As the first step of methylmercury (MeHg) entry into the aquatic food webs, MeHg uptake by phytoplankton is crucial in determining the final human MeHg exposure risks. MeHg availability to plankton is regulated by dissolved organic matter (DOM) in the water, while the extent of the impacts can vary largely based on the sources of DOM. Here, we investigated impacts of DOM sources on MeHg bioconcentration by three freshwater phytoplankton species (i.e. S. quadricauda, Chlorella sp., Microcystis elabens) in the laboratory system. We found that algae-derived DOM would prohibited the cellular MeHg bioconcentration by a percent up to 77–93%, while the soil-derived DOM didn't show similar inhibition effects. DOM characterization by the excitation‒emission matrices, Fourier transform infrared spectrum, ultra‒high performance liquid chromatography‒tandem quadrupole time of flight mass spectrometry shown that the molecular size of S-containing compound, rather than thiol concentration, has played a crucial role in regulating the MeHg uptake by phytoplankton. Climate change and increasing nutrient loadings from human activities may affect plankton growth in the freshwater, ultimately changing the DOM compositions. Impacts of these changes on cellular MeHg uptakes by phytoplankton should be emphasized when exploring the aquatic Hg cycling and evaluating their risks to human beings and wild life.

Arsenite [As(III)] toxicity causes impeded growth, inadequate productivity of plants and toxicity through the food chain. Using various chemical residues for priming is one of the approaches in conferring arsenic tolerance in crops. We investigated the mechanism of abscisic acid (ABA)-induced As(III) tolerance in rice genotypes (cv. Swarna and Swarna Sub1) pretreated with 10 μM of ABA for 24 h and transferred into 0, 25 and 50 μM arsenic for 10 days. Plants showed a dose-dependent bioaccumulation of As(III), oxidative stress indicators like superoxide, hydrogen peroxide, thiobarbituric acid reactive substances and the activity of lipoxygenase. As(III) had disrupted cellular redox that reflecting growth indices like net assimilation rate, relative growth rate, specific leaf weight, leaf mass ratio, relative water content, proline, delta-1-pyrroline-5-carboxylate synthetase and electrolyte leakage. ABA priming was more protective in cv. Swarna Sub1 than Swarna for retrieval of total glutathione pool, non-protein thiols, cysteine, phytochelatin and glutathione reductase. Phosphate metabolisms were significantly curtailed irrespective of genotypes where ABA had moderated phosphate uptake and its metabolizing enzymes like acid phosphatase, alkaline phosphatase and H⁺/ATPase. Rice seedlings had regulated antioxidative potential with the varied polymorphic expression of those enzymes markedly with antioxidative enzymes. The results have given the possible cellular and physiological traits those may interact with ABA priming in the establishment of plant tolerance with As(III) over accumulation and, thereby, its amelioration for oxidative damages. Finally, cv. Swarna Sub1 was identified as a rice genotype as a candidate for breeding program for sustainability against As(III) stress with cellular and physiological traits serving better for selection pressure.

The widespread production and use of silver nanomaterials (AgNMs) in consumer and medical products have been raising environmental concerns. Once in the environment, the soil is one of the major sinks of AgNMs due to e.g. sewage sludge applications, and invertebrates are directly exposed. In this study, we investigate the potential of N-acetylcysteine (NAC) to reduce the toxic effects of Ag NM300 K (and AgNO3) on the soil invertebrate Enchytraeus crypticus. Ag NM300 K induces mortality, reproduction impairment, and avoidance. The addition of NAC to the soil showed a remarkable reduction in the toxicity of Ag, indicating that NAC can act as a detoxifying agent for terrestrial organisms exposed to Ag materials. That the reduction in toxicity likely is caused by thiol groups, was confirmed by GSH and GSSH studies. Identifying the mechanisms and hence alternatives that allow the recovery of contaminated soils is an important mitigation measure to promote environmental safety and reduce the associated risks to human health. Further, it may inform on strategies to implement in safe-by-design industry development.

Phytochelatins (PCs) play a vital role in the tolerance and enrichment of cadmium (Cd) in higher plants by chelating with Cd2+. The aim of this study was to perform a full-scale metabolomics analysis of metabolic responses highly correlated with PCs generation. These metabolites and metabolic pathways were expected to promote PCs generation and further optimize Cd absorption in plants. In the current study, Amaranthus hypochondriacus, a potential species for phytoremediation, was first adopted to investigate physiological responses to Cd stress via LCMS/MS-based metabolomics and the HPLC based determination of thiol compounds. The results showed that the leaves of A. hypochondriacus under high Cd stress accumulated 40 times the amount of Cd compared to the leaves of the plants not under Cd stress and had an increased content of three types of PCs. Metabolomics qualitatively identified 12084 substances in total, among which 41 were significantly different metabolites (SDMs) between the two groups and involved in 7 metabolic pathways. Among the SDMs, 12 metabolites were highly linearly correlated with PCs involved in three pathways (Val, Leu and Ile biosynthesis; Ala, Asp and Glu metabolism; and Arg and Pro metabolism). These results provide an innovative method to promote PCs synthesis for the restoration of Cd-contaminated-soil.

