Rice consumption is the major pathway for human methylmercury (MeHg) exposure in inland China, especially in mercury (Hg) contaminated regions. MeHg production, a microbially driven process, depends on both the chemical speciation of inorganic divalent mercury, Hg(II), that determines Hg bioavailability for methylation. Studies have shown that Hg(II) speciation in contaminated paddy soils is mostly controlled by natural organic matter and sulfide levels, which are typically thought to limit Hg mobility and bioavailability. Yet, high levels of MeHg are found in rice, calling for reconsideration of the nature of Hg species bioavailable to methylators in paddy soils. Here, we conducted incubation experiments using a multi-isotope tracer technique including ¹⁹⁸Hg(NO₃)₂, natural organic matter bond Hg(II) (NOM-¹⁹⁹Hg(II)), ferrous sulfide sorbed Hg(II) (≡FeS-²⁰⁰Hg(II)), and nanoparticulate mercuric sulfide (nano-²⁰²HgS), to investigate the relative importance of geochemically diverse yet relevant Hg(II) species on Hg methylation in paddy soils across a Hg concentration gradient. We show that methylation rates for all Hg(II) species tested decreased with increasing Hg concentrations, and that methylation rates using NOM-¹⁹⁹Hg(II) and nano-²⁰²HgS as substrates were similar or greater than rates obtained using the labile ¹⁹⁸Hg(NO₃)₂ substrate. ≡FeS-²⁰⁰Hg(II) yielded the lowest methylation rate in all sites, and thus the formation of FeS is likely a sink for labile ¹⁹⁸Hg(NO₃)₂ in sulfide-rich paddy soils. Moreover, the variability in the methylation data for a given site (1 to 5-fold variation depending on the Hg species) was smaller than what was observed across the Hg concentration gradient (10³–10⁴ fold variation between sites). These findings emphasize that at broad spatial scales, site-specific characteristics, such as microbial community structure, need to be taken into consideration, alongside the nature of the Hg substrate available for methylation, to determine net MeHg production. This study highlights the importance of developing site-specific strategies for remediating Hg pollution.

Freshwater ecosystems are the main source of water for sustaining life on earth, and the biodiversity they support is the main source of valuable goods and services for human populations. Despite growing recognition of the impairment of freshwater ecosystems by micropollutant contamination, different conceptual and methodological considerations can newly be addressed to improve our understanding of the ecological impact into these ecosystems. Here, we originally combined in situ ecotoxicology and community ecology concepts to unveil the mechanisms structuring macroinvertebrate communities along a regional contamination gradient. The novelty of our study lies in the use of an innovative biomonitoring approach (measurement of metal contents in caged crustaceans) allowing to quantify and compare on a regional scale the levels of bioavailable metal contamination to which stream communities are exposed. We were hence able to identify 23 streams presenting a significant gradient of bioavailable metal contamination within the same catchment area in the South West of France, from which we also obtained data on the composition of resident macroinvertebrate communities. Analyses of structural and functional integrity of communities revealed an unexpected decoupling between taxonomic and functional diversity of communities in response to bioavailable metal contamination. We show that despite the negative impact of bioavailable metal contamination exposure on taxonomic diversity (with an average species loss of 17% in contaminated streams), functional diversity is maintained through a process of non-random species replacement by functional redundant species at the regional scale. Such unanticipated findings call for a deeper characterization of metal-tolerant communities’ ability to cope with environmental variability in multi-stressed ecosystems.

