Elevated toxins in soybeans extensively threaten Asian residents and over one billion vegetarians worldwide. An integrated dataset of toxic trace metal(loid)s especially cadmium (Cd) analysis in soybean grain samples (n = 5217) from 12 countries/regions of origin was compiled for risk analysis. Worldwide grain Cd averaged 0.093 mg kg⁻¹, but mean values varied 16-fold between regions, with South China (0.32 mg kg⁻¹) > Argentina (0.15 mg kg⁻¹) = German (0.13 mg kg⁻¹) > Japan (0.11 mg kg⁻¹) > the United States (0.064 mg kg⁻¹) > Central-North China (0.020–0.60 mg kg⁻¹) ≥ Iran (0.042 mg kg⁻¹) = Brazil (0.023 mg kg⁻¹) = South Korea (0.020 mg kg⁻¹). Regression analysis suggested widespread contamination and acidic soil features significantly contributed the elevated food Cd contamination worldwide. Arsenic (As) and lead (Pb) are also of concern because excessive levels were often observed in grains. Given that soil Cd bioavailability is generally low in alkaline pH ranges, the feasibility of producing safe food from contaminated land was investigated by greenhouse experiments with one low-Cd soybean cultivar grown on 20 contaminated calcareous soils. Equilibrium-based approaches i.e., 0.01 M CaCl₂ and in-situ porewater extractions, and diffusion-based diffusive gradients in thin-films technique were used to determine the plant-available fractions of soil metal(loid)s to explain the bioaccumulation variation. The results suggested that soybean grains bioaccumulated mean 0.76 mg Cd kg⁻¹, ranging from 0.16 to 2.1 mg kg⁻¹, whereas As and Pb bioaccumulation was low. Cadmium accumulation was closely correlated with plant-available Cd fractions especially the 0.01 M CaCl₂-extractable Cd, but negatively correlated with soil pH. Even in the alkaline pH range, a slight decrease of soil pH would increase grain Cd significantly. Study region and those arable lands that have similar soil conditions are not recommended for growing soybean unless novel remediation strategies are developed.

Increased metal concentrations in aquatic habitats come as a result of both anthropogenic and natural sources. Emerging aquatic insects that play an indispensable role in these environments, transferring resources and energy to higher trophic levels in both aquatic and terrestrial habitats, may inadvertently also act as biovectors for metals and other contaminants. This study measured levels of 22 different metals detected in biofilm, aquatic and terrestrial life stages of Trichoptera and Odonata, as well as riparian spiders, to examine the uptake and transfer from freshwater to terrestrial ecosystems. We show that emerging insects transfer metals from aquatic to terrestrial ecosystems, however with large losses observed on the boundary of these two environments. Significantly lower concentrations of most metals in adult insects were observed in both hemimetabolous (Odonata) and holometabolous insect orders (Trichoptera). In holometabolous Trichoptera, however, this difference was greater between aquatic life stages (larvae to pupae) compared to that between pupae and adults. Trophic transfer may have also played a role in decreasing metal concentrations, as metal concentrations generally adhered to the following pattern: biofilm > aquatic insects > terrestrial invertebrates. Exceptions to this observation were detected with a handful of essential (Cu, Zn, Se) and non-essential metals (Cd, Ag), which measured higher concentrations in adult aquatic insects compared to their larval counterparts, as well as in aquatic and terrestrial predators compared to their prey. Overall, all metals were found to be bioavailable and biotransferred from contaminated waters to terrestrial invertebrates to some degree, suggesting that risks associated with metal-contaminated freshwaters could extend to terrestrial systems through the emergence of these potential invertebrate biovectors.

