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The primary objective was to evaluate the toxicity of triflumezopyrim (TFP) on P. fuscipes larvae and adults at lethal and sublethal levels through topical application. Sublethal effects were assessed by examining developmental period, fecundity, life-table parameters, and fitness parameters. Enzymatic and transcriptional analyses were conducted to determine the impact of TFP on P. fuscipes physiology and gene expression. The LC 50 , LC 30 , and LC 10 of TFP against P. fuscipes larvae and adults were lower than the field-recommended dose (48.75 mg a.i. L−1), indicating direct toxicity and sublethal effects during immature stages. Exposure to LC 30 of TFP extended developmental periods for 2nd-instar larvae and pupae, reduced oviposition, larval predation efficiency, and body weight in both sexes. Sublethal concentrations affected antioxidant, detoxification, and energy reservoir enzymes significantly. Transcriptional analysis revealed impacts on insecticide detoxification, resistance, and stress-related genes. KEGG analysis showed glycerolipid metabolism is the most regulated pathway, and UGT2B10 regulated several detoxification-related pathways under TFP stress. These findings prompt reconsideration of the role of TFP in paddy field IPM due to its adverse effects on P. fuscipes , emphasizing the importance of assessing its ecological impacts before widespread application in agricultural practices. [Display omitted] • Triflumezopyrim (TFP) is toxic to Paederus fuscipes at immature stage on sublethal level. • TFP impacts P. fuscipes fitness at sublethal level. • TFP cause imbalance in antioxidants and Detox enzymes in P. fuscipes. • The energy reserves of P. fuscipes drains during TFP detoxification. • Glycerolipid metabolism pathway and UGT2B10 gene save P. fuscipes from TFP direct toxicity. [ABSTRACT FROM AUTHOR]

Consento (CON) poses a significant environmental hazard as a systemic fungicide, adversely affecting the health of non-target organisms. Nitric oxide (NO), a signaling molecule, is known to play a crucial role in plant physiology and abiotic stress tolerance. However, whether NO plays any role to enhance fungicide CON tolerance in wheat seedlings is yet unclear. Therefore, we conducted a hydroponic experiment i) to investigate the morpho-physio-biochemical changes of wheat seedlings to fungicide CON stress, and ii) to examine the effects of NO and fungicide CON treatments on oxidative damage, antioxidant system, secondary metabolism and detoxification of systemic fungicide in wheat seedlings. The results showed that CON fungicide at the highest (4X) concentration significantly decreased wheat seedlings fresh weight (46.89%), shoot length (40.26%), root length (56.11%) and total chlorophyll contents (67.44%) in a dose response relationship. Moreover, CON significantly increased hydrogen peroxide, malondialdehyde, catalase, ascorbate peroxidase, glutathione-S-transferase, and peroxidase activities while decreased reduced glutathione (GSH) content. This ultimately impaired the redox homeostasis of cells, leading to oxidative damage in cell membrane. Under fungicide treatment, the addition of NO reduced the fungicide phytotoxicity, with an increase of over 60% in seedling growth. The NO application mitigated CON phytotoxicity as reflected by significantly increased chlorophyll pigments (69.88%) and decreased oxidative damage in wheat leaves. Indeed, the NO alleviatory effect was able to increase the tolerance of seedlings to fungicide, which resulted increments in antioxidant and detoxification enzymes activity, with the enhanced GSH level (78.54%). Interestingly, NO alleviated CON phytotoxicity through the phenylpropanoid pathway by enhancing the activity of secondary metabolism enzymes such as phenylalanine ammonia-lyase (47.28%), polyphenol oxidase (9%), and associated metabolites such as phenolic acids (77.62%), flavonoids (34.33%) in wheat leaves. Our study has provided evidence that NO plays a key role in the metabolism and detoxification of systemic fungicide in wheat through enhanced activity of antioxidants, detoxifications and secondary metabolic enzymes. [Display omitted] • Consento fungicide causes oxidative damage and phytotoxicity in wheat seedlings. • NO alleviates Consento toxicity by scavenging ROS and improved carotenoid content. • NO regulates enzymatic and non-enzymatic antioxidants in wheat exposed to Consento. • NO stimulates PPO and PAL enzymatic pathway to detoxify Consento toxicity in wheat. [ABSTRACT FROM AUTHOR]

Agrochemicals play a vital role in protecting crops and enhancing agricultural production by reducing threats from pests, pathogens and weeds. The toxicological status of honey bees can be influenced by a number of factors, including pesticides. While extensive research has focused on the lethal and sublethal effects of insecticides on individual bees and colonies, it is important to recognise that fungicides and herbicides can also affect bees' health. Unfortunately, in the field, honey bees are exposed to mixtures of compounds rather than single substances. This study aimed to evaluate the effects of a commercial fungicide and a commercial herbicide, both individually and in combination, on honey bees. Mortality assays, biomarkers and learning and memory tests were performed, and the results were integrated to assess the toxicological status of honey bees. Neurotoxicity (acetylcholinesterase and carboxylesterase activities), detoxification and metabolic processes (glutathione S-transferase and alkaline phosphatase activities), immune system function (lysozyme activity and haemocytes count) and genotoxicity biomarkers (Nuclear Abnormalities assay) were assessed. The fungicide Sakura® was found to activate detoxification enzymes and affect alkaline phosphatase activity. The herbicide Elegant 2FD and the combination of both pesticides showed neurotoxic effects and induced detoxification processes. Exposure to the herbicide/fungicide mixture impaired learning and memory in honey bees. This study represents a significant advance in understanding the toxicological effects of commonly used commercial pesticides in agriculture and contributes to the development of effective strategies to mitigate their adverse effects on non-target insects. [Display omitted] • Effects of commercial fungicide and herbicide, single and in combination, were evaluated. • Mortality assay, biomarkers and learning and memory tests were performed on honey bees. • Neurotoxic effects after both mixture treatments could be attributed to the herbicide. • Herbicide and pesticide mixtures compromise honey bees' behaviour. [ABSTRACT FROM AUTHOR]

Pesticides are typically present as combinations within soil ecosystems and have detrimental effects on untamed surroundings. However, the collective impacts and fundamental mechanisms of pesticides on soil living beings are currently inadequately assessed. In our current work, we evaluated the interactive consequences of clothianidin (CLO) and prochloraz (PRO) on earthworms (Eisenia fetida) using several toxicological tests, such as acute adverse effects, biocatalytic activity, and alterations in transcriptional activity. The findings revealed that CLO (with a 14-day LC 50 value of 6.08 mg kg−1) exhibited greater toxicity compared to PRO (with a 14-day LC 50 value of 79.41 mg kg−1). Moreover, the combinations of CLO and PRO had synergistic acute effects on E. fetida. Additionally, the activities of POD, CAT, and GST were significantly varied in most instances of single and mixed treatments when compared to the control. Surprisingly, the transcriptional levels of four genes (gst , sod , crt , and ann), related to oxidative load, metabolic detoxification systems, endoplasmic reticulum, and oxytocin neuropeptide, respectively, were also altered in response to single and mixture exposures, as compared to the control. Alterations in enzyme activity and gene transcriptional level could serve as early indicators for detecting co-exposure to pesticides. The findings of this research offered valuable holistic understanding regarding the toxicity of pesticide combinations on earthworms. Further research should be conducted to investigate the persistent effects of pesticide mixtures on terrestrial invertebrates in order to draw definitive conclusions about the associated risks. [Display omitted] • The acute toxicity of clothianidin was higher than prochloraz to the earthworms. • The combinations of clothianidin and prochloraz induced synergistic acute effects. • CarE possessed important role in the synergism of clothianidin and prochloraz. • Activities of CAT and GST were significantly increased after most of the exposures. • Expression levels of 4 genes in mixtures produced greater changes than individuals. [ABSTRACT FROM AUTHOR]

