Bioavailability and health risk of toxic heavy metals (As, Hg, Pb and Cd) in urban soils: A Monte Carlo simulation approach.

Toxic heavy metals pollution in urban soil has become a major global issue due to its adverse effects on the environment and human health. In this paper, 26 soil samples were analyzed to assess the speciation, bioavailability and human health risk of Arsenic (As), Mercury (Hg), Lead (Pb) and Cadmium (Cd) in urban soils of a heavy industrial city in NE China by using a Monte Carlo simulation approach. The results showed that As, Hg, Pb and Cd concentrations in the soil all exceed the corresponding background value of study area. Mercury displays the highest value of geo-accumulation index (Igeo), followed by Cd, Pb and As. The pollution load index (PLI) value (>2) indicates a moderate pollution level in the study area. The chemical speciation of HMs mainly exists in residual fraction except Cd. The probabilistic health risk assessment demonstrated that the mean values of Total Carcinogenic Risk (TCR) and Hazard Index (HI) calculated with total concentration are at the unacceptable level, with a higher risk to children than adults. However, the mean values calculated with bioavailable fraction are all within the acceptable level. The mean value of TCR and HI obtained by bioavailable fraction is about 96% and 95% lower than that obtained by total concentration, respectively. Thus, this study suggested that the bioavailable fraction of HMs is a more reliable parameter for health risk assessment, while the total concentration of HMs can overestimate the true risk. The results of this study provide some insight into the speciation, bioavailability and health risks of toxic heavy metals in urban soils in those heavy industrial cities.

An alternative approach to bioaccumulation assessment of methyl-Hg, total-Hg, Cd, Pb, Zn in bivalve Anomalocardia brasiliana from Rio de Janeiro bays.

We present an alternative approach for establishing in situ bioaccumulation assessment of methyl-Hg (MeHg), total-Hg, Cd, Pb and Zn in bivalve Anomalocardia brasiliana from four bays of Rio de Janeiro presenting varying degrees of eutrophication, acid volatile sulfides (2-55 µmol g-1), simultaneously extracted metals (SEM) and total metals (TM) in sediments. Using metal concentrations of composite samples from three size classes of bivalve and their incorporation rates (IR = metal concentration / total length), which depend on exposure time, we calculated asymptotic IR and respective consequent metal concentrations. Both IR and the metal concentration presented inverse relationships with total length (excepting MeHg) and bay contamination. Lead and zinc concentrations were above Brazilian legal criteria in the most anoxic and contaminated bay, suggesting significant metal bioavailability (SEM/TM between 8% and 63%).

Biological risk assessment of heavy metals in sediments and health risk assessment in bivalve mollusks from Kaozhouyang Bay, South China.

The concentrations of heavy metals (Cd, Pb, Cr, Ni, Cu, Zn, Hg and As) in surface sediments and bivalve mollusks in Kaozhouyang Bay were investigated. A biological risk analysis of the sediments indicated that ten sites (about 76.92% of the total number of sites) had a 21% incidence probability of toxicity. A health risk analysis of the bivalve mollusks indicated that Cu and As posed low risks to consumer health. On the basis of the target hazard quotient (THQ), adverse effects may occur based on total THQ (TTHQ). The highest TTHQ was found in the species, Ostrea rivularis, which had the highest capacity for the bioaccumulation (factor > 38) of Cd.

Mercury Levels in Fish for Human Consumption from the Southeast Gulf of California: Tissue Distribution and Health Risk Assessment.

We assessed human health risk due to mercury (Hg) concentrations in fish from three coastal lagoons (Urías, Huizache, and Teacapán) in the SE Gulf of California. We also determined Hg distribution in muscle and liver of analyzed ichthyofauna and compared the results among studied areas according to tissue, season, and lagoon system by using multivariate analyses. Levels of Hg in most of the analyzed fish followed the sequence liver > muscle. The highest Hg levels in muscle (2.80 µg g-1 dw) and liver (9.51 µg g-1 dw) were measured in Cynoscion reticulatus and Pomadasys macracanthus, respectively, although according to the multivariate analyses, statistical differences of Hg concentrations were not found according to the season and the tissue but were found according to the system. It seems that the higher concentrations were associated with areas where the hydrological regime is lower. With respect to health risk assessment, the highest hazard quotients were estimated for Cynoscion reticulatus (0.45) and Stellifer furthii (0.29) from Urías and Pomadasys macracanthus (0.35) from Huizache. None of the studied fish represent a risk for consumers in terms of Hg levels in the edible portion.