Historical mining activities cause widespread, long-term trace metal contamination of freshwater ecosystems. However, measuring trace metal bioavailability has proven difficult, because it depends on many factors, not least concentrations in water, sediment and habitat. Simple tools are needed to assess bioavailabilities. The use of biomonitors has been widely advocated to provide a realistic measure. To date there have been few attempts to identify ubiquitous patterns of trace metal accumulation within and between freshwater biomonitors at geographical scales relevant to trace metal contamination. Here we address this through a nationwide collection of freshwater biomonitors (species of Gammarus, Leuctra, Baetis, Rhyacophila, Hydropsyche) from 99 English and Welsh stream sites spanning a gradient of high to low trace metal loading. The study tested for inter-biomonitor variation in trace metal body burden, and for congruence amongst accumulations of trace metals within taxa and between taxa across the gradient. In general, significant differences in trace metal body burden occurred between taxa: Gammarus sp. was the most different compared with insect biomonitors. Bivariate relationships between trace metals within biomonitors reflected trace metal profiles in the environment. Strong correlations between some trace metals suggested accumulation was also influenced by physiological pathways. Bivariate relationships between insect biomonitors for body burdens of As, Cu, Mn and Pb were highly consistent. Our data show that irrespective of taxonomic or ecological differences, there is a commonality of response amongst insect taxa, indicating one or more could provide consistent measures of trace metal bioavailability.

The biogeochemical cycling of sulfur in soil is closely associated with the mobility and bioavailability of heavy metals; however the influence of sulfur on the behavior of metal-based nanoparticles has not yet been studied. The influence of S fertilizer (S⁰ and Na₂SO₄) applied in paddy soils on CuO NPs behavior in soil pore water was explored in the present study. Synchrotron-based techniques were applied to investigate the migration and speciation transformation of CuO NPs in soil pore water colloids. The application of sulfur fertilizer increased the zeta potential of soil colloids from the rice rhizosphere region and reduced the size of the colloids. Sulfur fertilization decreased the concentration of Cu in soil pore water in the rice rhizosphere region. S⁰ fertilizer reduced the Cu concentration in soil colloids (by 55.8%–73.5%), while Na₂SO₄ increased the Cu concentration in soil colloids (by 173.8%–265.1%). Sulfur fertilization changed the spatial distribution of Fe³⁺ and Cu²⁺ in colloids, making these ions more likely to be aggregated on the edges of soil colloids. Speciation transformation of CuO NPs happened during the process of migration. The main Cu speciation in the soil colloids were CuO NPs, Cu-Cysteine, Cu₂S and Cu-Citrate. Sulfur fertilization increased the proportion of Cu₂S (by 40.5%) in soil pore water colloids from the rice rhizosphere region, while the proportion of CuO NPs was reduced (by 18.4%). Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids.

Selenium (Se) is an essential micronutrient for animals with a narrow margin between essentiality and toxicity. Se toxicity is largely related to inorganic forms of Se in soil, i.e., selenite and selenate that enter food chains through plant uptake, threatening higher trophic level organisms. This experiment investigated effects of earthworm activity on Se bioavailability in soil and the subsequent plant uptake, using earthworm Eisenia fetida and bean plant Phaseolus vulgaris L, both exposed to either selenite or selenate at 1 or 4 mg Se kg⁻¹ for 16 weeks. Plants took up selenate (up to 221-fold) faster than selenite, with up to 84% of the Se rapidly transported to shoots. In the presence of earthworms, Se accumulation obviously increased for selenate-supplied plants, leading to an up to 4% increase in Se translocation factor for all treatments except for 1 mg kg⁻¹ selenite treatment. Earthworms also concentrated Se faster in tissues (up to 274 mg kg⁻¹ DW) at exposure to selenate. For Se toxicity, Se speciation analysis was conducted on the plants and earthworms using XAS. Compared to worm-free treatments, the percentage of organo-Se, i.e., SeMet and CysSeSeCys, increased in beans (up to 34%) in the presence of earthworms for selenate, while the elemental Se portion was significantly reduced or absent, opposite to the results for selenite. Surprisingly, elemental Se (up to 65%) dominated earthworms, regardless of the form of Se supplied. In conclusion, earthworms clearly enhanced Se uptake and translocation in plants, leading to elevated Se levels in shoots. To prevent resulting hazards to humans and other animals, caution should be taken while consuming the shoots, particularly beans, harvested from the Se contaminated soil where earthworm activity is high. Finally, the significant reduction in soil Se suggests phytoextraction of Se from the soil could be improved using earthworms as an aid to plants.

