risk assessment framework proposed by the U.S. Environmental Protection Agency was used to plan the assessment of human and ecological risks posed by the high concentrations of metals scattered in the vicinity of S. Domingos mine, a cuprous pyrite mine located in the Southeast Alentejo (Portugal). This study presents the problem formulation phase of the assessment. It includes all the scientific information available for the area, a conceptual model, and an analysis plan for the risk assessment process. Following a tiered approach, several tasks were planned in order to acquire chemical, toxicological, and ecological information, in order to compensate for the lack of toxicity data for site-specific species.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Health Risks of Metals in Soil,Water, and Major Food Crops in Hamedan Province,Iran

Food, drinking water, soil, and air are the main routes of exposure to trace metals, thus the assessment of the risks posed to humans by these elements is important. Wheat, potatoes, and maize are very important parts of the Iranian diet. The objectives of this study were to estimate the non-carcinogenic and carcinogenic health risks of Hg, Pb, Cd, Cr, Se, As, and Ni to adults and children via soil, water, and major food crops consumed in Hamedan Province, northwest Iran, using the total non-cancer hazard quotient (THQ) and cancer risk assessment estimates. Total non-cancer hazard of Ni and Hg, were greater than 1, and total cancer risk of As and Pb was greater than 1 × 10^?6. Food consumption was identified as the major route of human exposure to metals, and consuming foodstuff threatens the health of the studied population. In Hamedan Province, consumption of wheat is the main source of intake of metals from foodstuff for adults, and in children, the soil ingestion route is also important.     

Environmental Monitoring of Heavy Metal Status and Human Health Risk Assessment in the Agricultural Soils of the Jinxi River Area,China

Soil contamination with heavy metals is one of the main environmental concerns in China, mainly owing to rapid industrialization and mining activities in certain areas. The current study aimed at monitoring the levels of heavy metals in soils of the industrial areas along the Jinxi River and surrounding Lake Qingshan. In addition, a health risk assessment for humans in contact with these soils was also conducted. The results revealed that the soils of the studied areas were contaminated with Cr, Cu, As, Se, Cd, Pb, and Zn and that the industrial activities were the main source of soil contamination therein. Furthermore, soils of the sites adjacent to Lin’an city exhibited higher levels of heavy metals than the upstream and Lake Qingshan sites. Most of the studied heavy metals tended to concentrate in the fine soil fractions (PM100, PM10, and PM2.5). Calculation of the hazard index (HI) revealed that humans, especially children, have potential health risks. Moreover, As was found to contribute to more magnitude of cancer risks. Thus, we concluded that the unmanaged development negatively affects the Chinese environment and human health. Furthermore, fine fractions of soil particles should be considered for risk assessment.