Bioavailability and risk assessment of potentially toxic elements in garden edible vegetables and soils around a highly contaminated former mining area in Germany.

Although soil contamination by potentially toxic elements (PTEs) in Europe has a history of many centuries, related problems are often considered as having been dealt with due to the enforcement of tight legislations. However, there are many unsolved issues. We aimed to assess PTE levels in highly contaminated soils and in garden edible vegetables using human health risk indices in order to evaluate the availability and mobilization of arsenic (As), copper (Cu), manganese (Mn), mercury (Hg), lead (Pb), and zinc (Zn). In four gardens in Germany, situated on, or in the vicinity of, a mine dump area, we planted beans (Phaseolus vulgaris ssp. nanus), carrots (Daucus sativus) and lettuce (Lactuca sativa ssp. capitata). We examined soil-to-plant mobilization of elements using transfer coefficient (TC), as well as soil contamination using contamination factor (CF), enrichment factor (EF), and bioaccumulation index (Igeo). In addition, we tested two human health risk assessment indices: Soil-induced hazard quotient (HQS) (representing the "direct soil ingestion" pathway), and vegetable-induced hazard quotient (HQV) (representing the "vegetable intake" pathway). The studied elements were highly elevated in the soils. The values in garden 2 were especially high (e.g., Pb: 13789.0 and Hg: 36.8 mg kg-1) and largely exceeded the reported regulation limits of 50 (for As), 40 (Cu), 400 (Pb), 150 (Zn), and 5 (Hg) mg kg-1. Similarly, element concentrations were very high in the grown vegetables. The indices of CF, EF and Igeo were enhanced even to levels that are rarely reported in the literature. Specifically, garden 2 indicated severe contamination due to multi-element deposition. The contribution of each PTE to the total of measured HQS revealed that Pb was the single most important element causing health risk (contributing up to 77% to total HQS). Lead also posed the highest risk concerning vegetable consumption, contributing up to 77% to total HQV. The presence of lead in both cases was followed by that of As, Mn and Hg. We conclude that in multi-element contamination cases, along with high-toxicity elements (here, Pb, As and Hg) other elements may also be responsible for increasing human health risks (i.e., Mn), due to the possibility of adverse synergism of the PTEs.

Modified Dietary Fiber from Cassava Pulp and Assessment of Mercury Bioaccessibility and Intestinal Uptake Using an In Vitro Digestion/Caco-2 Model System.

The ability of modified dietary fiber (MDF) generated from cassava pulp to modulate the bioaccessibility and intestinal absorption of heavy metals may be helpful to mitigate health risk associated with select foods including select fish high in methyl mercury. Using a coupled in vitro digestion/Caco-2 human intestinal cell model, the reduction of fish mercury bioaccessibility and intestinal uptake by MDF was investiaged. MDF was prepared from cassava pulp, a byproduct of tapioca production. The highest yield (79.68%) of MDF was obtained by enzymatic digestion with 0.1% α-amylase (w/v), 0.1% amyloglucosidase (v/v) and 1% neutrase (v/v). MDF and fish tissue were subjected to in vitro digestion and results suggest that MDF may reduce mercury bioaccessibility from fish to 34% to 85% compared to control in a dose-dependent manner. Additionally, accumulation of mercury from digesta containing fish and MDF was only modestly impacted by the presence of MDF. In conclusion, MDF prepared from cassava pulp may be useful as an ingredient to reduce mercury bioavailability from food such as fish specifically by inhibiting mercury transfer to the bioaccessibile fraction during digestion.

Assessment of mercury exposure in human populations: A status report from Augusta Bay (southern Italy).

Here we investigate mercury concentrations in the blood (HgB), urine (HgU) and human hair (HgH) of 224 individuals from a coastal area (Eastern Sicily, SE Italy) strongly affected by Hg contamination from one of the largest chlor-alkali plants in Europe. The factors affecting the distribution of Hg and the extent of the exposure of individuals have been explored with a multidisciplinary approach. Multiple regression analyses, together with evidence of high levels of HgB (exceeding the HBMI recommended levels in 50% of cases) and HgH (exceeding the EPA reference dose in 70% of cases), primarily suggest that the consumption of local fish is the main source of Hg for humans. no. significant exposure to inorganic mercury was identified. Toxicokinetic calculations produced a provisional tolerable weekly intake (PTWI) level that, in most cases, exceeds international recommendations, particularly for residents in the studied area.

A comprehensive assessment of mercury exposure in penguin populations throughout the Southern Hemisphere: Using trophic calculations to identify sources of population-level variation.