Diet is an important route of mercury (Hg) uptake in marine organisms. Trophic transfer of Hg throughout the food webs may be influenced by various factors, including diet and Hg speciation. Bivalves such as oysters are widely used as bioindicators of trace element pollution such as Hg. Nevertheless, our current knowledge regarding their ability to accumulate Hg from their diet is mainly based on experiments performed using phytoplankton. In their natural environment, oysters feed on a variety of food items including ciliates, detritus, in addition to phytoplankton. The present study aimed at examining the influence of diet composition on the trophic transfer of inorganic Hg (iHg) and methylmercury (MeHg) in the Pacific cupped oyster Crassostrea gigas. The pulse-chase feeding method was used with two radiolabeled food items: a heterotrophic protist (Uronema marinum) and a phytoplanktonic diatom (Thalassiosira pseudonana). Depuration of dietary Hg in the oysters was followed for 50 d. Kinetic parameters including assimilation efficiency (AE) and efflux rate constant (kₑ) were calculated. Our results showed that oysters fed on ciliates assimilated 96 ± 1% and 31 ± 2% of the ingested MeHg and iHg, respectively whereas these elements were similarly assimilated in the oysters fed on phytoplankton (78 ± 3% and 86 ± 4% for MeHg and iHg, respectively). Mercury assimilation in oyster is thus diet dependent (significant differences in AE, p < 0.05), metal species-dependent and likely resulting from variations in Hg bioavailability in the two food items tested and a gut passage time-dependent of the ingested matrix.

The occurrence of emergent contaminants, 24 polybrominated diphenyl ethers (PBDEs), di(2-ethylhexyl)phthalate (DEHP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), diethyl phthalate (DEP), dimethyl phthalate (DMP), di-n-octyl phthalate (DnOP), bisphenol A (BPA) and nonylphenol (NP), was investigated in sediments and fishes collected from the Tamsui River system to determine the factors that influence their distribution and their risk to aquatic ecosystems and human health. The concentrations of total PBDEs, DEHP, DBP, BBP, DEP, DMP, DnOP, BPA and NP in sediments were 1–955, ND-23570, <50–411, <50–430, ND-80, ND-<50, ND-<50, 1–144, 3–19624 μg/kg dw, respectively. The spatial-temporal distribution trends of these compounds in sediments could be attributed to urbanization, industrial discharge and effluents from wastewater treatment plants. The PBDE congener distribution patterns (BDE-209 was the dominant congener) in sediments reflected the occurrence of debromination of BDE-209 and the elution of penta-BDE from the treated products. The concentrations of total PBDEs, DEHP, DBP, BBP, DEP, DMP, DnOP, BPA and NP in fish muscles were 2–66, 17–1046, <10–231, <10–66, <30, ND-<30, ND-<30, 0.4–7 and 3–440 μg/kg ww, respectively. The species-specific bioaccumulation of these compounds by fish was found and four species particularly showed high bioaccumulation potential. BDE-47 was the predominant BDE congener in fish muscles, suggesting high bioavailability and bioaccumulation of this compound. The results of biota–sediment accumulation factors showed that BDE-47, 99, 100, 153 and 154 had relatively high bioavailability and bioaccumulation potential for some fish species. The ecological risk assessment showed that the concentrations of BPA and NP in sediments were likely to have adverse effects on aquatic organisms (risk quotients > 1). The human health risk assessment according to hazard quotients (HQs) and carcinogenic risks (CRs) revealed no remarkable risk to human health through consumption of fish contaminated with BDE-47, 99, 100, 154, 209, DEHP, BPA and NP.

