The concentration and speciation of heavy metals (Cu, Co, Ni, Zn, Cr, Pb and Cd) were studied in surface sediment from the Yangtze River(YR)to the East China Sea (ECS) shelf. The results showed that high contents of metals were found in the YR estuary (YRE) and in the nearshore muddy area, while lower concentrations were found in the YR channel and the ECS shelf. However, after standardization, the total content of most heavy metals from the YR showed little change or slightly increased during the transport process from the river to the estuary but decreased significantly outside the estuary, especially in the sediments of the ECS shelf. The residual fraction is the dominant fraction for all the metals, while the oxidizable and reducible fractions are the most important forms of the nonlithogenic fractions. The total amount of heavy metals from the YR to the continental shelf is mainly affected by the filtration of the estuary and the barrier impacts of the coastal current in the ECS. The environmental physicochemical conditions that vary significantly in the turbidity zone greatly influence the associated forms of metals. The metals in the acid-soluble fraction are mostly affected by the pH change in the sediment and the discharge of human activities, while the reducible fraction is significantly affected by the bottom water DO. The oxidizable fraction was affected by oxidation-reduction potential (ORP), primary productivity, as well as OM content. Therefore, with changes in the physicochemical conditions of the environment, the metals have undergone significant changes in their speciation from the YR to the ECS shelf. Various complex effects in the estuary area have not only a large filtration effect on the total amount of metals but also a major impact on the geochemical forms of the metals.

We conducted an exposure experiment with Diffusive Gradients in Thin- Films (DGT), fathead minnow (Pimephales promelas), and yellow lampmussel (Lampsilis cariosa) to estimate bioavailability and bioaccumulation of Cu. We hypothesized that Cu concentrations measured by DGT can be used to predict Cu accumulation in aquatic animals and alterations of water chemistry can affect DGT's predict ability. Three water chemistries (control soft water, hard water, and addition of natural organic matter (NOM)) and three Cu concentrations (0, 30, and 60 μg/L) were selected, so nine Cu-water chemistry combinations were used. NOM addition treatments resulted in decreased concentrations of DGT-measured Cu and free Cu ion predicted by Biotic Ligand Model (BLM). Both hard water and NOM addition treatments had reduced concentrations of Cu ion and Cu-dissolved organic matter complexes compared to other treatments. DGT-measured Cu concentrations were linearly correlated to fish accumulated Cu, but not to mussel accumulated Cu. Concentrations of bioavailable Cu predicted by BLM, the species complexed with biotic ligands of aquatic organisms and, was highly correlated to DGT-measured Cu. In general, DGT-measured Cu fit Cu accumulations in fish, and this passive sampling technique is acceptable at predicting Cu concentrations in fish in waters with low NOM concentrations.

Correct characterization of metal speciation and reactivity is a prerequisite for the risk assessment and remedial activity management of contaminated soil. To better understand the intrinsic reactivity of Pb and Zn, nine heavily and poorly contaminated soils were investigated using the combined approaches of chemical extractions, multi-element stable isotopic dilution (ID) method, and multi-surface modelling. The ID results show that 0.1–38% of total Pb and 3–45% of total Zn in the studied soils are isotopically exchangeable after a 3-day equilibration. The intercomparison between experimental and modelling results evidences that single extraction with 0.43 M HNO3 solubilizes part of non-isotopically exchangeable fraction of Pb and Zn in the studied soils, and cannot be used as a surrogate for ID to assess labile Pb and Zn pools in soil. Both selective sequential extraction (SSE) and modelling reveal that Mn oxides are the predominant sorption surface for Pb in the studied soils; while Zn is predicted to be mainly associated with soil organic matter in the soil with low pH and Fe/Mn oxides in the soils with high pH. Multi-surface modelling can provide a reasonable prediction of Pb and Zn adsorption onto different soil constituents for the most of the studied soils. The modelling could be a promising tool to decipher the underlying mechanism that controls metal reactivity in soil, but the submodel for Mn oxides should be incorporated and the model parameters, especially for the 2-pK diffuse layer model for Mn oxides, should be updated in the further studies.

Toxic metalloids including arsenic (As) can neither be eliminated nor destroyed from environment; however, they can be converted from toxic to less/non-toxic forms. The form of As species and their concentration determines its toxicity in plants. Therefore, the microbe mediated biotransformation of As is crucial for its plant uptake and toxicity. In the present study the role of As tolerant Trichoderma in modulating As toxicity in chickpea plants was explored. Chickpea plants grown in arsenate spiked soil under green house conditions were inoculated with two plant growth promoting Trichoderma strains, M-35 (As tolerant) and PPLF-28 (As sensitive). Total As concentration in chickpea tissue was comparable in both the Trichoderma treatments, however, differences in levels of organic and inorganic As (iAs) species were observed. The shift in iAs to organic As species ratio in tolerant Trichoderma treatment correlated with enhanced plant growth and nutrient content. Arsenic stress amelioration in tolerant Trichoderma treatment was also evident through rhizospheric microbial community and anatomical studies of the stem morphology. Down regulation of abiotic stress responsive genes (MIPS, PGIP, CGG) in tolerant Trichoderma + As treatment as compared to As alone and sensitive Trichoderma + As treatment also revealed that tolerant strain enhanced the plant's potential to cope with As stress as compared to sensitive one. Considering the bioremediation and plant growth promotion potential, the tolerant Trichoderma may appear promising for its utilization in As affected fields for enhancing agricultural productivity.

Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that biosolids Ag concentrations have decreased significantly over recent decades. XANES revealed the importance of reduced-sulfur binding environments for Ag speciation in materials ranging from freshly produced sludge to biosolids weathered under ambient environmental conditions for more than 50 years. Isotopic dilution with 110mAg showed that Ag was predominantly non-labile in both fresh and aged biosolids (13.7% mean lability), with E-values ranging from 0.3 to 60 mg/kg and 5 mM CaNO3 extractable Ag from 1.2 to 609 μg/kg (0.002–3.4% of the total Ag). This study indicates that at the time of soil application, biosolids Ag will be predominantly Ag-sulfides and characterised by low isotopic lability.

We investigated the effects of arsenic species on As accumulation, plant growth and rhizospheric changes in As−hyperaccumulator Pteris vittata (PV). PV was grown for 60−d in a soil spiked with 200 mg kg−1 arsenate (AsV−soil) or arsenite (AsIII−soil). Diffusive gradients in thin−films technique (DGT) were used to monitor As uptake by PV. Interestingly AsIII−soil produced the highest PV biomass at 8.6 g plant−1, 27% and 46% greater than AsV−soil and the control. Biomass increase was associated with As−induced P uptake by PV. Although AsIII was oxidized to AsV during the experiment, As species impacted As accumulation by PV, with 17.5% more As in AsIII−soil than AsV−soil (36 vs. 31 mg plant−1). As concentration in PV roots was 30% higher in AsV−soil whereas As concentration in PV fronds was 7.9% greater in AsIII−soil, suggesting more rapid translocation of AsIII than AsV. These findings were important to understand the mechanisms of As uptake, accumulation and translocation by PV.

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectroscopy. After two weeks of ageing the E-values for Ag decreased by 20–90% with a further decrease of 10–40% after six months. The overall decrease in labile Ag for all soils after the 6 month ageing period was 50–100%. The ageing was more rapid and pronounced in the alkaline soils. XANES results for Ag in soils indicated that for the majority of soils the added Ag+ was reduced to metallic Ag over time, and associations with Fe-oxohydroxides and reduced S groups in organic matter also decreased Ag lability. Strong positive correlations were found between metallic Ag and non-labile Ag and between organic carbon and Ag bonded with S species.

Amending contaminated soils with organic wastes can influence trace element mobility and toxicity. Soluble concentrations of metals and arsenic were measured in pore water and aqueous soil extracts following the amendment of a heavily contaminated mine soil with compost and biochar (10% v:v) in a pot experiment. Speciation modelling and toxicity assays (Vibrio fischeri luminescence inhibition and Lolium perenne germination) were performed to discriminate mechanisms controlling metal mobility and assess toxicity risk thereafter. Biochar reduced free metal concentrations furthest but dissolved organic carbon primarily controlled metal mobility after compost amendment. Individually, both amendments induced considerable solubilisation of arsenic to pore water (>2500 μg l−1) related to pH and soluble phosphate but combining amendments most effectively reduced toxicity due to simultaneous reductions in extractable metals and increases in soluble nutrients (P). Thus the measure–monitor-model approach taken determined that combining the amendments was most effective at mitigating attendant toxicity risk.

Serious pollution is caused by heavy metals (HMs) emission during sludge combustion treatment, but the addition of minerals has the ability to alleviate the migration of HMs to the gaseous state. In this study, HMs (As, Cr, Zn and Cu) behavior, speciation, and environmental risk during sludge combustion with CaO and montmorillonite (MMT) additive was investigated in the lab-scale tube furnace. The results showed that the sludge combustion was mainly determined by volatile matter. In general, CaO inhibited the volatilization of Cr, Zn, and Cu, but promoted As volatilization. MMT inhibited the volatilization of HMs, but the effect was not obvious at high temperatures. Besides, the improvement of retention effect was not found for Cr and Cu with the increase of CaO at 1000 °C, there might exist threshold value for CaO on HMs retention process. Meanwhile, CaO increased acid-soluble fraction of As significantly at high temperatures, decreased residual fraction of Cr by oxidation, converted Zn and Cu to residual fraction. MMT increased the acid-soluble fraction of As and residual fraction of Cr. In view of the HMs environmental risk in ash, the combustion temperature of sludge was necessary to control under 1000 °C and minerals additive amount was needed to manage above 1000 °C.

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.