Many organic materials have been used to decrease heavy-metal bioavailability in soil via in-situ remediation due to its high efficiency and easy operation; meanwhile, cheap materials have also been pursued to decrease the cost of remediation. Agricultural wastes exhibit their potential in remediation materials due to their low cost; however, raw agricultural wastes have a low ability to immobilize heavy metals in soil. Attempts have been made to modify agricultural wastes to improve the efficiency of heavy-metal passivation. In this study, novel agricultural waste-based materials, raw sugarcane bagasse (SB), citric acid modified (SSB) and citric-acid/Fe₃O₄ modified (MSB) sugarcane bagasse at 0.5% and 1% addition rates, were compared for their effectiveness in soil Cd passivation and Cd accumulations in pakchoi plants in a 30-day pot experiment. The addition of SB did not decrease soil bioavailable Cd effectively and slightly decreased Cd accumulation in plant roots and leaves. In comparison, SSB and MSB exhibited a great potential to decrease the transformation, translocation and accumulation of Cd with the decrease being greater at 1% than 0.5% rate in the soil-pakchoi system. For example, the addition of SSB and MSB at 0.5% decreased the concentration of Cd in leaves by 10%, and 16%, and at 1% decreased the concentration by 25% and 30%, respectively. High pH and abundant functional groups of three amendments played important roles in Cd immobilization. The enhanced microbial activities might also contribute to Cd passivation. However, plant growth was decreased in the amended treatments except SSB at 0.5% rate. The results suggest that citric-acid-modified sugarcane bagasse at addition rate of 0.5% has a potential to immobilize Cd in soil and decrease Cd accumulation in edible part of pakchoi effectively without decreasing vegetable growth.

The properties and metal-binding abilities of dissolved organic matter (DOM) rely on its molecular weight (MW) structure. In this study, the spatial differences of DOM in compositions, MW structures, and binding mechanisms with copper (Cu²⁺) in Dongping Lake were investigated by applying excitation-emission matrix combining parallel factor analysis (EEM-PARAFAC), synchronous fluorescence (SF) spectra, two-dimensional correlation spectra (2D-COS), and Fourier transform infrared (FTIR) spectra. The EDOM for the entrance of the Dawen River and PDOM for the macrophyte-dominated region were divided from DOM of Dongping Lake based on hierarchical clustering analysis (HCA) and principal component analysis (PCA) and were size-fractioned into MW < 500 kDa and <100 kDa fractions. According to EEM-PARAFAC, Dongping Lake was dominated by tryptophan-like substances with MW < 500 kDa. The concentration of PDOM was higher than that of EDOM (p < 0.05). 2D-COS showed that protein-like components preceded humic-like components binding to Cu²⁺ regardless of sample type (215 nm > 285 nm > 310–360 nm). The Cu²⁺ binding capacity of DOM exhibited specific differences in space, components, and molecular weights. The humic-like component 1 (C1) and tryptophan-like component 4 (C4) of PDOM showed stronger binding abilities than those of EDOM. Endogenous tryptophan-like component 4 (C4) had a higher binding affinity for Cu²⁺ than humic-like components (logKₐ: C4 > C1 > C2) in PDOM irrespective of MW. Humic-like components with MW < 500 kDa displayed higher binding potentials for Cu²⁺. FTIR spectra showed that the main participants of DOM-Cu complexation included aromatic hydrocarbons, aliphatic groups, amide Ⅰ bands, and carboxyl functional groups. This study provides spatial-scale insights into the molecular weight structure of DOM in influencing the behavior, fate, and bioavailability of heavy metals in lakes.

Stable isotope fractionation of toluene under dynamic phase exchange was studied aiming at ascertaining the effects of gas-liquid partitioning and biodegradation of toluene stable isotope composition in liquid-air phase exchange reactors (Laper). The liquid phase consisted of a mixture of aqueous minimal media, a known amount of a mixture of deuterated (toluene-d) and non-deuterated toluene (toluene-h), and bacteria of toluene degrading strain Pseudomonas putida KT2442. During biodegradation experiments, the liquid and air-phase concentrations of both toluene isotopologues were monitored to determine the observable stable isotope fractionation in each phase. The results show a strong fractionation in both phases with apparent enrichment factors beyond −800‰. An offset was observed between enrichment factors in the liquid and the gas phase with gas-phase values showing a stronger fractionation in the gas than in the liquid phase. Numerical simulation and parameter fitting routine was used to challenge hypotheses to explain the unexpected experimental data. The numerical results showed that either a very strong, yet unlikely, fractionation of the phase exchange process or a – so far unreported – direct consumption of gas phase compounds by aqueous phase microorganisms could explain the observed fractionation effects. The observed effect can be of relevance for the analysis of volatile contaminant biodegradation using stable isotope analysis in unsaturated subsurface compartments or other environmental compartment containing a gas and a liquid phase.