Humic acid (HA) plays vital roles in regulating the environmental behaviors of metals and thus their toxicity to biota. However, the inner relation between metal bioavailability to soil organisms and the presence of HA with different molecular weight (Mw) is not well documented. In this study, we separated HAs into four fractions with Mw range of 5-30k Da, and discussed their ability to alleviating the toxicity of Cd and Pb to earthworm. The bioaccumulation capacities (Cₘₐₓ) increased in order of: UF1<UF2<UF3<UF4, which is in line with the variations of bioavailable concentrations of Cd and Pb in soil. Variations of Mw and binding capacities of HA determine the accumulation behavior in soil solution. The unsatisfactory of biotic ligand model fitting and the differences in fractions of the total biotic ligand sites (f) in earthworm bound by Cd and Pb suggested that only free species of Cd could be considered as biological available to earthworm, while the Pb–HAs complexes have potential ability to interact with earthworm membrane. Antioxidant enzymes are effective biomarkers, and HA with lower Mw play more important roles in restricting the toxicity of soil Cd and Pb to earthworm. These results reveal the different mechanism for HA controlling metal bioavailability between Cd and Pb in soil environment.

Soils have the ability to modify contaminant bioavailability and toxicity. Prediction the modifying effect of soil on arsenic phytoaccumulation and phytoavailability using either soil property data or soil chemical extraction data in risk assessment of contaminated soil is highly desirable. In this study, plant bioassays important to ecological receptors, were conducted with 20 soils with a wide range in chemical and physical soil properties to determine the relationships between As measured by soil chemical extraction (soil pore water, Bray-1, sodium phosphate solution, hydroxylamine hydrochloride, and acid ammonium oxalate) or soil physico/chemical properties on arsenic phytotoxicity and phytoaccumulation. Soil pore water As and Bray-1 extracted As were significantly (P < 0.01) correlated with lettuce tissue As and those extractants and sodium phosphate were correlated with ryegrass tissue As. Hydroxylamine and acid ammonium oxalate extractions did not correlate with plant bioassay endpoints. Simple regression results showed that lettuce tissue relative dry matter growth (RDMG) was inversely related to tissue As concentration (r² = 0.85, P < 0.01), with no significant relationship for ryegrass. Soil clay exhibited strong adsorption for As and significantly reduce tissue As for lettuce and ryegrass. In addition to clay content, reactive aluminum oxide (AlOx), reactive Fe oxide (FeOx) and eCEC was inversely related to ryegrass tissue As. Multiple regression equation was strongly predictive (r² = 0.83) for ryegrass tissue As (log transformed) using soil AlOx, organic matter, pH, and eCEC as variables. Soil properties can greatly reduce contaminant phytoavailability, plant exposure and risk, which should be considered when assessing contaminant exposure and site-specific risk in As-contaminated soils.

Periphyton plays a significant role in heavy metal transfer in wetlands, but its contribution to cadmium (Cd) bioavailability in paddy fields remains largely unexplored. The main aim of this study was to investigate the effect of periphyton on Cd behavior in paddy fields. Periphyton significantly decreased Cd concentrations in paddy waters. Non-invasive micro-test technology analyses indicated that periphyton can absorb Cd from water with a maximum Cd²⁺ influx rate of 394 pmol cm⁻² s⁻¹ and periphyton intrusion significantly increased soil Cd concentrations. However, soil Cd bioavailability declined significantly due to soil pH increase and soil redox potential (Eh) decrease induced by periphyton. With periphyton, more Cd was adsorbed and immobilized on organic matter, carbonates, and iron and manganese oxides in soil. Consequently, Cd content in rice decreased significantly. These findings give insights into Cd biogeochemistry in paddy fields with periphyton, and may provide a novel strategy for reducing Cd accumulation in rice.