International audience | Macrophytes are known to bioaccumulate metals, but a thorough understanding of tolerance strategies and molecular impact of metals in aquatic plants is still lacking. The present study aimed to compare Hg and Cd effects in a representative macrophyte, Elodea nuttallii using physiological endpoints and metabolite profiles in shoots and cytosol. Exposure 24 h to methyl-Hg (30 ng L), inorganic Hg (70 ng L) and Cd (280 μg L) did not affect photosynthesis, or antioxidant enzymes despite the significant accumulation of metals, confirming a sublethal stress level. In shoots, Cd resulted in a higher level of regulation of metabolites than MeHg, while MeHg resulted in the largest number of regulated metabolites and IHg treatment regulated no metabolites significantly. In cytosol, Cd regulated more metabolites than IHg and only arginine, histidine and mannose were reduced by MeHg exposure. Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis of data suggested that exposure to MeHg resulted in biochemical changes including aminoacyl-tRNA biosynthesis, glycine, serine and threonine metabolism, nitrogen metabolism, arginine and proline metabolism, cyanoamino acid metabolism, while the treatment of Cd stress caused significant variations in aminoacyl-tRNA biosynthesis and branched-chain amino acids pathways. Data supports an impact of MeHg on N homeostasis, while Cd resulted in an osmotic stress-like pattern and IHg had a low impact. Marked differences in the responses to MeHg and IHg exposure were evidenced, supporting different molecular toxicity pathways and main impact of MeHg on non-soluble compartment, while main impact of IHg was on soluble compartment. Metabolomics was used for the first time in this species and proved to be very useful to confirm and complement recent knowledge gained by transcriptomics and proteomics, highlighting the high interest of multi-omics approaches to identify early impact of environmental pollution.

Selenium (Se) radioactive wastes can be disposed through stabilization/solidification (S/S) based on the cementitious matrix on hydration products, where hydrocalumite (Ca₂Al-LDH) is expected to play an important role in the retention of SeO₄²⁻. Natural organic matters (NOMs) are known to be a risk to affect the transportation and mobility of undesirable chemical species in the pedosphere which receives the low level radioactive wastes (LLW). In the present work, five amino acids were selected as the simplified models of NOMs in the pedosphere to explore their effects on the stability of Ca₂Al-LDH after immobilized SeO₄²⁻ under alkaline conditions. As the loading amount of amino acids on Ca₂Al-LDH increasing, release of SeO₄²⁻ was enhanced in HGly, H₂Asp, and H₂Cys series, while no enhancement was observed in HPhe and HTrp series. Density functional theory (DFT) calculation predicted ion-exchange of amino acids and CO₃²⁻ with SeO₄²⁻ in a unit cell of LDH model. The intercalation of Asp²⁻ and CO₃²⁻ caused 003 peaks in XRD sharper and d₀₀₃ decreased from 8.15 Å to 7.70 Å which is assigned to Ca₂Al-LDH(Asp, CO₃). In H₂Cys series, the 003 peaks were kept broad and SeO₄²⁻ was still relatively maintained in LDH which was caused by the lower amounts of intercalated CO₃²⁻ in the presence of H₂Cys. Amino acids in the interlayer of Ca₂Al-LDH have several possible configurations, where the most stable one is prone to be in a horizontal direction through hydrogen bonds and Ca–O chemical bonds. This provides an insight on the stability of selenate immobilized in hydrocalumite, which can be produced in cement disposing in the pedosphere for a long term of burying. Not only carbonate but also small molecular organic matters like amino acids possibly give environmental impact on the mobility of low level anionic radionuclides in LDH.

It is highly likely that the toxicity of water accommodated fractions (WAF) will influence marine microalgae, and consequently lead to potential risk for the marine ecological environment. However, it was often neglected whether WAF can influence the transformation of relative compounds in organisms. The metabolism of amino acids (AAs) can be used to track physiological changes in microalgae because amino acids are the basis of proteins and enzymes. In this study, using marine Chlorophyta Platymonas helgolandica as the test organism, the effects of different concentrations of WAF on AA compositions and stable carbon isotope ratios (δ¹³C) of individual AAs of Platymonas helgolandica were investigated. The results showed that the WAF of #180 fuel oil had an obvious suppressing effect on the growth and chlorophyll a content of microalgae. The growth inhibitory rate at 96 h was 80.66% at a WAF concentration of 0.50 mg L⁻¹ compared with the control. Furthermore, seven among the 16 AAs, including alanine, cysteine, proline, aspartic acid, lysine, histidine and tyrosine, had relatively high abundance. Under the glycolysis pathway, the cysteine abundance was higher than control, meaning that the biosynthesized pathway of alanine through cysteine as a precursor could be damaged. Phosphoenolpyruvate (PEP) was an important synthesis precursor of alanine (leucine) and aromatic AA family (Phenylalanine and tyrosine), and played an important role in δ¹³CAAₛ fractionation under the WAF stress. Under the TCA pathway, to protect cell metabolism activities under WAF stress, the δ¹³C value of threonine and proline abundance in microalgae with the increase in WAF stress. Therefore, δ¹³CAAₛ fractionation can be used as a novel method for toxicity evaluation of WAF on future.