Organic and nanoparticle pollutants are the main environmental problems affecting marine species, which have received great attention. However, the combined effect of pollutants on marine life in the presence of predators needs to be clarified. In this study, the effects of pentachlorophenol (PCP) and titanium dioxide nanoparticles (nano-TiO 2) on the energy metabolism of mussels (Mytilus coruscus) in the presence of predators were assessed through cellular energy allocation (CEA) approach. Mussels were exposed to PCP (0, 1, and 10 μg/L), nano-TiO 2 (1 mg/L, 25 and 100 nm), and predators (Portunus trituberculatus presence/absence) for 14 days. Exposure to high concentrations of PCP (10 μg/L) with small particle size nano-TiO 2 (25 nm) decreased cellular energy stores (carbohydrates, lipids, and proteins) and increased cellular energy demand (measured as the activity of the mitochondrial electron transport system, ETS). During the first 7 days, energy was supplied mainly through the consumption of carbohydrates, while lipids are mobilized to participate after 7 days. The presence of predators caused a further decrease in energy stores. These findings demonstrate that PCP, nano-TiO 2 and predators have a negative impact on energy metabolism at the cellular level. Carbohydrates are not able to meet the metabolic demand, lipids need to be consumed, and energy metabolism was also mediated by the involvement of proteins. Overall, our results suggest that PCP, nano-TiO 2 and predators disrupt the cellular energy metabolism of mussels through reduced cellular energy allocation, small particles and predators drive mussels to exert energetic metabolic adjustments for detoxification reactions when toxic contaminants are present. [Display omitted] • The presence of predators increases the effect of nano-TiO 2 and PCP on cellular energy allocation of mussel. • The presence of nano-TiO 2 exacerbates PCP energy depletion in mussels. • Nano-TiO 2 , PCP and crabs have interaction on cellular energy allocation. • Mussels generated comparable patterns of cellular energy allocation in response to two different kinds of pollutants. [ABSTRACT FROM AUTHOR]

The European honey bee, Apis mellifera , serves as the principle managed pollinator species globally. In recent decades, honey bee populations have been facing serious health threats from combined biotic and abiotic stressors, including diseases, limited nutrition, and agrochemical exposure. Understanding the molecular mechanisms underlying xenobiotic adaptation of A. mellifera is critical, considering its extensive exposure to phytochemicals and agrochemicals present in the environment. In this study, we conducted a comprehensive structural and functional characterization of AmGSTD1, a delta class glutathione S-transferase (GST), to unravel its roles in agrochemical detoxification and antioxidative stress responses. We determined the 3-dimensional (3D) structure of a honey bee GST using protein crystallography for the first time, providing new insights into its molecular structure. Our investigations revealed that AmGSTD1 metabolizes model substrates, including 1-chloro-2,4-dinitrobenzene (CDNB), p -nitrophenyl acetate (PNA), phenylethyl isothiocyanate (PEITC), propyl isothiocyanate (PITC), and the oxidation byproduct 4-hydroxynonenal (HNE). Moreover, we discovered that AmGSTD1 exhibits binding affinity with the fluorophore 8-Anilinonaphthalene-1-sulfonic acid (ANS), which can be inhibited with various herbicides, fungicides, insecticides, and their metabolites. These findings highlight the potential contribution of AmGSTD1 in safeguarding honey bee health against various agrochemicals, while also mitigating oxidative stress resulting from exposure to these substances. [Display omitted] • The three-dimensional structure of AmGSTD1 was solved by X-ray crystallography. • G-site S34A and H-site F142A mutants exhibited the largest changes in kinetics. • Herbicides, fungicides, insecticides, and metabolites hindered AmGSTD1-ANS binding. • AmGSTD1 was highly expressed in the Malpighian tubules of both nurse and forager bees. [ABSTRACT FROM AUTHOR]

Abstract: Silk gland is a major organ of Bombyx mori for the synthesis and secretion of silk protein. Phoxim exposure can be toxic to B. mori and causes a decrease of fibroin synthesis, finally affecting the silk production in industry. To study the mechanism of metabolism and detoxification of silk gland under phoxim exposure, we measured the residual quantity of phoxim in silk gland and hemolymph after phoxim exposure, and the detoxifying enzymes-related genes and enzyme activity were also investigated. Results indicated that the residual amount of phoxim existed up to 24 h in silk gland compared with that in hemolymph, suggesting that phoxim can accumulate in the silk glands within a certain time course. The transcriptional levels of PI3K/Akt genes, including Akt, Tor1, p70s6k and 4e-bp , were up-regulated by 6.919, 1.358, 10.766 and 7.708-fold, respectively. The expression of two downstream genes ( CncC and Keap1 ) was up-regulated by 1.939 and 3.373-fold, respectively. In addition, the transcriptional levels of detoxification-related genes including CYP6AB, CYP3 06A , CarE2, GST1 and GSTd1 were up-regulated by 1.731, 1.221, 1.366, 1.376 and 6.591-fold, respectively. The enzymatic activity of CYP450, CarE and GST were increased over time. These results provided possible insights into the injury of silk gland and the transcriptional response to detoxifying enzymes-related genes in silkworm after phoxim exposure. [ABSTRACT FROM AUTHOR]

Bivalve mollusks from the cooling reservoirs of fuel power plants (PP) are acclimated to the chronic heating and chemical pollution. We investigated stress responses of the mussels from these ponds to determine their tolerance to novel environmental pollutant, zinc oxide nanoparticles (nZnO). Male Unio tumidus from the reservoirs of Dobrotvir and Burschtyn PPs (DPP and BPP), Ukraine were exposed for 14 days to nZnO (3.1 μM), Zn 2+ (3.1 μM) at 18 °C, elevated temperature (T, 25 °C), or nZnO at 25 °C (nZnO + T). Control groups were held at 18 °C. Zn-containing exposures resulted in the elevated concentrations of total and Zn-bound metallothionein (MT and Zn-MT) in the digestive gland, an increase in the levels of non-metalated MT (up to 5 times) and alkali-labile phosphates and lysosomal membrane destabilization in hemocytes. A common signature of nZnO exposures was modulation of the multixenobiotic-resistance protein activity (a decrease in the digestive gland and increase in the gills). The origin of population strongly affected the cellular stress responses of mussels. DPP-mussels showed depletion of caspase-3 in the digestive gland and up-regulation of HSP70, HSP72 and HSP60 levels in the gill during most exposures, whereas in the BPP-mussels caspase-3 was up-regulated and HSPs either downregulated or maintained stable. BPP-mussels were less adapted to heating shown by a glutathione depletion at elevated temperature (25 °C). Comparison with the earlier studies on mussels from pristine habitats show that an integrative ‘eco-exposome’-based approach is useful for the forecast of the biological responses to novel adverse effects on aquatic organisms. [ABSTRACT FROM AUTHOR]

Aleurolyphus ovatus Troupeau is one of the most predominant species of the Acaridae family worldwide. Recent reports have demonstrated that the accumulation of lead in stored grains and dietary items exceeds the required standards. However, the molecular mechanism of heavy metal stress on mites has not been reported. To understand the mechanism underlying the heavy metal response of A. ovatus , comparative transcriptome analysis was performed in this study using an Illumina high throughput mRNA sequencing (RNA-seq) platform. A. ovatus was fed on artificial diets containing two different concentrations of lead, namely, a low concentration of 12.5 mg/kg (LAO) and a high concentration of 100 mg/kg (HAO), while the mites in the control (NAO) group were not exposed to lead. A total of 44,362 unigenes, with an average length of 1547 bp, were identified. Of these, 996 unigenes were successfully annotated in seven functional databases. The number of differentially expressed genes (DEGs) in A. ovatus under different lead concentrations was compared. In NAO versus LAO group, including 310 up-regulated and 1580 down-regulated DEGs. In NAO versus HAO group, including 3928 up-regulated and 1761 down-regulated DEGs. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment indicated that detoxification enzyme genes were significantly expressed in pathways, such as cytochrome P450 foreign body metabolism, glutathione metabolism and drug metabolism-cytochrome pathway. The results of gene annotation and quantitative real-time PCR showed that high concentration of lead significantly stimulated the expression of metabolic detoxification enzyme genes such as glutathione S transferase (GST) and superoxide dismutase (SOD), while low concentration inhibited their expression. This study will provide a basis for the molecular mechanism of A. ovatus in response to heavy metal lead stimulation in stored grain. [Display omitted] • A comparative transcriptome analysis was conducted on Aleurolyphus ovatus under different lead exposures. • The number of DEGs between NAO and HAO was approximately 3-fold that between NAO and LAO. • High concentrations of lead activated various cellular processes, enzymes, and metabolic pathways. • High concentrations of lead stimulated the expression of metabolic detoxification enzyme genes by RT-qPCR. [ABSTRACT FROM AUTHOR]

