Estuaries are subject to intense human use globally, with impacts from multiple stressors, such as metal contaminants. A key challenge is extending beyond traditional monitoring approaches to understand effects to biota and system function. To explore the metabolic effects of complex metal contaminants to sediment dwelling (benthic) fauna, we apply a multiple-lines-of-evidence approach, coupling environmental monitoring, benthic sampling, total metals analysis and targeted metabolomics.We characterise metabolic signatures of metal exposure in three benthic invertebrate taxa, which differed in distribution across sites and severity of metal exposure: sipunculid (very high), amphipod (high), maldanid polychaete (moderate). We observed sediment and tissue metal loads far exceeding sediment guidelines where toxicity-related adverse effects may be expected, for metals including, As, Cd, Pb, Zn and Hg.Change in site- and taxa-specific metabolite profiles was highly correlated with natural environmental drivers (sediment total organic carbon and water temperature). At the most metal influenced sites, metabolite variation was also correlated with sediment metal loads. Using supervised multivariate regression, taxa-specific metabolic signatures of increased exposure and possibility of toxic effects were characterised against multiple reference sites. Metabolic signatures varied according to each taxon and degree of metal exposure, but primarily indicated altered cysteine and methionine metabolism, metal-binding and elimination (lysosomal) activity, coupled to change in complex biosynthesis pathways, responses to oxidative stress, and cellular damage.This novel multiple-lines-of-evidence approach combining metabolomics with traditional environmental monitoring, enabled detection and characterisation of chronic metal exposure effects in situ in multiple invertebrate taxa. With capacity for application to rapid and effective monitoring of non-model species in complex environments, these approaches are critical for improved assessment and management of systems that are increasingly subject to anthropogenic drivers of change.

Phytoremediation is potentially effective for managing excessive selenium (Se) in drainage sediment residing in the San Luis Drain in central California. This 2-year field study examined the feasibility of amending drainage sediment (containing 4.78 mg Se g 1) with methionine and casein to enhance volatilization without or with vegetation of Sporobolus airoides. Results show that without organic amendments, rates of Se volatilization were less than 25 mgm 2 d 1 in all plots. After amending the sediment with 71.4 mg methionine kg 1 soil, Se volatilization rates were 434 107 mgm 2 d 1 in vegetated plots and 289 117 mgm 2 d 1 in irrigated bare plots.With the amendment of 572 mg casein kg 1 soil, rates increased to 346 103 mgm 2 d 1 in irrigated bare plots and to 114 55 mgm 2 d 1 in vegetated plots. Both methionine and casein promoted biological remediation of Se via volatilization most effectively during the warmest months.

In current study, we investigated the changes of proteome profiles of Pycnoporus sanguineus after a single exposure of Cr(VI), TBBPA and a combined exposure of TBBPA and Cr(VI), with the goal of illuminating the cellular mechanisms involved in the interactions of co-existed TBBPA and Cr(VI) with the cells of P. sanguineus at the protein level. The results revealed that some ATP-binding cassette (ABC) transporters were obviously induced by these pollutants to accelerate the transportation, transformation and detoxification of TBBPA and Cr(VI). Cr(VI) could inhibit the bioremoval of its organic co-pollutants TBBPA through suppressing the expression of several key proteins related to the metabolism of TBBPA by P. sanguineus, including two cytochrome P450s, pentachlorophenol 4-monooxygenase and glutathione S-transferases. Furthermore, Cr(VI) possibly reduced the cell vitality and growth of P. sanguineus by enhancing the expression of imidazole glycerol phosphate synthase as well as by decreasing the abundances of proteins associated with the intracellular metabolic processes, such as the tricarboxylic acid cycle, purine metabolism and glutathione biosynthesis, thereby adversely affecting the biotransformation of TBBPA. Cr(VI) also inhibited the expression of peptidyl prolyl cis/trans isomerases, thus causing the damage of cell membrane integrity. In addition, some important proteins participated in the resistance to Cr(VI) toxicity were observed to up-regulate, including heat shock proteins, 26S proteasome, peroxiredoxins and three critical proteins implicated in S-adenosyl methionine synthesis, which contributed to reducing the hazard of Cr(VI) to P. sanguineus. The results of this study provide novel insights into the physiological responses and molecular mechanism of white rot fungi P. sanguineus to the stress of concomitant TBBPA and Cr(VI).

