Beyond cadmium accumulation: Distribution of other trace elements in soils and cacao beans in Ecuador.

Since cacao beans accumulate Cd in high levels and restrictions have been imposed on safe levels of chocolate consumption, concern about whether or not cacao trees store other toxic elements seems to be inevitable. Following a previous study in Ecuador examining Cd content in five cacao varieties collected in pristine areas and in places impacted by oil activities, we present here the concentrations of 11 trace elements (TEs) (As, Ba, Co, Cu, Cr, Mo, Mn, Ni, Pb, V and Zn) in soils, cacao tissues (leaves, pod husks, beans) and cocoa liquor (CL). Several TEs showed concentrations in topsoils above the Ecuadorian limits, and may have a mixed natural and anthropogenic origin. Ba and Mo concentrations in cacao tissues are slightly higher than those reported in other surveys, but this was not the case for toxic elements (As and Pb). TE contents are lower in CL, than in beans, except for Pb and Co, but no risk was identified for human health. Compared with control areas, Enrichment Factors were below 2 in impacted areas, except for Ba. Transfer factors (from soils to cacao) indicated that cacao does not accumulate TEs. A positive correlation was found between Cd and Zn in topsoils and cacao tissues for the CCN-51 variety, and between Cd and Ni for the Nacional variety. Identifying patterns of TE distribution and potential interactions in order to explain plant internal mechanisms, which is also dependent on the cacao variety, is a difficult task and needs further research.

Environmental and health impacts of fine and ultrafine metallic particles: assessment of threat scores.

This study proposes global threat scores to prioritize the harmfulness of anthropogenic fine and ultrafine metallic particles (FMP) emitted into the atmosphere at the global scale. (Eco)toxicity of physicochemically characterized FMP oxides for metals currently observed in the atmosphere (CdO, CuO, PbO, PbSO(4), Sb(2)O(3), and ZnO) was assessed by performing complementary in vitro tests: ecotoxicity, human bioaccessibility, cytotoxicity, and oxidative potential. Using an innovative methodology based on the combination of (eco)toxicity and physicochemical results, the following hazard classification of the particles is proposed: CdCl2~CdO>CuO>PbO>ZnO>PbSO(4)>Sb(2)O(3). Both cadmium compounds exhibited the highest threat score due to their high cytotoxicity and bioaccessible dose, whatever their solubility and speciation, suggesting that cadmium toxicity is due to its chemical form rather than its physical form. In contrast, the Sb(2)O(3) threat score was the lowest due to particles with low specific area and solubility, with no effects except a slight oxidative stress. As FMP physicochemical properties reveal differences in specific area, crystallization systems, dissolution process, and speciation, various mechanisms may influence their biological impact. Finally, this newly developed and global approach could be widely used in various contexts of pollution by complex metal particles and may improve risk management.

Foliar uptake and metal(loid) bioaccessibility in vegetables exposed to particulate matter.

At the global scale, high concentrations of particulate matter (PM) enriched with metal(loid)s are currently observed in the atmosphere of urban areas. Foliar lead uptake was demonstrated for vegetables exposed to airborne PM. Our main objective here was to highlight the health risk associated with the consumption of vegetables exposed to foliar deposits of PM enriched with the various metal(loid)s frequently observed in the atmosphere of urban areas (Cd, Sb, Zn and Pb). Leaves of mature cabbage and spinach were exposed to manufactured mono-metallic oxide particles (CdO, Sb2O3 and ZnO) or to complex process PM mainly enriched with lead. Total and bioaccessible metal(loid) concentrations were then measured for polluted vegetables and the various PM used as sources. Finally, scanning electronic microscopy coupled with energy dispersive X-ray microanalysis was used to study PM-phyllosphere interactions. High quantities of Cd, Sb, Zn and Pb were taken up by the plant leaves. These levels depended on both the plant species and nature of the PM, highlighting the interest of acquiring data for different plants and sources of exposure in order to better identify and manage health risks. A maximum of 2% of the leaf surfaces were covered with the PM. However, particles appeared to be enriched in stomatal openings, with up to 12% of their area occupied. Metal(loid) bioaccessibility was significantly higher for vegetables compared to PM sources, certainly due to chemical speciation changes. Taken together, these results confirm the importance of taking atmospheric PM into account when assessing the health risks associated with ingestion of vegetables grown in urban vegetable crops or kitchen gardens.

Influence of earthworm bioturbation on metals phytoavailability and human gastric bioaccessibility.