The occurrence of high arsenic concentrations (up to 3000 μg L−1) in water of soda lakes of the Pantanal wetland is a remarkable case of natural arsenic contamination in South America. However, little is known about arsenic speciation in this environment, particularly regarding speciation changes related to lake trophic status and seasonal variations. To fill this gap, arsenic speciation analysis was carried out in surface (SW) and subsurface (SSW) waters sampled in five soda lakes with different eutrophication status, in two dry and one wet season. As(V) was the dominant species in these waters, while As(III), DMA, MMA and likely complex organic species were present in lower amounts. The results allow to conclude that the arsenic speciation in SW and SSW varies seasonally according to the regional wet or dry periods and lake water levels. In eutrophic turbid and in oligotrophic vegetated soda lakes, arsenic speciation was also characterized by spatial differences between edge and center or between the SW and SSW. Cyanobacteria or macrophytes/algae are involved in arsenic biotransformation in soda lakes through its metabolic and detoxification processes. Significant variation in surface water arsenic speciation occurs as a result of seasonal primary production fluctuation or water arsenic concentration changes in the soda lakes, increasing organoarsenics in dry periods, whereas in flood periods, As(V) prevails. Spatial distribution of arsenic species is significantly impacted by biogeochemical conditions at the water/sediment interface in soda lakes. [Display omitted] • Arsenic species largely varied in surface and subsurface water of soda lakes. • Cyanobacteria or macrophytes/algae are involved in As biotransformation. • Arsenic speciation varies seasonally with lake water level and trophic condition. • Spatial distribution of As species varies with biogeochemical conditions. [ABSTRACT FROM AUTHOR]

Beta adrenergic antagonists like carvedilol are typical environmental pollutants detected in wastewater and surface water. Human metabolism of carvedilol is well investigated, while its environmental fates are still unknown. In recent years, there have been appearing reports on high toxicity of β-blockers toward aquatic organisms. In this paper the ability of the filamentous fungus C. echinulata to eliminate the β-blocker has been described for the first time. An 83% loss of carvedilol was observed after 120 h incubation of the tested fungus with the compound, where hydroxylated carvedilol metabolites were identified as the major biotransformation products. Carvedilol degradation by C. echinulata was proceeded by hydroxylation and conjugation reactions similar to its mammalian metabolism. Glucose conjugate was found in the fungi cultures, whereas glucuronide conjugates were detected in mammals. The impact of carvedilol on the functionality of fungal cells was also evaluated. A 2-fold decrease in the PC/PE ratio was noticed in the C. echinulata cell membrane after the exposition to carvedilol compared to control mycelium incubated without the β-blocker. The change can denote perturbation of fungal cell membrane integration by carvedilol. Moreover, 2.8-fold lower toxicity of postcultures supernatants toward D. magna were shown in contrast to abiotic control. [ABSTRACT FROM AUTHOR]

General population exposure to pesticides mainly occurs via food and water consumption. However, their risk assessment for regulatory purposes does not currently consider the actual co-exposure to multiple substances. To address this concern, relevant experimental studies are needed to fill the lack of data concerning effects of mixture on human health. For the first time, the present work evaluated on human microsomes and liver cells the combined metabolic effects of, chlorfenvinphos, ethion and linuron, three pesticides usually found in vegetables of the European Union. Concentrations of these substances were measured during combined incubation experiments, thanks to a new analytical methodology previously developed. The collected data allowed for calculation and comparison of the intrinsic hepatic clearance of each pesticide from different combinations. Finally, the results showed clear inhibitory effects, depending on the association of the chemicals at stake. The major metabolic inhibitor observed was chlorfenvinphos. During co-incubation, it was able to decrease the intrinsic clearance of both linuron and ethion. These latter also showed a potential for metabolic inhibition mainly cytochrome P450-mediated in all cases. Here we demonstrated that human detoxification from a pesticide may be severely hampered in case of co-occurrence of other pesticides, as it is the case for drugs interactions, thus increasing the risk of adverse health effects. These results could contribute to improve the current challenging risk assessment of human and animal dietary to environmental chemical mixtures. [ABSTRACT FROM AUTHOR]

Acylase I (ACY I) plays a role in the detoxication and bioactivation of xenobiotics as well in other physiological functions. In this context, an automated ACY I assay for the evaluation of ionic liquids' (ILs) toxicity was developed. The assay was implemented in a sequential injection analysis (SIA) system and was applied to eight commercially available ILs. The SIA methodology was based on the deacetylation of N -acetyl- l -methionine with production of l -methionine, which was determined using fluorescamine. ACY I inhibition in the presence of ILs was monitored by the decrease of fluorescence intensity. The obtained results confirmed the influence of ILs' structural elements on its toxicity and revealed that pyridinium and phosphonium cations, longer alkyl side chains and tetrafluoroborate anion displayed higher toxic effect on enzyme activity. The developed methodology proved to be robust and exhibited good repeatability (RSD < 1.3%, n = 10), leading also to a reduction of reagents consumption and effluents production. Thus, it is expected that the proposed assay can be used as a novel tool for ILs' toxicity screening. [ABSTRACT FROM AUTHOR]

Dinotefuran is a promising neonicotinoid insecticide with chiral structure. In the present study, the stereoselective toxicity of dinotefuran to Daphnia magna (D. magna) was studied. The present result showed that S -dinotefuran inhibited the reproduction of D. magna at 5.0 mg/L. However, both R -dinotefuran and S -dinotefuran had no genotoxicity to D. magna. Additionally, neither R -dinotefuran nor S -dinotefuran had negative influences on the motor behavior of D. magna. However, S -dinotefuran inhibited the feeding behavior of D. magna at 5.0 mg/L. Both R -dinotefuran and S -dinotefuran induced oxidative stress effect in D. magna after exposure. R -dinotefuran significantly activated the activities of superoxide dismutase (SOD) and glutathione S-transferase (GST), while S -dinotefuran showed the opposite effect. S -dinotefuran had more obvious activation effect on the acetylcholinesterase (AchE) activity and trypsin activity compared to R -dinotefuran. The transcriptome sequencing results showed that S -dinotefuran induced more DEGs in D. magna , and affected the normal function of ribosome. The DEGs were mainly related to the synthesis and metabolism of biomacromolecules, indicating the binding mode between dinotefuran enantiomer and biomacromolecules were different. Additionally, the present result indicated that the digestive enzyme activity and digestive gene expression levels in D. magna were greatly enhanced to cope with the inhibition of S -dinotefuran on the feeding. [Display omitted] • Both R -dinotefuran and S -dinotefuran had no genotoxicity to D. magna. • S -dinotefuran inhibited the feeding behavior of D. magna at 5.0 mg/L. • S -dinotefuran had stronger influence on ribosome than R -dinotefuran. • S -dinotefuran had activating effect on the digestive capacity of D. magna. [ABSTRACT FROM AUTHOR]

