We investigated heavy metal contamination in soils and plants at polluted sites in China including some with heavy industries, metal mining, smelting and untreated wastewater irrigation areas. We report our main findings in this paper. The concentrations of heavy metals, including Cd and Zn, in the soils at the investigated sites were above the background levels, and generally exceeded the Government guidelines for metals in soil. The concentrations of metals in plants served to indicate the metal contamination status of the site, and also revealed the abilities of various plant species to take up and accumulate the metals from the soil. Substantial differences in the accumulation of heavy metals were observed among the plant species investigated. Polygonum hydropiper growing on contaminated soils in a sewage pond had accumulated 1061 mg kg(-1) of Zn in its shoots. Rumex acetosa L. growing near a smelter had accumulated more than 900 mg kg(-1) of Zn both in its shoots and roots. Therefore these species have potential for phytoremediation of metal-contaminated sites. Our results indicate the need to elucidate the dynamics of soil metal contamination of plants and the onward movement of metal contaminants into the food chain. Also our results indicate that the consumption of rice grown in paddy soils contaminated with Cd, Cr or Zn may pose a serious risk to human health, because from 24 to 22% of the total metal content in the rice biomass was concentrated in the rice grain. Platanus acerifolia growing on heavily contaminated soil accumulated only very low levels of heavy metals, and this mechanism for excluding metal uptake may have value in crop improvement. Sources of metal entering the environmental matrices studied included untreated wastewater, tailings or slurries and dust depositions from metal ore mining, and sewage sludge. Pb, Zn or Cd concentrations declined with the distance from metal smelter in accordance with a good exponential correlation (R2>0.9), and this shows that metal dust deposition is an important contributor to metal contamination of soils.

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Ingestion of contaminated soil has been recognized as an important exposure pathway of cadmium (Cd) for humans, especially for children through outdoor hand-to-mouth activities. The effect of ageing process following the input of Cd into soil on the bioaccessibility of Cd in five typical soils of China was investigated using physiologically based in vitro test in this study. A sequential extraction procedure was employed with attempt to identify the bioaccessible fraction(s) of Cd in soils. The bioaccessibility of Cd in strongly acidic (≈ pH 4.5) soils reached nearly steady levels (76.5-76.9% and 52.0-52.6% in the gastric and small intestinal phases, respectively) after a sharp decline in the first week of ageing. In contrast, the bioaccessibility of Cd in higher pH (N 6.0) soils was found to be much lower (53.3-72.7% and 29.9-43.4% in gastric and small intestinal phases, respectively) and took 2 weeks of ageing to reach steady levels. The freshly spiked Cd was more labile than native Cd. The main proportion of spiked Cd was found in exchangeable Cd which was higher in strongly acidic soils (68.6-71.8%) than in higher pH soils (53.4-61.4%) at day 120 after a sharp decline to the nearly steady state in the first 1 and 2 weeks, respectively. Significant correlations between Cd bioaccessibility and either water soluble and exchangeable Cd individually, or the sum of water soluble and exchangeable Cd throughout the incubation period for all soils, indicate that these forms of Cd are likely to constitute the main proportion of bioaccessible Cd in soils.