Concerns about the environmental and human health implications of TiO₂ nanoparticles (nTiO₂) are growing with their increased use in consumer and industrial products. Investigations of the underlying molecular mechanisms of nTiO₂ tolerance in organisms will assist in countering nTiO₂ toxicity. In this study, the countermeasures exhibited by the slime mold Physarum polycephalum macroplasmodium against nTiO₂ toxicity were investigated from a physiological, transcriptional, and metabolic perspective. The results suggested that the countermeasures against nTiO₂ exposure include gene-associated metabolic rearrangements in cellular pathways involved in amino acid, carbohydrate, and nucleic acid metabolism. Gene-associated nonmetabolic rearrangements involve processes such as DNA repair, DNA replication, and the cell cycle, and occur mainly when macroplasmodia are exposed to inhibitory doses of nTiO₂. Interestingly, the growth of macroplasmodia and mammal cells was significantly restored by supplementation with a combination of responsive metabolites identified by metabolome analysis. Taken together, we report a novel model organism for the study of nTiO₂ tolerance and provide insights into countermeasures taken by macroplasmodia in response to nTiO₂ toxicity. Furthermore, we also present an approach to mitigate the effects of nTiO₂ toxicity in cells by metabolic intervention.

The residue of simazine herbicide in the environment is known as one of pollutant stress for lizards by crippling its fitness on direct toxic effects and indirect food shortage via the food chain effects. Both stressors were considered in our experiment in the simazine exposure and food availability to lizards (Eremias argus). The results revealed that starvation significantly reduced the lizard’s energy reserve and native immune function, while the accumulation of simazine in the liver was significantly increased. Simazine caused oxidative stress in the liver of lizards, but oxidative damage only occurred in the starved lizards. Simazine also changed the energy reserves, native immune function and detoxification of well-fed lizards, while the starved lizards showed different sensitivity to simazine. Simazine or starvation treatment independently activated the lizard HPA axis, but co-treatment caused the HPA axis inhibition. Besides, according to the variations on amino acid neurotransmitters, corticosterone hormone and thermoregulatory behavior, we inferred that lizards in threatens take the appropriate strategy on energy investment and allocation through neural, endocrine and behavioral pathways to maximize benefits in dilemma. Energy allocation was necessary, while suppression on any physiological process comes at a cost that is detrimental to long-term individual fitness.

Heavy metal stress in soil accelerates the plant root exudation of organic ligands. The degradation of exudate ligands can be fundamental to controlling the complexation of heavy metals. However, this process remains poorly understood. Here, we investigated the relationship between the transformation of glycine, a representative amino acid exudate, and cadmium/lead mobility in soils. Two 48-h incubation experiments were conducted after glycine addition to the soils. Parameters related to glycine distribution and degradation, Cd/Pb mobility, and the formation of glycine-Cd complex were analyzed. Glycine addition gradually decreased the Cd and Pb mobility throughout the 48-h incubation. By the end of the experiment, the CaCl₂-extracted Cd and Pb concentrations decreased by 63.5% and 43.6%, respectively. The glycine mineralization was strong in the first 6 h, as indicated by a sharp decrease in CO₂ efflux rates from 10.04 ± 0.62 to 3.51 ± 0.07 mg C–CO₂ kg⁻¹ soil h⁻¹. The mineralization rates notably decreased after 6 h. The comparisons of dissolved organic carbon and hydrolyzable amino acid contents indicated that glycine mineralization in solution (95.6%) was much stronger than that in soil solids (49.3%). At the end of incubation, 0.22 mmol kg⁻¹ glycine remained in soil solids. The remaining glycine provided sufficient sorption sites for Cd²⁺ and Pb²⁺, resulting in enhanced metal fixation via complexation. Comparisons of zeta potentials supported the formation of the glycine-Cd complex. The Cd and Pb immobilization processes could be attributed to metal-glycine complex formation, sorption re-equilibrium, and glycine degradation. These findings emphasize that the biogeochemical processes of glycine, derived from root exudates or protein degradation products, increased the sorption of heavy metals to soils and thus reduced their toxicity to plants.