The Nanfei River was one of dominant inflowing rivers of the fifth largest freshwater Chaohu Lake in China, which had been subjected to increasing nutrients and contaminants from population expansion, rapid industrialization and agricultural intensification in recent decades. In present study, surface sediment from the Nanfei River was collected to investigate the anthropogenic impact on distribution and bioavailability of heavy metals. Possible Cd sources along the river were constrained by using Cd isotope signatures and labile concentrations of heavy metals in sediment were determined through the DGT technique for risk assessment. Results showed that Cd in river sediment showed greatest enrichment (EF 0.8–9.4), indicating massive pollution from anthropogenic activities. Among the various possible Cd source materials, urban road dust, industrial soil and chicken manure, displayed higher Cd abundance and enrichment that might contribute to Cd accumulation in river sediment. Cadmium isotopic composition in river sediment was ranged from −0.21 ± 0.01‰ to 0.13 ± 0.03‰, whereas yielded relative variation from −0.31 ± 0.02‰ to 0.23 ± 0.01‰ in source materials. Accordingly, Cd sources along the river were constrained, i.e. traffic and industrial activities in the upper and middle reaches whereas agricultural activities in the lower reaches. Furthermore, the evaluation on ecological risk of heavy metals in sediment on basis of SQGs and DGT-labile concentrations demonstrated that Pb and Zn might pose higher risk on aquatic species. The present study confirmed that Cd isotopes were promising source tracer in environmental studies.

Under the climate change context, warming Southern Ocean waters may allow mercury (Hg) to become more bioavailable to the Antarctic marine food web (i.e., ice-stored Hg release and higher methylation rates by microorganisms), whose biomagnification processes are poorly documented. Biomagnification of Hg in the food web of the Antarctic Peninsula, one of the world's fastest-warming regions, was examined using carbon (δ¹³C) and nitrogen (δ¹⁵N) stable isotope ratios for estimating feeding habitat and trophic levels, respectively. The stable isotope signatures and total Hg (T-Hg) concentrations were measured in Antarctic krill Euphausia superba and several Antarctic predator species, including seabirds (gentoo penguins Pygoscelis papua, chinstrap penguins Pygoscelis antarcticus, brown skuas Stercorarius antarcticus, kelp gulls Larus dominicanus, southern giant petrels Macronectes giganteus) and marine mammals (southern elephant seals Mirounga leonina). Significant differences in δ¹³C values among species were noted with a great overlap between seabird species and M. leonina. As expected, significant differences in δ¹⁵N values among species were found due to interspecific variations in diet-related to their trophic position within the marine food web. The lowest Hg concentrations were registered in E. superba (0.007 ± 0.008 μg g⁻¹) and the highest values in M. giganteus (12.090 ± 14.177 μg g⁻¹). Additionally, a significant positive relationship was found between Hg concentrations and trophic levels (reflected by δ¹⁵N values), biomagnifying nearly 2 times its concentrations at each level. Our results support that trophic interaction is the major pathway for Hg biomagnification in Southern Ocean ecosystems and warn about an increase in the effects of Hg on long–lived (and high trophic level) Antarctic predators under climate change in the future.

