Hexabromocyclododecane (HBCD), a ubiquitous suspected contaminant, is one of the world's most prominent brominated flame retardants (BFRs). In the present study, earthworms (Eisenia fetida) were exposed to HBCD. The expression of selected antioxidant enzyme genes was measured, and the metabolic responses were assessed using nuclear magnetic resonance (NMR) to identify the molecular mechanism of the antioxidant stress reaction and the metabolic reactions of earthworms to HBCD. A significant up-regulation (p < 0.05) of superoxide dismutase (SOD) gene expression was detected, with the highest gene expression level of SOD appearing at a dose of 400 mg kg⁻¹ dw (2.06-fold, p < 0.01). However, the glutathione transferase (GST) gene expression levels did not differ significantly (p > 0.05). Principal component analysis (PCA) of the metabolic responses showed that all groups could be clearly differentiated, and the highest concentration dose group was the most distant from the control group. Except for fumarate, the measured metabolites, which included adenosine triphosphate (ATP), valine, lysine, glycine, betaine and lactate, revealed significant (p < 0.05) increases after 14 days of exposure to HBCD. HBCD likely induces high levels of anaerobic respiration, which would result in high levels of ATP and lead to the disintegration of proteins into amino acids, including valine and lysine, to produce energy. The observed changes in osmotic pressure were indicative of damage to the membrane structure. Furthermore, this study showed that NMR-based metabolomics was a more sensitive tool than measuring the gene expression levels for elucidating the mode of toxicity of HBCD in earthworm exposure studies.

Decabromodiphenyl ether (BDE-209), as a major component of brominated flame retardants, has been detected in the agricultural soil in considerable amount. Given that BDE-209 is toxic, ubiquitous and persistent, BDE-209 might induce toxic effects on rice cultivars planted in contaminated soil. A comparative study was conducted on phytotoxicities and GC-MS based antioxidant-related metabolite levels to investigate the differences of phytotoxicities of BDE-209 to rice cultivars in Yangtze River Delta of China. Rice seedlings were treated with BDE-209 at 0, 10, 50, 100 and 500 μg/L in a hydroponic setup. Results showed that BDE-209-induced phytotoxicites were cultivar-dependent and that the antioxidant defense systems in the cultivars were disturbed differently. Among the three selected cultivars (Jiayou 5, Lianjing 7 and Yongyou 9), Jiayou 5 and Lianjing 7 displayed lower toxic effects than Yongyou 9 in terms of the growth inhibition, lipid peroxidation and DNA damage. The increases of antioxidant enzymes were significantly higher in Jiayou 5 and Lianjing 7 than those in Yongyou 9. Multivariate analysis of antioxidant-related metabolites in the three cultivars indicated that l-tryptophan and l-valine were the most important ones among 10 metabolites responsible for the separation of cultivars. The up-regulation of l-tryptophan and l-valine were likely plant strategies to increase their tolerance. The current results provided an insight into the development of rice cultivars with higher BDE-209 tolerance.

Increased Cd concentrations in the environment impair plant growth, but plants properly supplied with S may develop greater tolerance to the damage caused by Cd and be used in the remediation of contaminated environments. The aim of this study was to evaluate the Cd-phytoextraction potential of Panicum maximum cv. Tanzania grown with S rates and to identify alterations in the concentrations of nutrients and amino acids and in the activity of some antioxidant enzymes under Cd stress conditions. Combinations of five S rates (0.1, 1.0, 1.9, 2.8, and 3.7 mmol L⁻¹) and five Cd rates (0.0, 0.5, 1.0, 1.5, and 2.0 mmol L⁻¹) in a nutrient solution were provided in two plant growth periods. Concentrations of N, P, and Zn increased, while K, Fe, and Mn decreased with exposure to Cd. The concentration of Ca decreased as the S supply was increased. Isoleucine, leucine, proline, and valine concentrations increased with exposure to Cd and with higher levels of S. The APX activity was higher at the highest Cd exposure level. Activity and number of SOD and GR isoforms in the roots and of CAT in the shoots of the regrown plant decreased at the highest level of contamination by Cd, which was lessened by the supply of greater S rates. Tanzania guinea grass grown with an adequate supply of S has the potential for phytoextraction of Cd-contaminated environments.