Mercury (Hg) is among the naturally occurring heavy metal with elemental, organic, and inorganic distributions in the environment. Being considered a global pollutant, high pools of Hg-emissions ranging from >6000 to 8000 Mg Hg/year get accumulated by the natural and anthropogenic activities in the atmosphere. These toxicants have high persistence, toxicity, and widespread contamination in the soil, water, and air resources. Hg accumulation inside the plant parts amplifies the traces of toxic elements in the linking food chains, leads to Hg exposure to humans, and acts as a potential genotoxic, neurotoxic and carcinogenic entity. However, excessive Hg levels are equally toxic to the plant system and severely disrupt the physiological and metabolic processes in plants. Thus, a plausible link between Hg-concentration and its biogeochemical behavior is highly imperative to analyze the plant-soil interactions. Therefore, it is requisite to bring these toxic contaminants in between the acceptable limits to safeguard the environment. Plants efficiently incorporate or absorb the bioavailable Hg from the soil thus a constructive understanding of Hg uptake, translocation/sequestration involving specific heavy metal transporters, and detoxification mechanisms are drawn. Whereas recent investigations in biological remediation of Hg provide insights into the potential associations between the plants and microbes. Furthermore, intense research on Hg-induced antioxidants, protein networks, metabolic mechanisms, and signaling pathways is required to understand these bioremediations techniques. This review sheds light on the mercury (Hg) sources, pollution, biogeochemical cycles, its uptake, translocation, and detoxification methods with respect to its molecular approaches in plants. [Display omitted] • Anthropogenic activities are expediting the generation and accumulation of mercury in soil, water, and other biological systems. • Mercury toxicity relies on its bioavailability, whereas its uptake in plants leads to its biomagnification into the biological food chains. • These toxicants hamper the plants metabolism as well as act neurotoxic and immunotoxic to human health. • Phytoremediation and microbial remediation strategies are sustainable methods and have an edge over conventional methods to treat Hg pollutants. • In plants the Hg detoxification mechanism involves the activation of certain enzymatic and non-enzymatic antioxidants and bacterial-associated Mer proteins. [ABSTRACT FROM AUTHOR]

Carbamazepine (CBZ) as an extensively distributed emerging pollutant has menaced ecological security. The degradation performance of CBZ by UV driven bisulfite process was investigated in this work. The kinetics results indicated that CBZ was high-efficiently degraded by UV/bisulfite following a pseudo first-order kinetic model (K obs = 0.0925 min−1). SO 4 •− and •OH were verified as the reactive oxidants by EPR test and the radicals scavenging experiment using MeOH and TBA. SO 4 •− played a dominant role for CBZ degradation. The Density functional theory (DFT) and LC-qTOF-MS/MS clarified that hydroxylation, ketonation, ring opening reaction, and ring contraction were main transformation patterns of CBZ. As to influence factors, CBZ degradation was significantly hindered in presence of CO 3 2−, HPO 4 2− and NOM. Toxicological analysis derived from metabonomics suggested that the remarkable alteration of metabolic profile was triggered by exposure to intermediates mixture. CBZ intermediates interfered in several key metabolic pathways, including pentose phosphate, amino acids, lysine degradation, glycerophospholipid, glutathione, nucleotides and carbohydrate, which was alleviated after UV/bisulfite treatment. This work provided a meaningful support to potential risk of CBZ intermediates products, which shed light on the future application in eliminating drugs using UV /bisulfite. [Display omitted] • UV driven bisulfite system high-efficiently removed carbamazepine. • SO 4.•− and •OH as the dominant contributors promoted carbamazepine degradation. • Seven intermediates were formed via hydroxylation, ketonation, ring contraction. • The low risk of intermediates was confirmed using nontargeted metabolomics. • Detoxification of carbamazepine was realized after UV/bisulfite system treatment. [ABSTRACT FROM AUTHOR]

Atrazine (ATR) as a toxic herbicide has become one of the seriously environmental contaminants worldwide due to its long-term intensive use in crop production. This study identified novel methyltransferases (MTs) involved in detoxification and degradation of ATR residues in rice plants. From a subset of MTs differentially expressed in ATR-exposed rice, forty-four O -methyltransferase genes were investigated. Total activities were significantly enhanced by ATR in rice tissues. To prove detoxifying capacity of the MTs in rice plants, two rice O -MTs (LOC_Os04g09604 and LOC_Os11g15040) were selected and transformed into yeast cells ( Pichia pastoris X-33). The positive transformants accumulated less ATR and showed less toxicity. Using UPLC-TOF-MS/MS, ATR-degraded products in rice and yeast cells were characterized. A novel O -methylated-modified metabolite (atraton) and six other ATR-derivatives were detected. The topological interaction between LOC_Os04g09604 enzyme and its substrate was specially analyzed by homology modeling programs, which was well confirmed by the molecular docking analysis. The significance of the study is to provide a better understanding of mechanisms for the specific detoxification and degradation of ATR residues in rice growing in environmentally relevant ATR-contaminated soils and may hold a potential engineering perspective for generating ATR-resistant rice that helps to minimize ATR residues in crops. [ABSTRACT FROM AUTHOR]

Acrylonitrile (ACN) wastewater generated during ACN production has been reported to be toxic to many aquatic organisms. However, few studies have evaluated toxicity removal of ACN wastewater during and after the treatment process. In this study, the detoxication ability of an ACN wastewater treatment plant (WWTP) was evaluated using Daphnia magna , Danio rerio and zebrafish embryo. This ACN WWTP has a combined anaerobic oxic-aerobic biological fluidized tank (A/O-ABFT) process upgraded from the traditional anaerobic oxic (A/O) process. Moreover, the potential toxicants of the ACN wastewaters were identified by gas chromatography-mass spectrometry (GC-MS). The raw ACN wastewater showed high acute and embryo toxicity. 3-Cyanopyridine, succinonitrile and a series of nitriles were detected as the toxic contributors of ACN wastewater. The A/O process was effective for the acute and embryo toxicity removal, as well as the organic toxicants. However, the A/O effluent still showed acute and embryo toxicity which was attributed by the undegraded and the newly generated toxicants during the A/O process. The residual acute and embryo toxicity as well as the organic toxicants in the A/O effluent were further reduced after going through the downstream ABFT process system. The final effluent displayed no significant acute and embryo toxicity, and less organic toxicants were detected in the final effluent. The upgrade of this ACN WWTP results in the improved removal efficiencies for acute and embryo toxicity, as well as the organic toxicants. [ABSTRACT FROM AUTHOR]

1,2-dichloroethane (1,2-DCA) is a chlorinated hydrocarbon used for polyvinyl chloride plastic production. As such, 1,2-DCA is a common persistent contaminant in saturated zones. While nanoscale zerovalent iron (NZVI) is considered an effective reductant for removing a wide range of chlorinated hydrocarbons, 1,2-DCA is resistant to reduction by NZVI as well as by modified forms of NZVI (e.g., sulfidated-NZVI). Hydroxyl radicals produced in Fenton's reaction can effectively degrade 1,2-DCA, but Fenton's reaction requires the acidification of saturated zones to achieve a groundwater pH of 3 to facilitate the catalytic reaction. To overcome this problem, this study has developed a sequential treatment process using an NZVI-induced Fenton-like reaction that can effectively degrade 1,2-DCA at an initially neutral pH range. The experiments were conducted using a high 1,2-DCA concentration (2000 mg/L) to evaluate the feasibility of using the treatment process at source zones. The process degraded 99% of 1,2-DCA with a pseudo-first-order rate constant of 0.49 h-1. Unlike the single-stage treatment process, the sequential treatment can control the used H 2 O 2 concentration in the system, thus sustaining the reaction and resulting in more efficient 1,2-DCA degradation. To mimic subsurface conditions, batch experiments were conducted to remove 1,2-DCA sorbed in contaminated soil. The results show that 99% removal of 1,2-DCA was obtained within 16 h. Additionally, this study suggests that the NZVI can be used for at least three consecutive 1,2-DCA degradation cycles while maintaining high removal efficiency. [Display omitted] • Sequential addition of H 2 O 2 prevented rapid inhibition of NZVI-based Fenton's. • Sequential addition yielded the most effective utilization of H 2 O 2. • No acidification was required as traditional Fenton's process. • NZVI was reusable and performed over 98% of 1,2-DCA removal. • The process was applicable to 1,2-DCA sorbed on soil for groundwater remediation. [ABSTRACT FROM AUTHOR]

