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.

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.

Arsenic contamination of ground water is a worldwide issue, causing a number of ailments in humans. As an engineered and integrated solution, a hybrid vertical subsurface flow constructed wetland (VSSF-CW) amended with BCXZM composite (Bacillus XZM immobilized on rice husk biochar), was found effective for the bioremediation of arsenic contaminated water. Biological filter was prepared by amending top 3 cm of VSSF-CW bed with BCXZM. This filter scavenged ∼64% of total arsenic and removal efficiency of ∼95% was achieved by amended and planted (As + P + B) VSSF-CW, while non-amended (As + P) VSSF-CW showed a removal efficiency of ∼55%. The unplanted and amended (As + B) VSSF-CW showed a removal efficiency of ∼70%. The symbiotic association of Bacillus XZM, confirmed by SEM micrographs, significantly (p ≤ 0.05) reduced reactive oxygen species (ROS) and malondialdehyde (MDA) accumulation in Typha latifolia, hence, increasing the plant growth (2 folds). An increase in the indole acetic acid (IAA) and arsenic accumulation in plant was also observed in As + P + B system. The removal efficiency of the system was compromised after 4th consecutive cycle and 48 h was observed as optimum retention time. The FTIR-spectra showed the involvement of -N-H bond, carboxylic acids, –CH₂ stretching of –CH₂ and –CH₃, carbonyl groups, -C-H, C–O–P and C–O–C, sulphur/thiol and phosphate functional groups in the bio-sorption of arsenic by BCXZM filter. Our study is a first reported on the simultaneous phytoextraction and biosorption of arsenic in a hybrid VSSF-CW. It is proposed that BCXZM can be applied effectively in CWs for the bioremediation of arsenic contaminated water on large scale.

Sulfur, an essential macronutrient, plays important roles in plant development and stress mitigation. Sulfur deficiency, a common problem in agricultural soils, may disturb plant stress resistance and xenobiotic detoxification. In the present study, the function and mechanism of limited sulfur nutrition on the residues and phtotoxicity of imidacloprid were investigated in lettuce plants. Sulfur deficiency significantly increased imidacloprid accumulation in lettuce tissues, exacerbated imidacloprid biological toxicity by enhancing the accumulation of toxic metabolites, like imidacloprid-olefin. Simultaneously, imidacloprid-induced detoxification enzymes including cytochromes P450, glutathione S-transferases (GSTs) and glycosyltransferases were inhibited under limited sulfur supply. On the other hand, sulfur deficiency further enhanced the generation of reactive oxygen species and exacerbated lipid peroxidation in lettuce tissues. Sulfur deficiency mainly reduced the abundance of thiol groups, which are essential redox modulators as well as xenobiotic conjugators, and significantly inhibited GSTs expression. These results clearly suggested that sulfur deficiency inhibited the synthesis of sulfur-containing compounds, leading to increased accumulation of pesticide residues and toxic metabolites as well as reduced detoxification capacity, consequently leading to oxidative damage to plants. Therefore, moderate sulfur supply in regions where neonicotinoid insecticides are intensively and indiscriminately used may be an efficient strategy to reduce pesticide residues and the potential risk to ecosystem.

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.

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 rootless duckweed Wolffia globosa can accumulate and tolerate relatively large amounts of arsenic (As); however, the underlying mechanisms were unknown. W. globosa was exposed to different concentrations of arsenate with or without l-buthionine sulphoximine (BSO), a specific inhibitor of γ-glutamylcysteine synthetase. Free thiol compounds and As(III)–thiol complexes were identified and quantified using HPLC – high resolution ICP-MS – accurate mass ESI-MS. Without BSO, 74% of the As accumulated in the duckweed was complexed with phytochelatins (PCs), with As(III)–PC₄ and As(III)–PC₃ being the main species. BSO was taken up by the duckweed and partly deaminated. The BSO treatment completely suppressed the synthesis of PCs and the formation of As(III)–PC complexes, and also inhibited the reduction of arsenate to arsenite. BSO markedly decreased both As accumulation and As tolerance in W. globosa. The results demonstrate an important role of PCs in detoxifying As and enabling As accumulation in W. globosa.

This study aimed to investigate the role of non-enzymatic antioxidants on adaptive skills over time in the bivalve Scrobicularia plana environmentally exposed to mercury. Inter-age (2⁺, 3⁺, 4⁺, 5⁺ year old) and organ-specific (gills, digestive gland) approaches were applied in bivalves collected from moderately and highly contaminated sites at Ria de Aveiro (Portugal). S. plana's adaptive skills were dependent on the contamination extent; under moderate contamination scenario, the intervention of the different antioxidants took place harmoniously, evidencing an adjustment capacity increasing with the age. Under higher contamination degree, S. plana failed to cope with mercury threat, showing an age-dependent deterioration of the defense abilities. In organ-specific approach, the differences were particularly evident for thiol-compounds, since only gills displayed the potential to respond to moderate levels by increasing non-protein thiols and total glutathione. Under high contamination degree, both organs were unable to increase thiol-compounds, which were compensated by the ascorbic acid elevation.

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.

Cadmium as a common environmental stressor may exert highly toxic effects on herbivorous insects. The question was whether possible elevation of an oxidative stress and imbalance of energetic reserves in insects may depend on developmental stage, sex and insect population’s multigenerational history of exposure to cadmium. So, the aim of this study was to compare of the development traits, total antioxidant capacity, lipid peroxidation, RSSR to RSH ratio and the concentration of carbohydrates, glycogen, lipids and proteins in whole individuals (larvae or pupae) of Spodoptera exigua originating from two strains: control and selected over 120 generations with sublethal metal concentration (44 Cd mg per dry weight of diet). Generally, the increase of the protein, carbohydrates, glycogen concentration and lipid peroxidation decrease with age of the larvae were found. Revealed cases of a higher mobilisation of carbohydrates and proteins, and changes in total antioxidant capacity or lipid peroxidation, in individuals being under metal exposure, occurred in strain-depended mode. Short-term Cd exposure effect was connected with possible higher engagement of proteins and glycogen in detoxification processes, but also higher concentration of lipid peroxidation. In turn, for long-term Cd exposure effect lower lipids concentration and higher thiols usage seemed to be more specific.