At the global scale, urban agriculture is increasingly developing in cities due to demographic growth and sustainable food concerns. But, urban soils are frequently polluted with metals. In urban gardens, organic matter is also commonly added both to valorize organic household waste and to promote biophysicochemical fertility. As earthworms promote the decomposition and the recycling of soil organic matter, they can also influence the biogeochemical cycle of metals in urban polluted soils. In order to produce safe vegetables in urban areas, it is crucial to highlight the mechanisms involved in complex soil-earthworm-plant ecosystems. An experiment was set up to examine these relationships using lettuce cultivated in controlled conditions with RHIZOtest® devices. Thanks to the RHIZOtest® devices, metal transfer and bioaccessibility were for the first time compared for urban polluted soil without (1-urban soil polluted with Pb, Cd, Cu, and Zn: essential or toxic metals currently found in environment, SNB) and with bioturbation (2-this metal-polluted soil subjected to earthworm bioturbation, SB) and earthworm casts (3-earthworm casts produced in this polluted soil and naturally enriched in organic matter and microorganisms, T). Metal concentration, phytoavailability, and human gastric bioaccessibility were determined in the different samples. Results showed that earthworm bioturbation increased the phytoavailability of all the metals. For the experimental condition SB, the phytoavailability of metals was increased up to 75% compared to SNB. In addition, surprisingly, metal phytoavailability was always superior in SB compared to earthworm casts (T). Moreover, earthworms led to an increase in Zn gastric bioaccessibility up to 10% in the soils in the same way as for phytoavailability, meaning Zn bioaccessibility in SB > T > SNB, whereas it remained unchanged in the lettuces. These data are important to promote sustainable agriculture activities in urban areas; actually, databases concerning different experimental conditions are needed to develop decision support tools.

Field isotopic study of lead fate and compartmentalization in earthworm-soil-metal particle systems for highly polluted soil near Pb recycling factory.

Earthworms are important organisms in soil macrofauna and play a key role in soil functionality, and consequently in terrestrial ecotoxicological risk assessments. Because they are frequently observed in soils strongly polluted by metals, the influence of earthworm bioturbation on Pb fate could therefore be studied through the use of Pb isotopes. Total Pb concentrations and isotopic composition ((206)Pb, (207)Pb and (208)Pb) were then measured in earthworms, casts and bulk soils sampled at different distance from a lead recycling factory. Results showed decreasing Pb concentrations with the distance from the factory whatever the considered matrix (bulk soils, earthworm bodies or cast samples) with higher concentrations in bulk soils than in cast samples. The bivariate plot (208)Pb/(206)Pb ratios versus (206)Pb/(207)Pb ratios showed that all samples can be considered as a linear mixing between metallic process particulate matter (PM) and geochemical Pb background. Calculated anthropogenic fraction of Pb varied between approximately 84% and 100%. Based on Pb isotopic signatures, the comparison between casts, earthworms and bulk soils allowed to conclude that earthworms preferentially ingest the anthropogenic lead fraction associated with coarse soil organic matter. Actually, soil organic matter was better correlated with Pb isotopic ratios than with Pb content in soils. The proposed hypothesis is therefore a decrease of soil organic matter turnover due to Pb pollution with consequences on Pb distribution in soils and earthworm exposure. Finally, Pb isotopes analysis constitutes an efficient tool to study the influence of earthworm bioturbation on Pb cycle in polluted soils.

Effects of historic metal(loid) pollution on earthworm communities.

The effects of metal(loid)s (Pb, Cd, Cu, Zn, As and Sb) from atmospheric fallout on earthworm communities were investigated in a fallow meadow located close to a 60-year-old lead recycling factory. We examined abundance and species diversity as well as the ratio of adult-to-juvenile earthworms, along five 140 m parallel transects. The influence of soil pollution on the earthworm community at the plot scale was put in context by measuring some physico-chemical soil characteristics (OM content, N content, pH), as well as total and bioavailable metal(loid) concentrations. Earthworms were absent in the highly polluted area (concentration from 30,000 to 5000 mg Pb·kg(-1) of dried soil), just near the factory (0-30 m area). A clear and almost linear relationship was observed between the proportion of juvenile versus mature earthworms and the pollution gradient, with a greater proportion of adults in the most polluted zones (only adult earthworms were observed from 30 to 50 m). Apporectodea longa was the main species present just near the smelter (80% of the earthworms were A. longa from 30 to 50 m). The earthworm density was found to increase progressively from five individuals·m(-2) at 30 m to 135 individuals·m(-2) at 140 m from the factory. On average, metal(loid) accumulation in earthworm tissues decreased linearly with distance from the factory. The concentration of exchangeable metal(loid)s in earthworm surface casts was higher than that of the overall soil. Finally, our field study clearly demonstrated that metal(loid) pollution has a direct impact on earthworm communities (abundance, diversity and proportion of juveniles) especially when Pb concentrations in soil were higher than 2050 mg·kg(-1).