The wide geographic distribution of penguins (Order Sphenisciformes) throughout the Southern Hemisphere provided a unique opportunity to use a single taxonomic group as biomonitors of mercury among geographically distinct marine ecosystems. Mercury concentrations were compared among ten species of penguins representing 26 geographically distinct breeding populations. Mercury concentrations were relatively low (⩽2.00ppm) in feathers from 18/26 populations considered. Population-level differences in trophic level explained variation in mercury concentrations among Little, King, and Gentoo penguin populations. However, Southern Rockhopper and Magellanic penguins breeding on Staten Island, Tierra del Fuego, had the highest mercury concentrations relative to their conspecifics despite foraging at a lower trophic level. The concurrent use of stable isotope and mercury data allowed us to document penguin populations at the greatest risk of exposure to harmful concentrations of mercury as a result of foraging at a high trophic level or in geographic 'hot spots' of mercury availability.

Mercury analysis in hair: Comparability and quality assessment within the transnational COPHES/DEMOCOPHES project.

Human biomonitoring (HBM) is an effective tool for assessing actual exposure to chemicals that takes into account all routes of intake. Although hair analysis is considered to be an optimal biomarker for assessing mercury exposure, the lack of harmonization as regards sampling and analytical procedures has often limited the comparison of data at national and international level. The European-funded projects COPHES and DEMOCOPHES developed and tested a harmonized European approach to Human Biomonitoring in response to the European Environment and Health Action Plan. Herein we describe the quality assurance program (QAP) for assessing mercury levels in hair samples from more than 1800 mother-child pairs recruited in 17 European countries. To ensure the comparability of the results, standard operating procedures (SOPs) for sampling and for mercury analysis were drafted and distributed to participating laboratories. Training sessions were organized for field workers and four external quality-assessment exercises (ICI/EQUAS), followed by the corresponding web conferences, were organized between March 2011 and February 2012. ICI/EQUAS used native hair samples at two mercury concentration ranges (0.20-0.71 and 0.80-1.63) per exercise. The results revealed relative standard deviations of 7.87-13.55% and 4.04-11.31% for the low and high mercury concentration ranges, respectively. A total of 16 out of 18 participating laboratories the QAP requirements and were allowed to analyze samples from the DEMOCOPHES pilot study. Web conferences after each ICI/EQUAS revealed this to be a new and effective tool for improving analytical performance and increasing capacity building. The procedure developed and tested in COPHES/DEMOCOPHES would be optimal for application on a global scale as regards implementation of the Minamata Convention on Mercury.

Assessment of mercury erosion by surface water in Wanshan mercury mining area.

Soil erosion is a main cause of land degradation, and in its accelerated form is also one of the most serious ecological environmental problems. Moreover, there are few studies on migration of mercury (Hg) induced by soil erosion in seriously Hg-polluted districts. This paper selected Wanshan Hg mining area, SW China as the study area. Revised universal soil loss equation (RUSLE) and Geographic information system (GIS) methods were applied to calculate soil and Hg erosion and to classify soil erosion intensity. Our results show that the soil erosion rate can reach up to 600,884tkm(-2)yr(-1). Surfaces associated with very slight and extremely severe erosion include 76.6% of the entire land in Wanshan. Furthermore, the cumulative erosion rates in the area impacted by extremely severe erosion make up 90.5% of the total. On an annual basis, Hg surface erosion load was predicted to be 505kgyr(-1) and the corresponding mean migration flux of Hg was estimated to be 3.02kgkm(-2)yr(-1). The erosion loads of Hg resulting from farmland and meadow soil were 175 and 319kgyr(-1) respectively, which were enhanced compared to other landscape types due to the fact that they are generally located in the steep zones associated with significant reclamation. Contributing to establish a mass balance of Hg in Wanshan Hg mining area, this study supplies a dependable scientific basis for controlling soil and water erosion in the local ecosystems. Land use change is the most effective way for reducing Hg erosion load in Wanshan mining area.

A human health risk assessment of mercury species in soil and food around compact fluorescent lamp factories in Zhejiang Province, PR China.