Exposure to PM₂.₅ is associated with an increased risk of lung diseases, and oxidative damage is the main reason for PM₂.₅-mediated lung injuries. However, little is known about the early molecular events in PM₂.₅-induced lung toxicity. In the present study, the metabolites in PM₂.₅-treated A549 cells were examined via a robust and nondestructive nuclear magnetic resonance (NMR)-based metabolic approach to clarify the molecular mechanism of PM₂.₅-induced toxicity. NMR analysis revealed that 12 metabolites were significantly altered in PM₂.₅-treated A549 cells, including up-regulation of alanine, valine, lactate, ω-6 fatty acids, and citrate and decreased levels of gamma-aminobutyric acid, acetate, leucine, isoleucine, D-glucose, lysine, and dimethylglycine. Pathway analysis demonstrated that seven metabolic pathways which included alanine, aspartate and glutamate metabolism, aminoacyl-tRNA biosynthesis, taurine and hypotaurine metabolism, arginine and proline metabolism, starch and sucrose metabolism, valine, leucine and isoleucine biosynthesis, and tricarboxylic acid cycle were mostly influenced. Our results indicate that NMR technique turns out to be a simple and reliable method for exploring the toxicity mechanism of air pollutant.

In this study, the metabolic effects of waterborne exposure of medaka (Oryzias latipes) to nominal concentrations of 20 (L group) and 2000 μg/L (H group) 2,4-dichlorophenol (DCP) were examined using a gas chromatography/mass spectroscopy (GC/MS) metabolomics approach. A principal component analysis (PCA) separated the L, H, and control groups along PC1 to explain the toxic effects of DCP at 24 h of exposure. Furthermore, the L and H groups were separated along PC1 at 96 h on the PCA score plots. These results suggest that the effects of DCP depended on exposure concentration and time. Changes in tricarboxylic cycle metabolites suggested that fish exposed to 2,4-DCP require more energy to metabolize and eliminate DCP, particularly at 96 h of exposure. A time-dependent response in the fish exposed to DCP was observed in the GC/MS data, suggesting that the higher DCP concentration had greater effects at 24 h than those observed in response to the lower concentration. In addition, several essential amino acids (arginine, histidine, lysine, isoleucine, leucine, methionine, phenylalanine, threonine, tryptophan, and valine) decreased after DCP exposure in the H group, and starvation condition and high concentration exposure of DCP could consume excess energy from amino acids.

The action mode of sulfonylurea herbicides is the inhibition of the acetohydroxyacid synthase (AHAS) required for the biosynthesis of amino acids valine and isoleucine in plants. However, this enzyme is also present in a range of non-targeted organisms, among which soil microorganisms are known for their pivotal role in ecosystem functioning. In order to assess microbial toxicity of sulfonylurea herbicide nicosulfuron (NS), a tiered microcosm (Tier I) to field (Tier II) experiment was designed. Soil bacteria harboring AHAS enzyme tolerant to the herbicide nicosulfuron were enumerated, isolated, taxonomically identified, and physiologically characterized. Results suggested that application of nicosulfuron drives the selection towards NS-tolerant bacteria, with increasing levels of exposure inducing an increase in their abundance and diversity in soil. Tolerance to nicosulfuron was shown to be widespread among the microbial community with various bacteria belonging to Firmicutes (Bacillus) and Actinobacteria (Arthrobacter) phyla representing most abundant and diverse clusters. While Arthrobacter bacterial population dominated community evolved under lower (Tier II) nicosulfuron selection pressure, it turns out that Bacillus dominated community evolved under higher (Tier I) nicosulfuron selection pressure. Different NS-tolerant bacteria likewise showed different levels of sensitivity to the nicosulfuron estimated by growth kinetics on nicosulfuron. As evident, Tier I exposure allowed selection of populations able to better cope with nicosulfuron. One could propose that sulfonylureas-tolerant bacterial community could constitute a useful bioindicator of exposure to these herbicides for assessing their ecotoxicity towards soil microorganisms.

The enzymatic hydrolysis using Prolyve BS coupled to membrane process (Ultrafiltration (UF) and nanofiltration (NF)) is a means of biotransformation of tuna protein waste to Tuna protein hydrolysate (TPH) with higher added values. This method could be an effective solution for the production of bioactive compounds used in various biotechnological applications and minimizing the pollution problems generated by the seafood processing industries. The amino acid composition, functional and antioxidant properties of produced TPH were evaluated. The results show that the glutamic acid, aspartic acid, glycine, alaline, valine and leucine were the major amino acids detected in the TPH profile. After membrane fractionation process, those major amino acids were concentrated in the NF retentate (NFR). The NFR and NF permeate (NFP) have a higher protein solubility (>95 %) when compared to TPH (80 %). Higher oil and water binding capacity were observed in TPH and higher emulsifying and foam stability was found in UF retentate. The NFP showed the highest DPPH radical scavenging activity (65 %). The NFR contained antioxidant amino acid (30.3 %) showed the highest superoxide radical and reducing power activities. The TPH showed the highest iron chelating activity (75 %) compared to other peptide fractions. The effect of the membrane fractionation on the molecular weight distribution of the peptide and their bioactivities was underlined. We concluded that the TPH is a valuable source of bioactive peptides and their peptide fractions may serve as useful ingredients for application in food industry and formulation of nutritional products.