Environmental and health risk assessment of Pb, Zn, As and Sb in soccer field soils and sediments from mine tailings: solid speciation and bioaccessibility.

Areas polluted by the persistent presence of metal(loid)s induce health problems, especially when recreational activities (on land or water) promote human exposure to the pollutants. This study focuses on one of the most encountered worldwide mining waste, i.e. those from the extraction of Pb-Zn-Ag. The representative Pb-Zn-rich tailing (about 64,100 m(3)) sampled is located near a soccer field and a famous river for fishing. The scientific interests is relative to: (1) mobility and bioaccessibility of metal(oid)s, (2) human risk assessments and (3) relationship between human risks and solid-bearing phases in the environment. Soccer field soils, tailings and sediments from the nearby river were sampled; moreover, metal(loid) speciation (from BCR experiments) and bioaccessibility were measured and solid speciation performed by X-ray diffraction and electron microscopy in order to highlight metal(loid) dispersion and impact. Results demonstrate that the soccer field is highly contaminated by Pb, Zn, As and Sb due primarily to waste runoff. In terms of risk assessment, Pb and As human bioaccessibility highlights the major health risk (48 and 22.5 % of human bioaccessibility, respectively). Since local populations are regularly in close contact with metal(loid)s, the health risk due to pollutant exposure needs to be reduced through sustainable waste disposal and the rehabilitation of polluted sites.

Earthworm bioturbation influences the phytoavailability of metals released by particles in cultivated soils.

The influence of earthworm activity on soil-to-plant metal transfer was studied by carrying out six weeks mesocosms experiments with or without lettuce and/or earthworms in soil with a gradient of metal concentrations due to particles fallouts. Soil characteristics, metal concentrations in lettuce and earthworms were measured and soil porosity in the mesocosms was determined. Earthworms increased the soil pH, macroporosity and soil organic matter content due to the burying of wheat straw provided as food. Earthworm activities increased the metals concentrations in lettuce leaves. Pb and Cd concentrations in lettuce leaves can increase up to 46% with earthworm activities … These results and the low correlation between estimated by CaCl2 and EDTA and measured pollutant phytoavailability suggest that earthworm bioturbation was the main cause of the increase. Bioturbation could affect the proximity of pollutants to the roots and soil organic matter.

Use of ecotoxicity test and ecoscores to improve the management of polluted soils: case of a secondary lead smelter plant.

With the rise of sustainable development, rehabilitation of brownfield sites located in urban areas has become a major concern. Management of contaminated soils in relation with environmental and sanitary risk concerns is therefore a strong aim needing the development of both useful tools for risk assessment and sustainable remediation techniques. For soils polluted by metals and metalloids (MTE), the criteria for landfilling are currently not based on ecotoxicological tests but on total MTE concentrations and leaching tests. In this study, the ecotoxicity of leachates from MTE polluted soils sampled from an industrial site recycling lead-acid batteries were evaluated by using both modified Escherichia coli strains with luminescence modulated by metals and normalized Daphnia magna and Alivibrio fischeri bioassays. The results were clearly related to the type of microorganisms (crustacean, different strains of bacteria) whose sensitivity varied. Ecotoxicity was also different according to sample location on the site, total concentrations and physico-chemical properties of each soil. For comparison, standard leaching tests were also performed. Potentially phytoavailable fraction of MTE in soils and physico-chemical measures were finally performed in order to highlight the mechanisms. The results demonstrated that the use of a panel of microorganisms is suitable for hazard classification of polluted soils. In addition, calculated eco-scores permit to rank the polluted soils according to their potentially of dangerousness. Influence of soil and MTE characteristics on MTE mobility and ecotoxicity was also highlighted.

Assessing ecotoxicity and uptake of metals and metalloids in relation to two different earthworm species (Eiseina hortensis and Lumbricus terrestris).

Due to diffuse atmospheric fallouts of process particles enriched by metals and metalloids, polluted soils concern large areas at the global scale. Useful tools to assess ecotoxicity induced by these polluted soils are therefore needed. Earthworms are currently used as biotest, however the influence of specie and earthworm behaviour, soil characteristics are poorly highlighted. Our aim was therefore to assess the toxicity of various polluted soils with process particles enriches by metals and metalloids (Pb, Cd, Cu, Zn, As and Sb) collected from a lead recycling facility on two earthworm species belonging to different ecological types and thus likely to have contrasted behavioural responses (Eiseina hortensis and Lumbricus terrestris). The combination of behavioural factors measurements (cast production and biomass) and physico-chemical parameters such as metal absorption, bioaccumulation by earthworms and their localization in invertebrate tissues provided a valuable indication of pollutant bioavailability and ecotoxicity. Soil characteristics influenced ecotoxicity and metal uptake by earthworms, as well as their soil bioturbation.