As the world burden of environmental contamination increases, it is of the utmost importance to develop streamlined approaches to environmental risk assessment in order to prioritize mitigation measures. Whole-cell biosensors or bioreporters and speciation modeling have both become of increasing interest to determine the bioavailability of pollutants, as bioavailability is increasingly in use as an indicator of risk. Herein, we examine whether bioreporter results are able to reflect expectations based on chemical reactivity and speciation modeling, with the hope to extend the research into a wider framework of risk assessment. We study a specific test case concerning the bioavailability of lead (Pb) in aqueous environments containing Pb-complexing ligands. Ligands studied include ethylene diamine tetra-acetic acid (EDTA), meso-2,3 dimercaptosuccinic acid (DMSA), leucine, methionine, cysteine, glutathione, and humic acid (HA), and we also performed experiments using natural water samples from Lake Tai (Taihu), the third largest lake in China. We find that EDTA, DMSA, cysteine, glutathione, and HA amendment significantly reduced Pb bioavailability with increasing ligand concentration according to a log-sigmoid trend. Increasing dissolved organic carbon in Taihu water also had the same effect, whereas leucine and methionine had no notable effect on bioavailability at the concentrations tested. We find that bioreporter results are in accord with the reduction of aqueous Pb2+ that we expect from the relative complexation affinities of the different ligands tested. For EDTA and HA, for which reasonably accurate ionization and complexation constants are known, speciation modeling is in agreement with bioreporter response to within the level of uncertainty recognised as reasonable by the United States Environmental Protection Agency for speciation-based risk assessment applications. These findings represent a first step toward using bioreporter technology to streamline the biological confirmation or validation of speciation modeling for use in environmental risk assessment.

To explore the mechanisms and influence factors on the production of 2,4,6-trichloroanisole (2,4,6-TCA) in surface waters, the 2,4,6-TCA formation potential (FP) test was conducted by incubating the real lake water with the addition of 2,4,6-trichlorophenol (2,4,6-TCP) precursor. Besides bacteria and fungi, two common cyanobacteria and algae species, i.e., Chlorella vulgaris and Anabaena flos-aquae, have been proved to have strong capabilities to produce 2,4,6-TCA, which may contribute the high 2,4,6-TCA FP (152.2 ng/L) of lake water. The microbial O-methylation of 2,4,6-TCP precursor is catalyzed by chlorophenol O-methyltransferases (CPOMTs), and their characteristics were identified by adding inductive methyl donors or excluding microorganisms via ultrafiltration. The results indicated both S-adenosyl methionine (SAM) dependent and non-SAM dependent CPOMTs played important roles; extracellular CPOMTs also participated in the biosynthesis of 2,4,6-TCA. Moreover, investigating the effects of various environmental factors revealed initial 2,4,6-TCP processor concentration, temperature, pH and some divalent metal cations (i.e., Mn2+, Mg2+ and Zn2+) had obvious effects on the production of 2,4,6-TCA.

Rising tropospheric ozone concentrations in Asia affect the yield and quality of rice. This study investigated ozone-induced changes in rice grain quality in contrasting rice genotypes, and explored the associated physiological processes during the reproductive growth phase. The ozone sensitive variety Nipponbare and a breeding line (L81) containing two tolerance QTLs in Nipponbare background were exposed to 100 ppb ozone (8 h per day) or control conditions throughout their growth. Ozone affected grain chalkiness and protein concentration and composition. The percentage of chalky grains was significantly increased in Nipponbare but not in L81. Physiological measurements suggested that grain chalkiness was associated with a drop in foliar carbohydrate and nitrogen levels during grain filling, which was less pronounced in the tolerant L81. Grain total protein concentration was significantly increased in the ozone treatment, although the albumin fraction (water soluble protein) decreased. The increase in protein was more pronounced in L81, due to increases in the glutelin fraction in this genotype. Amino acids responded differently to the ozone treatment. Three essential amino acids (leucine, methionine and threonine) showed significant increases, while seven showed significant treatment by genotype interactions, mostly due to more positive responses in L81. The trend of increased grain protein was in contrast to foliar nitrogen levels, which were negatively affected by ozone. A negative correlation between grain protein and foliar nitrogen in ozone stress indicated that higher grain protein cannot be explained by a concentration effect in all tissues due to lower biomass production. Rather, ozone exposure affected the nitrogen distribution, as indicated by altered foliar activity of the enzymes involved in nitrogen metabolism, such as glutamine synthetase and glutamine-2-oxoglutarate aminotransferase. Our results demonstrate differential responses of grain quality to ozone due to the presence of tolerance QTL, and partly explain the underlying physiological processes.

Platichthys flesus is often used as a sentinel species to monitor the estuarine water quality. In this study, we carried out an experimental contamination of fish using a PAHs/PCBs mixture, which was designed to mimic the concentrations found in the Seine estuary (C1) and 10 times these concentrations (C2). We used a proteomic approach to understand the molecular mechanisms implied in the response of P. flesus to these xenobiotics. We showed that 54 proteins were differentially accumulated in one or several conditions, which 34 displayed accumulation factors higher than two. 18 of these proteins were identified by MALDI TOF–TOF mass spectrometry. The results indicated the deregulation of oxidative stress- and glutathione metabolism-(GST, GPx) proteins as well as of several proteins belonging to the betaine demethylation pathway and the methionine cycle (BHMT, SHMT, SAHH), suggesting a role for these different pathways in the P. flesus response to chemical contamination.