This study investigated total mercury (THg) and methylmercury (MeHg) contamination in a major production center of compact fluorescent lamps (CFLs) located in Gaohong, Zhejiang Province, China. This was a result of the growing concern associated with the release of mercury into the environment from such components. The results of the study included the following mean concentrations for THg and MeHg of 157±11 (61-518)ng/gdw and 0.28±0.07 (0.07-0.67)ng/gdw in agricultural soil, respectively, and 18.6±6.5 (3.2-47.8)ng/gww and 0.11±0.03 (0.02-0.37)ng/gww in vegetable samples, respectively. A significant correlation was observed between THg in vegetables and corresponding soil samples (r=0.64, p<0.01). THg and MeHg in sediment samples had respective concentrations ranging from 28 to 1019ng/gdw and 0.11 to 3.15ng/gdw. Mud skipper bought from the local market contained the highest Hg (THg: 170±45ng/gww, MeHg: 143±37ng/gww) amongst all fish species (THg: 14-170; MeHg: 11-143ng/gww) of the study. The risk assessment indicated that fish consumption should not result in a MeHg EDI exceeding the RfD (0.1µg/kgbw/d) for both adults and children, when MeHg bioaccessibility is taken into account.

Neurodevelopment of Amazonian infants: antenatal and postnatal exposure to methyl- and ethylmercury.

Neurodevelopment as Gesell development scores (GDSs) in relation to mercury exposure in infants (<6 months of age) of one urban center and two rural villages, respectively, of fisherman and cassiterite miners. Mean total hair-Hg (HHg) concentrations of infants from Itapuã (3.95 ± 1.8 ppm) were statistically (P = 0.0001) different from those of infants from Porto Velho (3.84 ± 5.5 ppm) and Bom Futuro (1.85 ± 0.9 ppm). Differences in vaccine coverage among these populations resulted in significantly higher (P = 0.0001) mean ethylmercury (EtHg) exposure in urban infants (150 µg) than in infants from either village (41.67 µg, Itapuã; 42.39 µg, Bom Futuro). There was an inverse significant (Spearman r = -0.2300; P = 0.0376) correlation between HHg and GDS for infants from Porto Velho, but not for the rural infants from Bom Futuro (Spearman r = 0.1336; P = 0.0862) and Itapuã (Spearman r = 0.1666; P = 0.5182). Logistic regression applied to variables above or below the median GDS showed that EtHg exposure (estimated probability = -0.0157; P = 0.0070) and breastfeeding score (estimated probability = -0.0066; P = 0.0536) score were significantly associated with GDS. Conclusion. In nurslings whose mothers are exposed to different levels of fish-MeHg (HHg), a higher score of neurological development at six months was negatively associated with exposure to additional TCV-EtHg. Results should be interpreted with caution because of unaccounted variables.

Assessment of mercury bioaccumulation within the pelagic food web of lakes in the western Great Lakes region.

While mercury is a health hazard to humans and wildlife, the biogeochemical processes responsible for its bioaccumulation in pelagic food webs are still being examined. Previous studies have indicated both "bottom-up" control of piscivorous fish Hg content through methylmercury.(MeHg) supply, as well as site-specific trophic factors. We evaluated ten studies from the western Great Lakes region to examine the similarity of MeHg trophic transfer efficiency within the pelagic food web, and assessed regional-scale spatial variability. Analyses of bioaccumulation and biomagnification factors between water, seston, zooplankton, and preyfish indicated that the largest increases in MeHg occurred at the base of the food web, and that the relative extent of trophic transfer was similar between sites. Positive correlations were observed between aqueous unfiltered MeHg, total Hg, and dissolved organic carbon, and measures of the efficiency of MeHg trophic transfer were consistent across widely disparate systems (both natural and experimentally manipulated) throughout North America. Such similarity suggests that the aqueous supply of MeHg is largely controlling bioaccumulation in pelagic food webs, while local, lake-specific variability can result from an array of trophic (biological) factors.

Human risk assessment of heavy metals: principles and applications.

Humans are exposed to a number of "heavy metals" such as cadmium, mercury and its organic form methylmercury, uranium, lead, and other metals as wel as metalloids, such as arsenic, in the environment, workplace, food, and water supply. Exposure to these metals may result in adverse health effects, and national and international health agencies have methodologies to set health-based guidance values with the aim to protect the human population. This chapter introduces the general principles of chemical risk assessment, the common four steps of chemical risk assessment: hazard identification, hazard characterization, exposure assessment, risk characterization, and toxicokinetic and toxicity aspects. Finally, the risk assessments performed by international health agencies such as the World Health Organisation, the Environmental Protection Agency of the United States, and the European Food Safety Authority are reviewed for cadmium, lead, mercury, uranium, and arsenic.

Influence of mercury bioaccessibility on exposure assessment associated with consumption of cooked predatory fish in Spain.