Eisenia fetida earthworms were exposed to sub-lethal levels of imidacloprid for 48 h via contact filter paper tests and soil tests. After the exposure, ¹H nuclear magnetic resonance (NMR) metabolomics was used to measure earthworm sub-lethal responses by analyzing the changes in the polar metabolite profile. Maltose, glucose, malate, lactate/threonine, myo-inositol, glutamate, arginine, lysine, tyrosine, leucine, and phenylalanine relative concentrations were altered with imidacloprid exposure in soil. In addition to these metabolites (excluding leucine and phenylalanine), fumarate, ATP, inosine, betaine, scyllo-inositol, glutamine, valine, tryptophan, alanine, tyrosine, and isoleucine relative concentrations shifted with imidacloprid exposure during contact tests. Metabolite changes in E. fetida earthworms exposed to imidacloprid showed a non-linear concentration response and an upregulation in gluconeogenesis. Overall, imidacloprid exposure in soil induces a less pronounced response in metabolites glucose, maltose, fumarate, adenosine-5′-triphosphate (ATP), inosine, scyllo-inositol, lactate/threonine, and tyrosine in comparison to the response observed via contact tests. Thus, our study highlights that tests in soil can result in a different metabolic response in E. fetida and demonstrates the importance of different modes of exposure and the extent of metabolic perturbation in earthworms. Our study also emphasizes the underlying metabolic disruption of earthworms after acute sub-lethal exposure to imidacloprid. These observations should be further examined in different soil types to assess the sub-lethal toxicity of imidacloprid to soil-dwelling earthworms.

In this study, the influences of organic carbon sources (OCS, including xylose, glucose, maltose, sucrose, and starch) and inorganic and organic nitrogen sources (INS, including ammonia chloride and sodium nitrate; ONS, including arginine, alanine, proline, and valine) and metal ions (including Na⁺, K⁺, Mn²⁺, Zn²⁺ and Cu²⁺) on the growth, lipid accumulation, and nitrogen and phosphorus (N&P) removal capabilities of oleaginous Scenedesmus sp. LX1 under heterotrophic conditions were investigated. The results showed that glucose was the only OCS for Scenedesmus sp. LX1 to grow well with specific growth rate of 0.935 days⁻¹, maximum biomass of 1.72 g L⁻¹, and largest removal rates of N&P and organic carbon reaching 72.228%, 93.034%, and 19.208%, respectively. After 11 days of cultivation, the maximal biomass reached in the group with starch or glucose while maximal lipid and triacylglycerol (TAG) yields reached in the groups with maltose and sucrose, respectively. Sodium nitrate was best nitrogen source as the largest algal density, maximal yields of lipids and TAGs, and highest N&P removal rates reached up to 1.105 × 10⁷ cells·mL⁻¹, 196.70 mg L⁻¹, 5.19 mg L⁻¹, 89.61% and 100%, respectively. Scenedesmus sp. LX1 was found to have great tolerance to Na⁺, K⁺, Mn²⁺, and Zn²⁺ while 0.5 mg L⁻¹ Cu²⁺ had a strong inhibition on growth and N&P removal rate of Scenedesmus sp. LX1. Concentration increasing of five metal ions all caused the yield increases of microalgal lipid and TAGs. Graphical abstract

Concerns over the environmental and waste disposal problems created by the large amounts of by-products generated from fish processing industries are increasing worldwide. The bioconversion of those marine waste by-products through the enzymatic hydrolysis of their protein content offers the possibility for the development of bioactive peptides for use in various biotechnological applications. The present study aimed to investigate and evaluate the biological and functional properties of smooth hound (Mustelus mustelus) protein hydrolysates (SHPHs) obtained by treatment with intestinal and gastric enzyme preparations from M. mustelus viscera and porcine pancreatin. The results revealed that the SHPHs exhibited different degrees of hydrolysis and antioxidant activity. The hydrolysate produced by the intestinal crude extract presented the highest rate of antioxidative activity, showing an IC₅₀ value of 1.47 ± 0.07 mg/mL in 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging assays. The alkaline protease extract from the intestine of M. mustelus produced hydrolysate with the highest angiotensin I-converting enzyme (ACE) inhibitory activity (82 ± 1.52 % at 2 mg/mL). All the protein hydrolysates showed excellent solubility and interfacial properties that were governed by pH. The major amino acids detected in SHPHs were glutamic acid/glutamine, aspartic acid/asparagine, histidine and arginine, followed by methionine, phenylalanine, serine, valine and leucine. Overall, the results indicated that smooth hound by-products can be used to generate high value-added products, thus offering a valuable source of bioactive peptides for application in wide range of biotechnological and functional food applications.