The release of hexavalent chromium [Cr(VI)] into water bodies poses a major threat to the environment and human health. However, studies of the biological response to Cr(VI) are limited. In this study, a toxic bacterial mechanism of Cr(VI) was investigated using Pannonibacter phragmitetus BB (hereafter BB), which was isolated from chromate slag. The maximum Cr(VI) concentrations with respect to the resistance and reduction by BB are 4000 mg L−1 and 2500 mg L−1, respectively. In the BB genome, more genes responsible for Cr(VI) resistance and reduction are observed compared with other P. phragmitetus strains. A total of 361 proteins were upregulated to respond to Cr(VI) exposure, including enzymes for Cr(VI) uptake, intracellular reduction, ROS detoxification, DNA repair, and Cr(VI) efflux and proteins associated with novel mechanisms involving extracellular reduction mediated by electron transfer, quorum sensing, and chemotaxis. Based on metabolomic analysis, 174 metabolites were identified. Most of the upregulated metabolites are involved in amino acid, glucose, lipid, and energy metabolisms. The results show that Cr(VI) induces metabolite production, while metabolites promote Cr(VI) reduction. Overall, multi-enzyme expression and metabolite production by BB contribute to its high ability to resist/reduce Cr(VI). This study provides details supporting the theory of Cr(VI) reduction and a theoretical basis for the efficient bioremoval of Cr(VI) from the environment.

Triclosan is one of the most frequently detected emerging contaminants in aquatic environment. In this study, we investigated the biouptake, toxicity and biotransformation of triclosan in freshwater algae Cymbella sp. The influence of humic acid, as a representative of dissolved organic matter, was also explored. Results from this study showed that triclosan was toxic to Cymbella sp. with 72 h EC₅₀ of 324.9 μg L⁻¹. Humic acid significantly reduced the toxicity and accumulation of triclosan in Cymbella sp. SEM analysis showed that Cymbella sp. were enormously damaged under 1 mg L⁻¹ triclosan exposure and repaired after the addition of 20 mg L⁻¹ humic acid. Triclosan can be significantly taken up by Cymbella sp. The toxicity of triclosan is related to bioaccumulated triclosan as the algal cell numbers decreased when intracellular triclosan increased. A total of 11 metabolites were identified in diatom cells and degradation pathways are proposed. Hydroxylation, methylation, dechlorination, amino acids conjunction and glucuronidation contributed to the transformative reactions of triclosan in Cymbella sp., producing biologically active products (e.g., methyl triclosan) and conjugation products (e.g., glucuronide or oxaloacetic acid conjugated triclosan), which may be included in the detoxification mechanism of triclosan.

Bromoxynil is a widely used nitrile herbicide applied to maize and other cereals in many countries. To date, still little is known about bromoxynil turnover and the structural identity of bromoxynil non-extractable residues (NER) which are reported to occur in high amounts. Therefore, we investigated the microbial turnover of ¹³C-labeled bromoxynil for 32 days. A focus was laid on the estimation of biogenic NER based on the turnover of ¹³C into amino acids (AA). At the end, 25% of ¹³C₆-bromoxynil equivalents were mineralized, 2% assigned to extractable residues and 72.5% to NER. Based on 12% in the ¹³C-total AA and an assumed share of AA of 50% in microbial biomass we arrived at 24% of total ¹³C-biogenic NER. About 33% of the total ¹³C-NER could thus be explained by ¹³C-biogenic NER; 67% was unknown and by definition xenobiotic NER with potential for toxicity. The ¹³C label from ¹³C₆-bromoxynil was mainly detected in the humic acids (28.5%), but significant amounts were also found in non-humics (17.6%), fulvic acids (13.2%) and humins (12.7%). The ¹³C-total amino acids hydrolyzed from humic acids, humins and fulvic acids amounted to 5.2%, 6.1% and 1.2% of ¹³C₆-bromoxynil equivalents, respectively, corresponding to total ¹³C-biogenic NER amounts of 10.4%, 12.2% and 2.4%. The humins contained mostly ¹³C-biogenic NER, whereas the humic and fulvic acids may be dominated by the xenobiotic NER. Due to the high proportion of unknown ¹³C-NER and particularly in the humic and fulvic acids, future studies should focus on the detailed characterization of these fractions.

The ecological toxicity of hexabromocyclododecane (HBCD) on animals, including fish and mice, has been reported, but its effects in plants, particularly its toxic mechanism, have rarely been investigated. An untargeted metabolomics approach for comprehensive assessment was selected to study the alterations in the metabolic profiles in pak choi leaves induced by exposure to trace-level amounts of HBCD diastereomers over 30 days. A supervised orthogonal partial least-squares-discriminant analysis (OPLS-DA) was performed to investigate differences between the HBCD and control groups. The discriminating metabolites were identified using public databases. The results indicated that the toxicity of the HBCD diastereomers was ordered as γ-HBCD > α-HBCD > β-HBCD. 13 metabolites were identified as potential biomarkers to discriminate the presence of HBCD toxicity. The lipid, carbohydrate, nucleotide and amino acid metabolic pathways affected were found in accordance with animals and humans, and also HBCD could induce the interference of the secondary metabolite pathways. The system of the stress defences was activated, including signalling pathway, antioxidant defence system, shikimate and phenylpropanoid metabolism. The carbohydrate and amino acid metabolism were disturbed by HBCD intervention, and the lipid, amino acid and secondary metabolite metabolism were regulated for HBCD stress prevention. These results provide insights into the mechanism and degree of HBCD phytotoxicity.