Bitumen mining in the Athabasca oil sands region of northern Alberta results in the accumulation of large volumes of oil sands process-affected water (OSPW). The acid-extractable organic (AEO) fraction of OSPW contains a variety of compounds, including naphthenic acids, aromatics, and sulfur- and nitrogen-containing compounds that are toxic to aquatic and terrestrial organisms. We have studied the effect of AEO treatment on the transcriptome of root and shoot tissues in seedlings of the model plant, Arabidopsis thaliana . Several genes encoding enzymes involved in the xenobiotic detoxification pathway were upregulated, including cytochrome P450s (CYPs), UDP-dependent glycosyltransferases (UGTs), glutathione-S-transferases (GSTs), and membrane transporters. In addition, gene products involved in oxidative stress, β-oxidation, and glucosinolate degradation were also upregulated, indicating other potential mechanisms of the adaptive response to AEO exposure. These results provide insight into the pathways that plants use to detoxify the organic acid component of OSPW. Moreover, this study advances our understanding of genes that could be exploited to potentially develop phytoremediation and biosensing strategies for AEO contaminants resulting from oil sands mining. [ABSTRACT FROM AUTHOR]

Butyl benzyl phthalate (BBP) has been extensively used worldwide as a plasticizer in the polyvinyl chloride (PVC) industry and the manufacturing of many other products, and its presence in the aquatic environment is expected for decades. In the present study, the toxicity of BBP was investigated in Chironomus riparius aquatic larvae. The effects of acute 24-h and 48-h exposures to a wide range of BBP doses were evaluated at the molecular level by analysing changes in genes related to the stress response, the endocrine system, the energy metabolism, and detoxication pathways, as well as in the enzyme activity of glutathione S-transferase. BBP caused a dose and time-dependent toxicity in most of the selected biomarkers. 24-h exposures to high doses affected larval survival and lead to a significant response of several heat-shock genes ( hsp70 , hsp40 , and hsp27 ), and to a clear endocrine disrupting effect by upregulating the ecdysone receptor gene ( EcR ). Longer treatments with low doses triggered a general repression of transcription and GST activity. Furthermore, delayed toxicity studies were specially relevant, since they allowed us to detect unpredictable toxic effects, not immediately manifested after contact with the phthalate. This study provides novel and interesting results on the toxic effects of BBP in C. riparius and highlights the suitability of this organism for ecotoxicological risk assessment, especially in aquatic ecosystems. [ABSTRACT FROM AUTHOR]

Escherichia coli and Pseudomonas aeruginosa are gram-negative bacteria found in wastewater and biosolids. Spanning the inner and outer membrane are resistance-nodulation-cell division superfamily (RND) efflux pumps responsible for detoxification of the cell, typically in response to antibiotics and other toxicity inducing substrates. Here, we show that estrogenic endocrine disruptors, common wastewater pollutants, induce genes encoding chemical efflux proteins. Bacteria were exposed to environmental concentrations of the synthetic estrogen 17α-ethynylestradiol, the surfactant nonylphenol, and the plasticizer bisphenol-A, and analyzed for RND gene expression via q-PCR. Results showed that the genes acrB and yhiV were over-expressed in response to the three chemicals in E. coli , and support previous findings that these two transporters export hormones. P. aeruginosa contains 12 RND efflux pumps, which were differentially expressed in response to the three chemicals: 17α-ethynylestradiol, bisphenol-A, and nonylphenol up-regulated mexD and mexF , while nonylphenol and bisphenol-A positively affected transcription of mexK , mexW , and triC . Gene expression via q-PCR of RND genes may be used to predict the interaction of estrogen mimics with RND genes. One bacterial response to estrogen mimic exposure is to induce gene expression of chemical efflux proteins, which leads to the expulsion of the contaminant from the cell. [ABSTRACT FROM AUTHOR]

Microcystin-LR (MC-LR) is the most toxic and common among microcystins. In order to understand the possible molecular mechanisms of hepatic antioxidation and detoxification, the activities and transcriptional levels of antioxidant enzymes including catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPx) and glutathione S-transferases (GST), and glutathione (GSH) contents as well as histopathological changes were studied in the liver of female zebrafish injected intraperitoneally (i.p.) at doses of 50 and 200 μg MC-LR kg −1 body weight (BW) respectively. In the low dose group (50 μg MC-LR kg −1 ), zebrafish displayed a little unease at the initial 1 h post-injection (hpi), slight hepatic injury and quick recovery, and enhanced enzymatic activities and up-regulated gene expression of antioxidant enzymes. In contrast, high dose of MC-LR (200 μg MC-LR kg −1 ) resulted in uneasiness and frantic swimming, severe hepatic injury, and suppressed enzymatic activities and down-regulated gene expression of antioxidant enzymes. GSH depletion in both dose groups may be explained by enhanced antioxidant reactions and higher rates of MC conjugation, suggesting the crucial roles of GSH in both cellular antioxidant protection and MC-LR detoxification. This study demonstrated that administration of MC-LR caused a positive response in the low dose group but a negative response in the high dose group. Hepatic positive/negative responses in the low/high dose group might result from an increased/decreased synthesis of antioxidant enzymes at the molecular level, respectively. These results illustrated that antioxidant status played an important role in zebrafish protection against MC-LR-caused oxidative stress through regulating antioxidant enzyme gene expression and activities. [ABSTRACT FROM AUTHOR]

Bisphenols are endocrine-disrupting chemicals ubiquitously present in the environment, with the consequent exposure to humans. In humans, bisphenols are metabolized to glucuronide and sulfate conjugates. Recent studies indicate that sulfation represents an important bisphenol metabolic pathway for the most vulnerable humans, such as the growing fetus. Our aim was to evaluate sulfation kinetics of commonly detected bisphenols in biological samples: bisphenol A (BPA), bisphenol S (BPS), and bisphenol F (BPF). Furthermore, we evaluated estrogenic agonist potencies and long-term stability of these bisphenol sulfates. BPS and BPF sulfates were prepared by chemical synthesis. Sulfation kinetics of the selected bisphenols were tested in pooled human liver cytosol, as a source for soluble phase II enzymes, including liver sulfotransferases, with quantification by LC-MS/MS. A validated transactivation assay using the hERα-Hela 9903 cell line was used to determine estrogenic agonist potencies. Moreover, BPA, BPS, and BPF sulfate stabilities were examined under various conditions and during storage. In vitro sulfation of BPA and BPS followed Michaelis–Menten kinetics; BPF sulfation followed a substrate inhibition model. Sulfation rates were comparable for these bisphenols, although their K M values indicated some large differences in affinities. BPA and BPS sulfates are not hERα agonists. The bisphenol sulfates can be considered stable for at least 2 days under these tested media conditions. These data indicate that bisphenol sulfation is an important route in their biotransformation. Compared to glucuronidation, these bisphenols show slower sulfation rates but similar K M values. BPA and BPS metabolic biotransformation by sulfation provides their detoxification as they are without estrogenic activities. [Display omitted] • In vitro sulfation of BPA and BPS followed Michaelis–Menten kinetics. • BPF sulfation followed a substrate inhibition model. • BPA and BPS sulfates are not hERα agonists. • BPA, BPS, and BPF sulfates can be considered stable for at least 2 days. [ABSTRACT FROM AUTHOR]

Highlights: [•] Used biochemical biomarkers to screen for effects of polygodial on Perna canaliculus. [•] Examined markers of oxidative stress and a detoxification pathway. [•] Exposure to the IC99 against fouling ascidians had no effect in P. canaliculus. [•] Antioxidant enzyme activity increased in P. canaliculus exposed to 10× the IC99. [ABSTRACT FROM AUTHOR]

