Nitrogen fertiliser-domesticated microbes change the persistence and metabolic profile of atrazine in soil.

Pesticides and fertilisers are frequently used and may co-exist on farmlands. The overfertilisation of soil may have a profound influence on pesticide residues, but the mechanism remains unclear. The effects of chemical fertilisers on the environmental behaviour of atrazine and their underlying mechanisms were investigated. The present outcomes indicated that the degradation of atrazine was inhibited and the half-life was prolonged 6.0 and 7.6 times by urea and compound fertilisers (NPK) at 1.0 mg/g (nitrogen content), respectively. This result, which was confirmed in both sterilised and transfected soils, was attributed to the inhibitory effect of nitrogen fertilisers on soil microorganisms. The abundance of soil bacteria was inhibited by nitrogen fertilisers, and five families of potential atrazine degraders (Micrococcaceae, Rhizobiaceae, Bryobacteraceae, Chitinophagaceae, and Sphingomonadaceae) were strongly and positively (R > 0.8, sig < 0.05) related to the decreased functional genes (atzA and trzN), which inhibited hydroxylation metabolism and ultimately increased the half-life of atrazine. In addition, nitrogen fertilisers decreased the sorption and vertical migration behaviour of atrazine in sandy loam might increase the in-situ residual and ecological risk. Our findings verified the weakened atrazine degradation with nitrogen fertilisers, providing new insights into the potential risks and mechanisms of atrazine in the context of overfertilisation.

Oxytetracycline Increases the Residual Risk of Imidacloprid in Radish (Raphanus sativus) and Disturbs the Plant-Rhizosphere Microbiome Holobiont Homeostasis.

Antibiotics can be accidentally introduced into farmland by wastewater irrigation, and the environmental effects are still unclear. In this study, the effects of oxytetracycline on the residue of imidacloprid in soil and radishes were investigated. Besides, the rhizosphere microbiome and radish metabolome were analyzed. It showed that the persistence of imidacloprid in soil was unchanged, but the content of olefin-imidacloprid was increased by oxytetracycline. The residue of imidacloprid in radishes was increased by nearly 1.5 times, and the hazard index of imidacloprid was significantly raised by 1.5-4 times. Oxytetracycline remodeled the rhizosphere microbiome, including Actinobe, Elusimic, and Firmicutes, and influenced the metabolome of radishes. Especially, some amino acid metabolic pathways in radish were downregulated, which might be involved in imidacloprid degradation. It can be assumed that oxytetracycline increased the imidacloprid residue in radish through disturbing the plant-rhizosphere microbiome holobiont and, thus, increased the pesticide dietary risk.

Existence of antibiotic pollutant in agricultural soil: Exploring the correlation between microbiome and pea yield.

Due to sewage irrigation, manure fertilizer application or other agricultural activities, antibiotics have been introduced into farmland as an emerging contaminant, existing with other agrochemicals. However, the potential influences of antibiotics on the efficiency of agrochemicals and crops health are still unclear. In this work, the effect of antibiotics on fertilization efficiency and pea yield was evaluated, and the mechanism was explored in view of soil microbiome. Nitrogen utilization and pea yield were decreased by antibiotics. In specific, the weight of seeds decreased 9.5 % by 5 mg/kg antibiotics and decreased 25.1 % by 50 mg/kg antibiotics. For N nutrient in pea, antibiotics resulted in 62.5 %-63.7 % decrease in amino acid content and 8.3 %-35.3 % decrease in inorganic-N content. Further research showed that antibiotics interfered with N cycle in soil, inhibiting urea decomposition and denitrification process by reducing function genes ureC, nirK and norB in soil, thus decreasing N availability. Meanwhile, antibiotics destroyed the enzyme function in N assimilation. This work evaluated the environmental risk of antibiotics from fertilization efficiency and N utilization in crop. Antibiotics could not only affect N cycle, limiting the decomposition of N fertilizer, but also affect N utilization in plants, thus affecting the yield and even the quality of leguminous crops.

Effects of the presence of triclocarban on the degradation and migration of co-occurring pesticides in soil.

Triclocarban (TCC), a bactericide widely used in personal care products, is frequently detected in soil and surface water, which may affect the environmental behavior of other environmental pollutants by changing the community structure of environmental microorganisms. This work evaluated the effects of TCC on the degradation and migration of seven herbicides and five fungicides in soil under co-occurrence conditions. TCC significantly increased the persistence of the pesticides in soil, and this effect increased with TCC concentration. For example, the half-life of metolachlor, atrazine, metribuzin, and metamitron increased 44%, 38%, 153%, and 33%, respectively, with 10 mg/kg TCC and increased 60%-640% with 100 mg/kg TCC. After 90 days, the residue of the pesticides in soil treated with TCC was significantly elevated relative to the control. TCC treatment could also increase the potential leaching risk of the herbicides in the soil, as indicated by an increased Groundwater Ubiquity Score (GUS) index. The reduced abundance of soil bacteria by TCC might be an essential reason for the impacts on the environmental behavior of the pesticides. This study confirmed that TCC could slow down the degradation of pesticides in soil, increase their persistence and even affect the leaching behavior, thus influencing the risks of the pesticides to the environment.

Co-exposure of Monensin Increased the Risks of Atrazine to Earthworms.