BACKGROUND: Predatory fish tend to accumulate high levels of mercury (Hg). Food safety assessment of these fish has been carried out on the raw product. However, the evaluation of the risk from Hg concentrations in raw fish might be modified if cooking and bioaccessibility (the contaminant fraction that solubilises from its matrix during gastrointestinal digestion and becomes available for intestinal absorption) were taken into account. Data on Hg bioaccessibility in raw predatory fish sold in Spain are scarce and no research on Hg bioaccessibility in cooked fish is available. The aim of the present study was to evaluate Hg bioaccessibility in various kinds of cooked predatory fish sold in Spain to estimate their health risk. RESULTS: Both Hg and bioaccessible Hg concentrations were analysed in raw and cooked fish (swordfish, tope shark, bonito and tuna). There were no changes in Hg concentrations during cooking. However, Hg bioaccessibility decreased significantly after cooking (42 ± 26% in raw fish and 26 ± 16% in cooked fish), thus reducing in swordfish and tope shark the Hg concentration to which the human organism would be exposed. CONCLUSION: In future, cooking and bioaccessibility should be considered in risk assessment of Hg concentrations in predatory fish.

Assessment of mercury(II) bioavailability using a bioluminescent bacterial biosensor: practical and theoretical challenges.

Critical methodological challenges in the microbial biosensor approach to assessing Hg(II) bioavailability were evaluated from the perspective of analytical chemists. The main challenge stems from the fact that the chemical speciation of Hg(II) in natural waters exerts a major control on its bioavailability, yet its natural complexation equilibria are extensively altered during conventional bioassays. New data, obtained using a bioluminescent Hg(II)-biosensor, that illustrate these challenges are presented and potential solutions proposed.

Assessment of chronic mercury exposure within the U.S. population, National Health and Nutrition Examination Survey, 1999­2006.

The purpose of this study was to assess chronic mercury exposure within the US population. Time trends were analyzed for blood inorganic mercury (I-Hg) levels in 6,174 women, ages 18-49, in the NHANES, 1999-2006 data sets. Multivariate logistic regression distinguished a significant, direct correlation within the US population between I-Hg detection and years since the start of the survey (OR = 1.49, P < 0.001). Within this population, I-Hg detection rose sharply from 2% in 1999-2000 to 30% in 2005-2006. In addition, the population averaged mean I-Hg concentration rose significantly over that same period from 0.33 to 0.39 µ/L (Anova, P < 0.001). In a separate analysis, multivariate logistic regression indicated that I-Hg detection was significantly associated with age (OR = 1.02, P < 0.001). Furthermore, multivariate logistic regression revealed significant associations of both I-Hg detection and mean concentration with biomarkers for the main targets of mercury deposition and effect: the liver, immune system, and pituitary. This study provides compelling evidence that I-Hg deposition within the human body is a cumulative process, increasing with age and in the population over time, since 1999, as a result of chronic mercury exposure. Furthermore, our results indicate that I-Hg deposition is associated with the significant biological markers for main targets of exposure, deposition, and effect. Accumulation of focal I-Hg deposits within the human body due to chronic mercury exposure provides a mechanism which suggests a time dependent rise in the population risks for associated disease.

Mercury distribution in key tissues of fish (Liza aurata) inhabiting a contaminated estuary-implications for human and ecosystem health risk assessment.

This study brings a new viewpoint based on multiple-tissue analyses to form the basis for a predictive mode of mercury accumulation dynamics in fish body under field conditions. Total mercury (T-Hg) was determined in key tissues of Liza aurata captured along an estuarine contamination gradient, displaying the following hierarchy: kidney > liver > muscle > brain > gills > blood. Brain was the tissue that better reflected the mercury contamination extent, closely followed by liver and muscle. Organic mercury (O-Hg) measured in muscle and liver represented more than 85% and less than 30% of the T-Hg, respectively. The lowest O-Hg percentage was found in the most contaminated area, for both muscle and liver. Mercury distribution and accumulation patterns showed dependence on the specific tissue. The high mercury levels found in organs involved in vital physiological processes point out the risk to autochthonous fish fauna. Human risk associated to the ingestion of fish living in the surveyed areas cannot be excluded.

Assessment of total mercury levels in Clarias gariepinus from the Sagua la Grande River, Cuba.

Total mercury levels (Thg) were quantified in Clarias gariepinus captured from the Sagua la Grande River (Cuba) in the vicinity of an active chlor-alkali plant, and relationships among place of capture; fish size, weight, and sex; and THg levels were assessed. THg levels ranged from 67 to 375 ng/g ww in collected fish, never exceeding the Cuban recommended maximum limit for fish consumption of 500 ng/g ww. No significant correlation was observed between mercury levels and fish allometric characteristics (p < 0.05); however, levels were significantly higher in fish captured below the chlor-alkali facility, suggesting a connection between mercury bioaccumulation and plant discharges.