Abstract: Organic solvents, such as dimethylsulfoxide (DMSO) and methanol are widely used as vehicles to solubilise lipophilic test compounds in toxicity testing. However, the effects of such solvents upon innate detoxification processes in aquatic organisms are poorly understood. This study assessed the effect of solvent exposure upon cytochrome P450 (CYP)-mediated xenobiotic metabolism in Daphnia magna and zebrafish larvae (4d post fertilisation). Adult D. magna were demonstrated to have a low, but detectable, metabolism of ethoxyresorufin in vivo and this activity was not modulated by pre-exposure to DMSO or methanol (24h, up to 0.1% and 0.05% v/v, respectively). In contrast, the metabolism of ethoxyresorufin in zebrafish larvae was significantly reduced by both solvents (0.1% and 0.05% v/v, respectively) after 24h of exposure. In zebrafish, these observed decreases in activity towards ethoxyresorufin were accompanied by decreased expression of a variety of genes coding for drug metabolising enzymes (corresponding to CYP1, CYP2, CYP3 and UDP-glucuronyl transferase [UGT] family enzymes), measured by quantitative PCR. Reduction of gene expression and CYP1 enzyme activities by methanol (0.05% v/v) in zebrafish larvae was partially reversed by co-exposure with Aroclor 1254 (100μgL−1). Overall this study suggests that relatively low concentrations of organic solvents can impact upon the biotransformation of certain xenobiotics in zebrafish larvae, and that this warrants consideration when assessing compounds for metabolism and toxicity in this species. [Copyright &y& Elsevier]

Abstract: The aim of this study was to test if pharmaceuticals could explain observed responses of field collected and transplanted invertebrate species (Hydropsyche exocellata, Echinogammarus longisetosus, and Daphnia magna). The study was performed in the middle and lower course of Llobregat river basin, which is affected by pharmaceuticals and other pollutants coming from sewage treated effluents. Up to 10 different endpoints including enzyme activities related with detoxication mechanisms (i.e. glutathione S transferase, catalase, esterases), the oxidative stress damage marker (lipid peroxidation), and individual responses (mortality, post-exposure feeding rates) were assessed. Biological responses were complemented with a detailed chemical analysis of metals, detergents, pesticides, pharmaceuticals and other general water quality variables to allow identifying causal abiotic factors. Estimated hazard indexes of measured pollutants indicated that pesticides and metals accounted for most of the predicted toxicity (>95%) in the most contaminated site and that the predicted toxicity of pharmaceuticals was marginal (<5%). The three species showed a clear impact across the studied gradient indicated by higher levels of feeding inhibition and of mortality towards lower reaches. Specific responses such as inhibition of cholinesterase activities were closely related to high and presumable toxic levels of diazinon, whereas unspecific responses such as enhanced levels of antioxidant defensive mechanism and of lipid peroxidation levels were associated with most pollutant classes as well as with high and presumable toxic levels of salt and ammonia. These results indicate that pesticides, salinity, ammonia probably had greater effects on the studied species than pharmaceuticals. [Copyright &y& Elsevier]

Abstract: Gene expression experiments were targeted in order to monitor the ABC efflux transporters, which is potentially involved in cellular detoxification/defense. Changes in expression levels of different ABC genes in kidney of Oncorhynchus mykiss fed with melamine and melamine+cyanuric acid enriched diets were recorded in both treated groups by mRNA ΔΔCT relative quantification method. Expression profiles of eight different ABC genes basically showed low alterations in melamine group and more consistent changes in melamine+cyanuric acid treated fish, compared with own control. In the last group ABCC2 gene over expression was the more evident alteration. These results suggest that ABC efflux system could be involved in mobilization of hydrophilic molecules in the forcing condition of chronic exposure. [Copyright &y& Elsevier]

Abstract: Multiple isoenzymes of the detoxification enzyme family Glutathione S-transferase are expressed in the brine shrimp Artemia. The number of the major ones detected in crude extract by means of chromatofocusing varied between three and four, depending on the age. Two isoenzymes, one alkaline and one neutral (with corresponding isoelectric points of 8.5 and 7.2) appear to be dominant in all three developmental stages studied, (24, 48, and 72h after hatching). Culturing Artemia for 48h after hatching, in artificial sea water prepared by municipal wastewater effluent resulted to significant alterations of the isoenzyme profile. In comparison to organisms cultured for the same period of time in artificial sea water prepared by filtered tap water, the expression of the alkaline isoenzyme decreased by 62% while that of the neutral isoenzyme increased by 58%. Furthermore, the enzyme activity of the major isoenzyme of the acidic area increased by more than two folds. It is worth mentioning that although the specific activity of the total enzyme in the whole body homogenate was elevated, no statistically significant alteration of the Km value was observed. These findings suggest that study of the isoenzyme profile of Glutathione S-transferase may offer high sensitivity in detecting environmental pollution and needs to be further investigated. [Copyright &y& Elsevier]

Abstract: The aim of the present study is the comparative examination of accumulation and detoxification of Cu and Hg in digestive gland and gills of mussels Mytilus galloprovincialis, using atomic absorption spectrophotometry and autometallography. Mussels were exposed to 0.08mgL−1 Cu, 0.08mgL−1 Hg, as well as to a mixture of 0.08mgL−1 Hg and 0.08mgL−1 Cu for 11d. After the experimental exposure, animals were kept under laboratory conditions for a detoxification period of 7d. An antagonistic effect of Cu against to Hg accumulation was noted in the digestive gland of mussels after the experimental exposure, as well as after the detoxification period, supporting the protective role of Cu against to Hg toxicity in this tissue. Digestive gland was suggested as a main organ for Hg accumulation and gills as a target position for Cu accumulation. Additionally, lower time was evaluated for Hg detoxification in the digestive gland and gills of mussels, in relation to those addressed for Cu detoxification in the same tissues. The evaluation of black silver deposits (BSD) extent performed in digestive gland and gills was suggested as a less sensitive approach, in relation to atomic absorption spectrophotometry (AAS), to indentify the concentration of heavy metals in tissues of mussels. The toxic effects of Hg, Cu and a mixture of them on lysosomal system of the digestive cells are also discussed. [Copyright &y& Elsevier]

Abstract: The impacts of radiological and chemical toxicity from naturally occurring radionuclides are discussed in the context of protecting freshwater ecosystems from radiation exposure. The present study aimed to determine the toxicity of 232Th and it stable chemical analogue Ce to the green alga Chlorella vulgaris Beijerinck (thermophilic strain). Parameters of the regression equation for the concentration-effect relationship and concomitant Effective concentration (50%), EC50, showed that 232Th was more toxic to chlorella after a 24-h exposure than Ce. However, the No-observable-effect concentration (NOEC) and Lowest-observable-effect concentration (LOEC) for 232Th were approximately equal to those for Ce. NOEC, LOEC and EC50 for 232Th were 1.6μM, 2.2μM and 15.4 respectively. Those for Ce were 1.8, 2.1 and 35.7μM respectively. Consideration of the results obtained suggests differences in the main detoxification pathways of 232Th and Ce (III). It was found that 0.02mM caffeine (used as DNA metabolism disturbance reagent) has no effect on Ce toxic action, but 0.02mM BSO (as a selective inhibitor of γ-ECS, a glutathione biosynthetic pathway enzyme) enhanced it. In contrast, 0.02mM caffeine significantly increased the toxic action of 232Th, but 0.02mM BSO has no effect on it. The peculiarities mentioned were suggested to be caused by differences in the physicochemical properties of the elements. The combined potential detrimental effect of 232Th acting both as a radiation source (α-, β- and γ-emitter) and a chemically toxic element is discussed. [Copyright &y& Elsevier]