Many naturally seleniferous soils are faced with Cd contamination problem, which severely limits crop cultivation in these areas. Straw returning has been widely applied in agricultural production due to its various benefits to soil physicochemical properties, soil fertility, and crops yield. However, effects of straw application on the fates of Se and Cd in Cd-contaminated seleniferous soils remain largely unclear. Therefore, the effects of straw application on the fates of Se and Cd in Cd-contaminated seleniferous soils were investigated in this study. The results showed that iron reduction driven by Clostridium and Anaeromyxbacter was responsible for the variations in Se and Cd fates in soil. Straw application respectively increased the gene copy numbers of Clostridium and Anaeromyxbacter by 19.5–56.3% and 33.6–39.8%, thus promoting iron reductive dissolution, eventually resulting in a high release amount of Se and Cd from Fe(III) (oxyhydr) oxides. Under reducing conditions, the released Cd was adsorbed by the newly formed metal sulfides or reacted with sulfides to generate CdS precipitates. Straw application decreased the soil exchangeable Se and soil exchangeable Cd concentration during flooding phase. However, straw application significantly increased Se/Cd in soil solution which had the highest bioavailability during flooding. In addition, straw application increased soil exchangeable Se concentration, but it had no significant effects on soil exchangeable Cd concentration after soil drainage. Taken together, straw application increased Se bioavailability and Cd mobility. Therefore, straw application is an effective method for improving Se bioavailability, but it is not suitable for the application to Cd-contaminated paddy soils. In the actual agricultural production, straw could be applied in seleniferous soils to improve Se bioavailability. At the same time, straw application should be cautious to avoid the release of Cd from Cd-contaminated soil.

The negative impact of microplastics (MPs) act as metals vectors to environment and ecosystem have been paid more and more attention, and the accumulation risk of them to human body through the food chains and food webs needs to attract attention. In addition, the MPs bonded with heavy metals transport from river into the sea with high salinity may also have metals release risk. Herein, natural aged microplastics prepared from artificially broken macroplastics adsorbed with heavy metals accumulated from the natural environment were tested for their states and release risk in several simulated solution (NaCl and gastrointestinal solutions) to understand their effects on environment and human health. The adsorption capacity of different heavy metals on MPs was different during natural aging process proved by four-acid digestion method. Metals with high accumulation (including Pb, As, Cr, Mn, Ni, Zn, Co, Cu and Cd) on NAMPs were selected for further study. Results obtained via three-step extraction method showed that these heavy metals were mainly present as acid-extractable and reducible ions, which were characterized by high bioavailability. Release experiments suggested the notable Mn, Zn, As, Cr, Cu and Ni release in NaCl solution, and significant release of Mn, Zn, As, Cr, Cu, Pb and Ni in gastrointestinal solutions. The high metal release ratio in the simulated gastric solution was attributed to the weak binding of metal ions to NAMPs in acidic environment. This study will play a vital rule in assessing the ecological risks associated with MPs in natural environment.

The derivation of sediment quality guideline values (SQGVs) presents significant challenges. Arguably the most important challenge is to conduct toxicity tests using contaminated sediments with physico-chemistry that represents real-world scenarios. We used a novel metal spiking method for an experiment that ultimately aims to derive a uranium SQGV. Two pilot studies were conducted to inform the final spiking design, i.e. percolating a uranyl sulfate solution through natural wetland sediments. An initial pilot study that used extended mixing equilibration phases produced hardened sediments not representative of natural sediments. A subsequent percolation method produced sediment with similar texture to natural sediment and was used as the method for spiking the sediments. The range of total recoverable uranium (TR-U) concentrations achieved was 8–3200 mg/kg. This reflected the concentrations found in natural wetlands and water management ponds found on a uranium mine site and was above natural levels. Dilute-acid extractable uranium (AE-U) concentrations were >80% of total concentrations, indicating that much of the uranium in the spiked sediment was labile and potentially bioavailable. The portion of TR-U extractable as AE-U was similar at the start and end of the 4.5-month field-deployment. Porewater uranium (PW–U) analyses indicated that partition coefficients (Kd) were 2000–20,000 L/kg, and PW-U was greater in post- than pre-field-deployed samples when TR-U was ≤1500 mg/kg, indicating the binding became weaker during the field-deployment period. At higher spiked-U concentrations, the PW-U was lower post-field-deployment. Comparing the physico-chemical data of the spiked sediments with environmental monitoring data from sediments in the vicinity of a uranium mining operation indicated that they were representative of sediments contaminated by mining and that the U-spiked sediments had a clear U concentration gradient. This confirmed the suitability of the spiking procedure for preparing sediments that were suitable for deriving a SQGV for uranium.