The combined pollution of radionuclides and heavy metals has been given rise to widespread concern during uranium mining. The influence of As(V) on U(VI) immobilization by Mucor circinelloides (M. circinelloides) was investigated using batch experiments. The activity of antioxidative enzymes and concentrations of thiol compounds and organic acid in M. circinelloides increased to respond to different U(VI) and As(V) stress. The morphological structure of M. circinelloides changed obviously under U(VI) and As(V) stress by SEM and TEM analysis. The results of XANES and EXAFS analysis showed that U(VI) was mainly reduced to nano-uraninite (nano-UO2, 30.1%) in U400, while only 9.7% of nano-UO2 was observed in the presence of As(V) in U400-As400 due to the formation of uranyl arsenate precipitate (Trögerite, 48.6%). These observations will provide the fundamental data for fungal remediation of uranium and heavy metals in uranium-contaminated soils.

The impact of calcium-enriched biochar (BC, containing Ca, Al, Fe and P as dominant elements in the range of 6.9–1.3% with alkaline pH) obtained from sewage sludge (0.1 or 0.5% in the final soil) on cadmium-induced toxicity (final dose of 1.5 mg Cd/kg in control and 4.5 or 16.5 mg Cd/kg soil in low and high Cd treatment) was tested in medicinal plant Matricaria chamomilla. Low Cd dose had typically less negative impact than high Cd dose at the level of minerals and metabolites and the effect of BC doses often differed. Contrary to expectations, 0.5% BC with a high Cd dose increased Cd accumulation in plants about 2-fold. This was reflected in higher signals of reactive oxygen species, but especially the high dose of BC increased the amount of antioxidants (ascorbic acid and non-protein thiols), minerals and amino acids in shoots and/or roots and usually mitigated the negative effect of Cd. Surprisingly, the relationship between BC and soluble phenols was negative at high BC + high Cd dose, whereas the effect of Cd and BC on organic acids (mainly tartaric acid) differed in shoots and roots. Interestingly, BC alone applied to the control soil (1.5 mg total Cd/kg) reduced the amount of Cd in the plants by about 30%. PCA analyses confirmed that metabolic changes clearly distinguished the high Cd + high BC treatment from the corresponding Cd/BC treatments in both shoots and roots. Thus, it is clear that the effect of biochar depends not only on its dose but also on the amount of Cd in the soil, suggesting the use of Ca-rich biochar both for phytoremediation and safer food production.

Inoculation of soil or seeds with plant growth promoting bacteria ameliorates metal toxicity to plants by changing metal speciation in plant tissues but the exact location of these changes remains unknown. Knowing where the changes occur is a critical first step to establish whether metal speciation changes are driven by microbial metabolism or by plant responses. Since bacteria concentrate in the rhizosphere, we hypothesised steep changes in metal speciation across the rhizosphere. We tested this by comparing speciation of zinc (Zn) in roots of Brassica juncea plants grown in soil contaminated with 600 mg kg⁻¹ of Zn with that of bulk and rhizospheric soil using synchrotron X-ray absorption spectroscopy (XAS). Seeds were either uninoculated or inoculated with Rhizobium leguminosarum bv. trifolii and Zn was supplied in the form of sulfide (ZnS nanoparticles) and sulfate (ZnSO₄). Consistent with previous studies, Zn toxicity, as assessed by plant growth parameters, was alleviated in B. juncea inoculated with Rhizobium leguminosarum. XAS results showed that in both ZnS and ZnSO₄ treatments, the most significant changes in speciation occurred between the rhizosphere and the root, and involved an increase in the proportion of organic acids and thiol complexes. In ZnS treatments, Zn phytate and Zn citrate were the dominant organic acid complexes, whilst Zn histidine also appeared in roots exposed to ZnSO₄. Inoculation with bacteria was associated with the appearance of Zn cysteine and Zn formate in roots, suggesting that these two forms are driven by bacterial metabolism. In contrast, Zn complexation with phytate, citrate and histidine is attributed to plant responses, perhaps in the form of exudates, some with long range influence into the bulk soil, leading to shallower speciation gradients.