Abstract: This study aims to evaluate the feasibility of stabilizing copper-laden sludge by the application of alumina-based ceramic products. The processing temperature, material leaching behaviour, and the effect of detoxification were investigated in detail. CuO was used to simulate the copper-laden sludge and X-ray Diffraction was performed to monitor the incorporation of copper into the copper aluminate spinel (CuAl2O4) phase in ceramic products. It was found that the development of CuAl2O4 increased with elevating temperatures up to and including 1000°C in the 3h short-sintering scheme. When the sintering temperature went above 1000°C, the CuAl2O4 phase began to decompose due to the high temperature transformation to CuAlO2. The leachability and leaching behaviour of CuO and CuAl2O4 were compared by usage of a prolonged leaching test modified from US EPA’s toxicity characteristic leaching procedure. The leaching results show that CuAl2O4 is superior to CuO for the purpose of copper immobilization over longer leaching periods. Furthermore, the detoxification effect of CuAl2O4 was tested through bacterial adhesion with Escherichia coli K12, and the comparison of bacterial adhesion on CuO and CuAl2O4 surfaces shows the beneficial detoxification effect in connection with the formation of the CuAl2O4 spinel. This study demonstrates the feasibility of transforming copper-laden sludge into the spinel phase by using readily available and inexpensive ceramic materials, and achieving a successful reduction of metal mobility and toxicity. [Copyright &y& Elsevier]

Abstract: The impact of lead nitrate (Pb(NO3)2; 0.5mM) on steady-state accumulation of messengers corresponding to stress responsive genes was studied in two local lines of 11-d grass pea (Lathyrus sativus L.) plants exposed for 96h in a hydroponic system. Real-time reverse transcription polymerase chain reaction technique was used with grass pea-specific primers designed from newly isolated partial cDNA. Increases in accumulation of glutathione reductase, ascorbate peroxidase and glutathione S-transferase transcripts suggested that roots enhanced detoxification mechanisms involving glutathione. In the leaves where no lead was translocated, the pollutant indirectly triggered increases in expression of several genes. This process probably resulted from systemic signals originating from the roots where lead accumulated in large amounts, approximately 150mg Pbg−1 dry weight. A preventive and/or adaptive role for the signal is assumed, since it concerned genes implicated in reactive oxygen species scavenging (ascorbate peroxidase), protein protection (heat shock protein 70) and proteolysis (cysteine and aspartic proteases). [Copyright &y& Elsevier]

Abstract: This paper describes seasonal changes of microcystin-LR (MC-LR) and its glutathione (MC-LR-GSH) and cysteine conjugates (MC-LR-Cys) in three aquatic animals – snail (Bellamya aeruginosa), shrimp (Macrobrachium nipponensis) and silver carp (Hypophthalmichthys molitrix) collected from Lake Taihu, China. MC-LR, MC-LR-GSH, and MC-LR-Cys were determined by liquid chromatography electrospray ionization mass spectrum (LC–ESI-MS). The mean MC-LR concentrations in the hepatopancreas of snail and shrimp and liver of silver carp were 6.61, 0.24, and 0.027μgg−1 dry weight (DW), respectively; while the average MC-LR-Cys concentrations were 0.50, 0.97, and 5.72μgg−1 DW, respectively. MC-LR-GSH was usually not detectable in these samples. The above results suggest that: (1) in aquatic animals, especially fish, the main excretion form of MC-LR could be MC-LR-Cys, but not MC-LR-GSH, whereas MC-LR-Cys might play an important role in detoxication of MC-LR and (2) that efficiency of MC-LR-Cys formation differs among species. The main detoxication pathway of MC-LR in aquatic animals is suggested as follows: when MC-LR enters into liver/hepatopancreas, it firstly conjugates with polypeptide or protein (including GSH, PP-1 and 2A) containing Cys residues, perhaps also some free cysteine; subsequently, MC-LR-Cys is degraded from these polypeptide or protein; and finally is excreted from animals by the compound of MC-LR-Cys. [Copyright &y& Elsevier]

Tilapia fish (Oreochromis niloticus) were fed with enriched diets containing broccoli and its phytochemical sulforaphane over 30d. The levels of cytochrome P450, superoxide dismutase, catalase, lipid peroxidation and glutathione-S-transferase activities were measured. Basal value of cytochrome P450 activity was significantly increased as consequence of the broccoli and sulforaphane enriched diets, while no statistically significant changes were found on catalase and lipid peroxidation activities. After benzo(a)pyrene exposure, the cytochrome P450 activity increased to higher levels in the fish feed with broccoli and sulforaphane when compared with the control fish. Activities of antioxidant enzymes also varied but without significant difference with the control fish. Supported by the lower concentrations of BaP metabolites in bile from fish fed with broccoli or with sulforaphane enriched diets (indicating a better xenobiotic elimination) the cytochrome P450 induction could be considered beneficial for the detoxification because this transformation is the first step for PAH elimination by the phase II system. The protection of aquaculture organism against pollution effects by designing special diets able to modulate the enzymes involved in the phase-I and phase-II detoxification mechanism are discussed. [Copyright &y& Elsevier]

High level of PCDD+PCDF contamination in bulk milk (9.7pgWHO-TEg−1 fat) from 1604 Holstein Fresian lactacting cows was observed just four weeks after the beginning of their exposure to a feed supplement contaminated at 10.4ngWHO-TEkg−1 dry matter. In-farm produced hay and silage showed levels not exceeding 0.2ngWHO-TEkg−1 dry matter. After the supplement withdrawal, it was possible to monitor the depletion phase for a following 75-day period in milk, until the levels dropped well below 3.0pgWHO-TEg−1 fat, the EU regulatory Maximum Residue Level for PCDD+PCDF. During this phase, the half-life was calculated as 17±3 days, on WHO-TEQ basis. The full availability of farm data on both cow nutrition and milk production allowed the calculation of the carry-over rate (COR) (PCDD+PCDF milk excretion vs. feed), which was 46% at the end of the exposure. This COR value is justified from the main TE contribution of Penta-CDD and -CDF congeners (63%), and the half-life is among the shortest of all those described in the literature both for experimental and naturally-exposed dairy cows. A fugacity-based model predicts a bulk milk contamination of 5pgWHO-TEg−1 fat, compared to the 10pgWHO-TEg−1 fat level observed. Such findings are discussed in light of the lactation and metabolic status of the herd for which the transition period, characterised by a negative metabolic energy balance and a consequent adipose tissue mobilization, could play a relevant role. [Copyright &y& Elsevier]

Cyanobacterial blooms tend to be more common in warm and nutrient-enriched waters and are increasing in many aquatic water bodies due to eutrophication. The aim of this work is to study the accumulation and depuration of anatoxin-a by Mytilus galloprovincialis a widespread distributed mussel living in estuarine and coastal waters and recognized worldwide as a bioindicator (e.g. Mussel Watch programs). Research on the distribution and biological effects of anatoxin-a in M. galloprovincialis is important. Nevertheless, the risk of human intoxication due to the consumption of contaminated bivalves should also be considered. A toxic bloom was simulated in an aquarium with 5×105 cellml−1 of Anabaena sp. (ANA 37), an anatoxin-a producing strain. Mussels were exposed to Anabaena for 15 days and then 15 days of depuration followed. Three or more animals were sampled every 24h for total toxin quantification and distribution in soft tissues (edible parts). Water samples were also taken every 24h in order to calculate total dissolved and particulate anatoxin-a concentrations. Anatoxin-a was quantified by HPLC with fluorescence detection. No deaths occurred during accumulation and depuration periods. One day after the beginning of depuration, the toxin could not be detected in the animals. Anatoxin-a is distributed in the digestive tract, muscles and foot and is probably actively detoxified. [Copyright &y& Elsevier]

The plants of Brassica juncea (L) were grown in the presence of NaCl and/or NiCl2 and were sprayed with 1μM of 24-epibrassinolide (EBL) at 15 days after sowing (DAS) and were sampled at 30 DAS. The plants exposed to NaCl and/or NiCl2 exhibited a significant decline in growth, the level of pigments and photosynthetic parameters. However, the follow up treatment with EBL detoxified the stress generated by NaCl and/or NiCl2 and significantly improved the above parameters. The NaCl and/or NiCl2 increased electrolyte leakage and lipid peroxidation, and decreased the membrane stability index (MSI) and relative water content. However, the EBL treatment in absence of the stress improved the MSI and relative water content but could not influence electrolyte leakage and lipid peroxidation. The antioxidative enzymes and the level of proline exhibited a significant increase in response to EBL as well as to NaCl and/or NiCl2 stress. [Copyright &y& Elsevier]