Arsenic (As) speciation and distribution are two important factors in assessing human health risk from As-contaminated soil. In this study, we used the combination of physiologically based extraction test (PBET) and Simulator of Human Intestinal Microbial Ecosystem (SHIME) to determine soil As metabolism by human gut microbiota. The results showed that the percentage of soil arsenate [As(V)] transformation reached 22.1−38.2%, while that of arsenite [As(III)] attained 66.5−92.0%; 30.1−56.4% of As(V) transformed was attached to the soil solid phase. In comparison to sequential extraction results, almost all amorphous Fe/Al-oxide-bound As was liberated in the colon phase. An X-ray absorption nearedge structure (XANES) showed that the As(III) percentage in the soil solid phase reached 16.6−26.9% and reached 73.4% (soil 1) in the colon phase. Additionally, plenty of As(III) and different extents of methylation were also observed in colon extraction solution. As bioaccessibility in the colon phase was 1.8−2.8 times that in the small intestinal phase. Our results indicated that human gut microbiota increased As bioaccessibility, and large amounts of As(III) were adsorbed onto the soil solid phase as a result of microbial reduction. Determining As speciation and distribution in extraction solution and soil solid phases will allow for an accurate assessment of the risk to human health upon soil As exposure. ■ INTRODUCTIONArsenic (As) is a common toxic contaminant that is extensively distributed in the environment. 1 Human exposure to As in soils is a major public concern and is associated with serious risks to human health because As species are known carcinogens. 2,3 In most cases, human exposure to soil As occurs via inhalation, inadvertent oral ingestion, and dermal contact. 4,5 Inadvertent oral ingestion has been considered an important exposure route for soil As, especially ingestion through outdoor hand-to-mouth activities by children. 6 The estimation of As bioaccessibility (gastric and small intestinal phases) in contaminated soils through in vitro methods has been used for human health risk assessment. On the basis of previous studies, 7−9 simple, fast, and inexpensive in vitro methods can effectively estimate in vivo relative As bioavailability. Generally, bioaccessibility is defined as the fraction of As that is soluble in the gastrointestinal environment of humans and available for absorption, whereas bioavailability is determined by the fraction of As that is absorbed into the systemic circulation. 7,8 Currently, As bioaccessibility in the gastric and small intestinal phases may underestimate its harm to human health. 10 Studies have clearly illustrated that gut microbiota significantly affect As metabolism by, for example, reduction, methylation, and thiolation. 11 As metabolism in contaminated soil by human gut microbiota can affect As bioaccessibility and speciation. 10,12 Therefore, As biotransformation must be considered an essential part of the risk assessment of oral soil As exposure using i...

The pH dependent solid-solution distribution of arsenate and phosphate in five Dutch agricultural soil samples was measured in the pH range 4-8, and the results were interpreted using the LCD (ligand and charge distribution) adsorption modeling. The pH dependency is similar for both oxyanions, with a minimum soluble concentration observed around pH 6-8. This pH dependency can be successfully described with the LCD model and it is attributed mainly to the synergistic effects from Ca adsorption. The solubility of phosphate is much lower than that of arsenate. This big difference cannot be sufficiently explained by the reduction of small amount of As(V) into As(III), neither by slow desorption/adsorption. The difference between phosphate and arsenate in their solid-solution distribution becomes larger with the increase of aluminum (hydr)oxides (Al-oxides) contribution to the total amount of metal (Al and Fe) (hydr)oxides. The influence of Al-oxides is much larger than its relative amount extracted from the soils. When Al-oxides account for >40% of the soil oxides, the whole adsorbents behave apparently similarly to that of pure Al-oxides. These results indicated that surface coating and substitution may have modified significantly oxyanion adsorption to Fe-oxides in soils, and how to account for this complexity is a challenge for geochemical modeling.

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The physiological response to application of elemental sulphur (S) and cadmium (Cd) of maize (Zea mays L.) grown for 60 days in pot soil was studied. The S was added into the soil with 2 rates (0 and 50 mmol/kg) and Cd was added in solution in 4 rates (0, 20, 50, 100 mg/kg). All the S and Cd were added before planting. Shoot biomass decreased with the application of Cd to the soil whether S was applied or not. The application of S and Cd to soil led to an increasing accumulation of Cd in the shoots of maize. The concentration of chlorophyll was reduced significantly in Cd-treated plants with or without supplementary S. The content of malondialdehyde (MDA) was increased significantly in treatments with S and Cd, compared to the control. The activity of peroxidases (POD) was increased but catalase (CAT) was decreased in plants treated with Cd, again with or without S, in comparison with control. POD and CAT activities decreased in all the Cd treated plants with S, as compared to the plants without S. The results suggest that Cd reduces the crop growth, concentration of chlorophyll and activity of CAT, but increases the content of MDA and activity of POD. S supplies decrease the content of MDA, activities of POD and CAT, as compared to zero S supplies at the same rate of Cd application.

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