Microcystis is a well-known toxic cyanobacterium in eutrophic environments, and an increasing number of Microcystis blooms have emerged in salty reservoirs and coastal rivers. This study observed that many Microcystis were identified in a coastal river in June 2020. The relative abundance of Microcystis decreased from 81.2 to 10.2% in the sampling sites from a salinity of 0 (Sal. 0) to a salinity of 12 (Sal. 12). Hepatotoxic microcystins (MCs) were identified in the coastal river and its estuary. Of the samples, those with a salinity of 5 (Sal. 5) had the highest concentration of MCs at 7.81 ± 0.67 μg L⁻¹. In a saline water simulation experiment, the results showed that salt inhibited Microcystis (M.) aeruginosa growth, enhanced the activity levels of superoxide dismutase (SOD) and catalase (CAT) and stimulated microcystin production. Transcription analysis showed that the expression levels of the psaB and rbcL genes controlling photosymbiotic processes were downregulated, and capD and csaBgene-related polysaccharide productions were upregulated by salt incubation. Notably, metabolism analysis showed that the total polysaccharides, proteins and small molecular matter, such as sucrose, methionine and N-acetyl-D-glucosamine, in the Microcystis cells increased substantially to resist the extracellular hyperosmotic pressure caused by the high salinity levels in culture. These findings indicate that increased salt in a natural aquatic body shifts the phytoplankton community by influencing the physiological metabolism of cyanobacteria and poses a high risk of microcystin exposure during cyanobacterial blooms in coastal rivers.

Cold plasma (CP) application has increasing interest due to its environmental-friendly, high efficient, and low cost aspects to mitigate deletion effects of heavy metals on plants. A pot experiment was carried out to evaluate the CP application on yield, physiological, and fatty acid profile of wheat (Triticum aestivum L.) in a completely randomized design (CRD) with five replicates. Cadmium (Cd) was applied at four levels (0, 50, 100, and 150 μM), and CP were used on germinated seeds at three levels (0, 60, and 120 s) in a hydroponic system. The results showed CP alleviated the Cd accumulation in roots, shoots, and grains. The significant reduction of grain yield (GY) and thousand grain yield (TGY) was observed in plants exposed to 100 and 150 μM compared with the control plants; however, CP improved GY and TGY particularly at severe Cd stress. The minimum chlorophyll (Chl) and relative water content (RWC) were observed in plants exposed in 100 μM Cd and non-CP treatments. Proline increased by Cd stress but decreased with CP in most treatments. Unlike proline, methionine showed significant reduction under Cd stress. The fatty acid profile of wheat represented that severe Cd stress decreased monounsaturated fatty acid (MUFA) but increased polyunsaturated fatty acid (PUFA). Heat map (HM) showed that GY and methionine were the most sensitive traits under treatments of Cd and CP. Totally, we suggest the use of 120 s of CP to mitigate Cd stress on wheat plants.

Heavy metal accumulation in crop grains due to hazardous metal contamination is considered a great concern. However, phytobeneficial fungi are reported to have important abilities for the biosafety of crops grown in contaminated soil. Therefore, the current study was undertaken to explore the mutualistic association of plant growth-promoting endophytic fungi in reducing heavy metal concentration in the seeds of soybean plants subsequently grown in contaminated soil, without comprising seed quality and biochemical profile. The results revealed that endophytic Paecilomyces formosus LHL10 and Penicillium funiculosum LHL06 synergistically produced higher amounts of GAs and IAA in a co-cultured medium. Moreover, the co-inoculation of LHL06 and LHL10 to soybean plants grown under multi-metal toxic conditions significantly mitigated the adverse effects of heavy metal toxicity and increased the seed production (number of pods per plants, number of seeds per pod, and 100 seed weight) of soybean plants grown under control and multi-metal toxic conditions. Moreover, the levels of carbohydrates (glucose, sucrose, and fructose), minerals (iron, calcium, magnesium, and potassium), amino acids (serine, glutamic acids, glycine, methionine, lysine, arginine, and proline), and antioxidants (superoxide dismutase, catalase, and peroxidase) were significantly enhanced in sole and co-inoculated plants under control and stress conditions. Whereas organic acids (citric acid, tartaric acid, malic acid, and succinic acid), lipid peroxidation (MDA) products, multi-metal accumulation (nickel, cadmium, copper, lead, chromium, and aluminum), and stress-responsive endogenous abscisic acid levels were significantly decreased in seeds of soybean plants grown under control and multi-metal toxic conditions upon LHL06 and LHL10 sole and co-inoculation. The current results suggested the positive biochemical regulation in seeds for improving the nutritional status and making it safe for human consumption.