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5–35h depending on soil characteristics, a fraction of the applied CGs (0.9–3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50μgl−1 total cyanide for drinking water and 85% exceeded the US threshold of 5μgl−1 for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance. [Copyright &y& Elsevier]

The present study is aimed at evaluating the genotype frequency of detoxifying genes such as GSTM1, GSTT1 and NQO1 in Maharastrian population of central India. The study revealed about 64.6% of GSTM1-positive and 35.4% GSTM1-null population. GSTT1-positive genotype was found to be 87.5% and GSTT1-null showed 12.5%. The NQO1 genotype of Maharastrian population showed 52.3% of C/C, 42.48% C/T and 5.18% T/T. The NQO1 of this population does not deviate from the expected Hardy−Weinberg equilibrium. The genotype frequencies GSTM1 and GSTT1 of the population when compared with other ethnic groups of Asia and Caucasians show distinct nature of Maharastrian population from other Asian and Caucasian population. [Copyright &y& Elsevier]

N-Nitrosodimethylamine (NDMA) is a disinfection by-product shown to be carcinogenic, mutagenic, and teratogenic. A feasible detoxification pathway for NDMA is a three-step bio-reduction that leads to ammonia and dimethylamine. This study examines the bio-reduction of NDMA in a H2-based membrane biofilm reactor (MBfR) that also is active in nitrate and sulfate reductions. In particular, the study investigates the effects of H2 availability and the relative loadings of NDMA, nitrate, and sulfate, which potentially are competing electron acceptors. The results demonstrate that NDMA was bio-reduced to a major extent (i.e., at least 96%) in a H2-based MBfR in which the electron-equivalent fluxes from H2 oxidation were dominated by nitrate and sulfate reductions. NDMA reduction kinetics responded to NDMA concentration, H2 pressure, and the presence of competing acceptors. The most important factor controlling NDMA-reduction kinetics was the H2 availability, controlled primarily by the H2 pressure, and secondarily by competition from nitrate reduction. [Copyright &y& Elsevier]

Mechanisms underlying cadmium (Cd) detoxification were compared in two aquatic macrophytes commonly used in phytoremediation, namely Pistia stratiotes L. And Eichhornia crassipes (Mart. ) Solms. To simulate Cd pollution in the open environment, plants growing in outdoor artificial lakes were exposed for 21d to either 25 or 100μM Cd, in two consecutive years. Toxicity symptoms were absent or mild in both species. Metal accumulation was much higher in the roots of P. Stratiotes, whereas in E. Crassipes a comparatively higher fraction was translocated to the leaves. In both species, Cd was neither included in phenolic polymers or Ca-oxalate crystals, nor altered the levels of Cd-complexing organic acids. Glutathione levels were constitutively remarkably higher and much more responsive to Cd exposure in P. Stratiotes than in E. Crassipes. Abundant phytochelatin synthesis occurred only in P. Stratiotes, both in roots and in leaves. In E. Crassipes, on the other side, the constitutive levels of some antioxidant enzymes and ascorbate were higher and more responsive to Cd than in P. Stratiotes. Thus, in these two aquatic plants grown in the open, different detoxification mechanisms might come into play to counterbalance Cd acute stress. [Copyright &y& Elsevier]

UV/TiO2/H2O2, UV/TiO2 and UV/H2O2 were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50mgl−1, UV/TiO2/H2O2 treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO2 and UV/H2O2. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r 2 >0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3h, respectively, were achieved during UV/TiO2/H2O2 treatment. No pollutant removal was observed in the controls conducted with H2O2 or TiO2 only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO2/H2O2-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100mgl−1. COD and Cl mass balances indicated UV, UV/H2O2, and UV/TiO2 treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated. [Copyright &y& Elsevier]

Increasing evidence indicates that insect resistance to synthesized insecticides is regulated by the nuclear receptors. However, the underlying mechanisms of this regulation are not clear. Here, we demonstrate that inhibition of hepatocyte nuclear factor 4 (HNF4) confers imidacloprid resistance in the brown planthopper (BPH) Nilaparvata lugens by regulating cytochrome P450 and UDP-glycosyltransferase (UGT) genes. An imidacloprid-resistant strain (Res) exhibited a 251.69-fold resistance to imidacloprid in comparison to the susceptible counterpart (Sus) was obtained by successive selection with imidacloprid. The expression level of HNF4 in the Res strain was lower than that in Sus, and knockdown of HNF4 by RNA interference significantly enhanced the resistance of BPH to imidacloprid. Comparative transcriptomic analysis identified 1400 differentially expressed genes (DEGs) in the HNF4 -silenced BPHs compared to controls. Functional enrichment analysis showed that cytochrome P450- and UGT-mediated metabolic detoxification pathways were enriched by the up-regulated DEGs after HNF4 knockdown. Among of them, UGT-1-7 , UGT-2B10 and CYP6ER1 were found to be over-expressed in the Res strain, and knockdown of either gene significantly decreased the resistance of BPH to imidacloprid. This study increases our understanding of molecular mechanisms involved in the regulation of insecticide resistance and also provides potential targets for pest management. Image 1 • Hepatocyte nuclear factor 4 (HNF4) negatively regulates imidacloprid resistance. • Transcriptomic analysis identified seven metabolic resistance pathways after HNF4 silencing. • Inhibition of HNF4 activates P450s and UDP-glycosyltransferases (UGTs). • P450s and UGTs are involved in the imidacloprid resistance. [ABSTRACT FROM AUTHOR]

Direct Red 28 (DR28) is a benzidine-based azo dye widely used in several countries. It has also been a subject of intense research for its anti-prion activity. Like other benzidine-based azo dyes, it is also carcinogenic and toxic. However, there are very few studies addressing its detoxification. In the present study, a Bacillus velezensis strain was used for detoxification of DR28. Toxicity was checked by a battery of highly sensitive genotoxicity assays like comet assay, DNA ladder formation, terminal deoxynucleotidyl transferase-mediated dUTP nick-end labeling assay and flow cytometric Annexin V binding assay. HL-60 cell line was used as the test system. All the assays showed an initial increase in toxicity upon biodegradation due to release of mutagenic products, like benzidine and 4-aminobiphenyl, from the dye. These intermediates caused significant DNA damage and induced apoptosis in HL-60 cells. Then the culture degraded these mutagenic intermediates, due to which the toxicity was reduced gradually, finally resulting in nearly complete detoxification. [Copyright &y& Elsevier]

The aryl hydrocarbon receptor (AhR) plays a key role in the regulation of gene expression in metabolic machinery and detoxification systems. In the recent years, this receptor has attracted interest as a therapeutic target for immunological, oncogenic and inflammatory conditions. In the present report, in silico and in vitro approaches were combined to study the activation of the AhR. To this end, a large database of chemical compounds with known AhR agonistic activity was employed to build 5 classifiers based on the Adaboost (AdB), Gradient Boosting (GB), Random Forest (RF), Multilayer Perceptron (MLP) and Support Vector Machine (SVM) algorithms, respectively. The built classifiers were examined, following a 10-fold external validation procedure, demonstrating adequate robustness and predictivity. These models were integrated into a majority vote based ensemble, subsequently used to screen an in-house library of compounds from which 40 compounds were selected for prospective in vitro experimental validation. The general correspondence between the ensemble predictions and the in vitro results suggests that the constructed ensemble may be useful in predicting the AhR agonistic activity, both in a toxicological and pharmacological context. A preliminary structure-activity analysis of the evaluated compounds revealed that all structures bearing a benzothiazole moiety induced AhR expression while diverse activity profiles were exhibited by phenolic derivatives. Image 1 • Classification models for AhR agonism were built using a large and balanced dataset. • A 10-fold external validation demonstrated the robustness and predictiveness of built QSARs. • In vitro experimental validation corroborated the predictivity of the built ensemble classifier. • The benzothiazoles were the most prominent group among the AhR agonists. • The built QSARs may be useful in guiding the screening of AhR agonists. [ABSTRACT FROM AUTHOR]