The toxicity of mercury (Hg), is generally known, and around 90% of Hg exist as methylmercury (CH₃Hg⁺) in marine organism. Mercury concentrates in sharks and whales, which are at the top of the food chain as predators to cephalopods. The concentrations of Hg in liver and muscle of blue shark, caught in Sagami Bay, and in digestive gland and mantles of Todarodes pacificus, Sepia madokai, and Uroteuthis edulis caught in East China Sea were measured and analyzed. The Hg concentrations in the sharks, squids, and cuttlefishes determined in this study were almost same as those in the other sea regions. In addition, the Hg concentration in the blue shark was higher in the muscle than in the liver. In S. madokai and U. edulis, Hg accumulated in the digestive gland but not in the mantle. Although the Hg concentration in the digestive gland of T. pacificus is lower than those of S. madkai and U edulis, Hg concentration in the mantle is critically higher. More than 90% of Hg is present as CH₃Hg⁺ in muscle of blue shark and mantle of T. pacificus. This feature is explained due to amino acids with the thiol groups and chain genes in the muscle of blue shark as well as in the mantle of T. pacificus. Myosin in the mantle of T. pacificus and blue shark enhances the stability of CH₃Hg⁺. The amount of Hg in the digestive gland of T. pacificus could be too large to store; thus, Hg is released to the mantle, whereas the nutrients in the digestive gland of T. pacificus are supplied to other tissues. It is considered that the muscle fiber of T. pacificus is strong; therefore, large amounts of myosin levels may be present in T. pacificus than in S. madokai and U. edulis.

A novel trithiocyanuric acid-modified corn bract (TCA-CCB) was prepared, and its removal properties for Hg²⁺ were investigated. TCA-CCB showed a remarkable absorbability for Hg²⁺ in mixed ion solutions. Adsorption kinetics experiments indicated that the removal of Hg²⁺ on TCA-CCB was quick, with a removal rate of 99.07% within 5 min. In addition, the removal rate of Hg²⁺ exceeded 98% over all pH conditions. The adsorption process can be best described by pseudo-second-order kinetic and Hill isotherm models. The saturated adsorption capacity of TCA-CCB for Hg²⁺ was 390 mg/g. The TCA-CCB could efficiently adsorb Hg²⁺ from the simulated wastewater and reduce the Hg²⁺ concentration from 10 ppm to 12.35 ppb, which was lower than the greatest allowable value of 50 ppb and satisfied the emission standards required by the Chinese government. Moreover, the removal rate of Hg²⁺ was beyond 99% after three cycles. The results of the zeta potential and X-ray photoelectron spectroscopy (XPS) implied that the chelation and ion exchange between amino/thiol groups and Hg²⁺ played a significant role in the improvement of the adsorption properties.The corn bract modified by trithiocyanuric acid exhibits apparent advantages in the removal of Hg²⁺ from ppm to ppb due to its high selectivity, adsorption capacity and stability.

This study aimed at evaluating the interactive effects of acetaminophen (AC; 400 mg kg−1) and silicon dioxide nanomaterial (nano-SiO2;3 mg kg−1) on soil-grown barley. After 14 days of growth, plant growth, evaluated in terms of fresh and dry weight, was greatly inhibited by AC, independently of being or not co-treated with nano-SiO2. Plants growing under high levels of AC did not show any increase in malondialdehyde (MDA) nor thiols contents, though levels of superoxide anion (O2.-) and hydrogen peroxide (H2O2) were increased in leaves and roots, respectively. When plants were co-treated with nano-SiO2, reactive oxygen species (ROS) content remained unchanged, but lipid peroxidation (LP) was diminished and the thiol redox network was up-regulated in roots. The evaluation of the response of the antioxidant system showed that AC affected both non-enzymatic and enzymatic components in an organ-specific manner: proline levels and superoxide dismutase (SOD) activity were enhanced, whilst catalase (CAT) activity decreased in leaves; ascorbate content and CAT activity were diminished in roots. In response to the nano-SiO2 co-treatment, this pattern was not vastly altered, despite for ascorbate peroxidase (APX), whose activity was greatly enhanced in both organs. Overall, combining biometric, biochemical and molecular approaches, this study revealed that, although AC impaired plant growth and development, it did not trigger a harsh oxidative stress condition. Maybe by this reason, the ameliorating potential of nano-SiO2 was not so evident; yet, nano-SiO2 was able to reduce LP and to stimulate thiol content and APX activity, possibly as a defense mechanism against AC-induced stress.