Antibiotics could enter farmlands through sewage irrigation or manure application, causing combined pollution with pesticides. Antibiotics may affect the environmental fate of pesticides and even increase their bioavailability. In this study, the influence of monensin on the degradation, toxicity, and availability of atrazine in soil-earthworm microcosms was investigated. Monensin inhibited the degradation of atrazine, changed the metabolite patterns in soil, and increased the bioavailability of atrazine in earthworms. Atrazine and monensin had a significant synergistic effect on earthworms in the acute toxic test. In long-term toxicity tests, co-exposure of atrazine and monensin also led to worse effects on earthworms including oxidative stress, energy metabolism disruption, and cocoon production compared to single exposure. The expression of tight junction proteins was down-regulated significantly by monensin, indicating that the intestinal barrier of earthworms was weakened, possibly causing the increased bioavailability of atrazine. The expressions of heat shock protein 70 (Hsp70) and reproductive and ontogenetic factors (ANN, TCTP) were all downregulated in binary exposure, indicating that the resilience and cocoon production of earthworms were further weakened under combined pollution. Monensin disturbed the energy metabolism and weakened the intestinal barrier of earthworms. These results showed that monensin increased the risks of atrazine in agricultural areas.

Effects of three surfactants on the degradation and environmental risk of metolachlor in aquatic environment.

Surfactants and pesticides can be simultaneously detected in the environment by the reason of their widespread use and large amounts of emissions. Due to the special amphipathicity of surfactants, it may have special effects on the environmental behaviors and toxic effects of other substances in the environment. There are few relevant studies at present. In this study, the effects of three surfactants on the degradation of the amide pesticide metolachlor in water-sediment system were investigated. The study found that the three surfactants had no significant effect on the degradation of metolachlor in the system at environmental concentrations. However, at critical micelle concentration, cationic surfactant octadecyl trimethyl ammonium bromide and nonionic surfactant nonylphenol polyoxyethylene ether promoted the degradation of metolachlor in water-sediment system. Anionic surfactant odium dodecylbenzene sulfonate (SDBS) prolonged the degradation half-life of metolachlor. The presence of surfactants not only affected the environmental behavior of pesticides. When they coexisted with pesticides, the joint toxicity to aquatic organisms cannot be ignored. This study found that the combined effects of three surfactants and metolachlor on the acute developmental toxicity of zebrafish embryos were all synergistic effects. The combined effects of two ionic surfactants and metolachlor on the acute toxicity of adult zebrafish were synergistic effects. Further study showed that co-exposure of SDBS and metolachlor increased the absorption of metolachlor by zebrafish. Combined exposure of SDBS and metolachlor caused oxidative stress in brain, gill and liver of zebrafish. The results showed that the simultaneous presence of anionic surfactants and pesticides in the environment may increase the environmental risk of pesticides.

Enantioselective degradation of prothioconazole in soil and the impacts on the enzymes and microbial community.

In this work, the stereoselective degradation of prothioconazole in five soils was investigated and the metabolite prothioconazole-desthio was determined. The effects of prothioconazole on soil enzymes activities and microbial community were also studied. The dissipation of prothioconazole fitted with a first-order kinetic equation with half-lives ranging from 3.45 to 9.90 days. In addition, R-prothioconazole degraded preferentially than S-prothioconazole in all soils with EF values >0.5. Prothioconazole-desthio formed rapidly with preference in R-enantiomer, and the concentration kept at a considerable level even at the end of the incubation, indicating it was relatively persistent in soil. Prothioconazole and its metabolite inhibited the activity of dehydrogenase, catalase and urease in soils, and could affect the diversity of the soil microbiota as well. Redundancy analysis (RDA) and Spearman analysis showed the abundance of Proteobacteria, Fusobacteria, Firmicutes, Thaumarchaeota, Saccharibacteria, Chloroflexi, Chlorobi, Actinobacteria and Nitrospirae might be related to the enantioselective degradation. The work was helpful for understanding the environmental behavior of the fungicide prothioconazole and its primary metabolite on an enantiomeric level.

Accumulation, distribution and removal of triazine pesticides by Eichhornia crassipes in water-sediment microcosm.

After application, pesticides remained in the field may contaminate water resources through surface runoff and leaching, posing a threat to aquatic ecosystem. In the current study, the accumulation, translocation, distribution and removal of four triazine pesticides (simazine, atrazine, terbuthylazine and metribuzin) by free floating aquatic plant Eichhornia crassipes (E. crassipes) in water-sediment microcosm were investigated and the removal mechanisms were explored. E. crassipes was exposed to an initial concentration of 50 µg·L-1 and the pesticide levels in water, sediment, roots and shoots of E. crassipes were monitored during 30 days. The results demonstrated that E. crassipes was capable of accumulating triazine pesticides with the bio-concentration factor (BCF) ranging from 0.8 to 18.4. Triazine pesticides were mainly stored in roots, and root accumulation and translocation amount depend on the hydrophobicity of the pesticides. The removal of the pesticides in water were significantly accelerated by the presence of E. crassipes, with the removal efficiency ranging from 66% to 79% after 30 days of treatment. Though phytoaccumulation only constituted 2-18% of the total spiked pesticides in the microcosm, E. crassipes played a vital role in removing simazine, atrazine and metribuzin. However, microbial degradation in sediment was the main pathway for the removal of terbuthylazine in the microcosm. This study demonstrated the potential application of E. crassipes to accelerate removal of contaminants from aquatic environment.

Toxicity and fate of chiral insecticide pyriproxyfen and its metabolites in zebrafish (Danio rerio).

Pyriproxyfen is a juvenile hormone analogue insecticide used worldwide. At present, the potential threat of pyriproxyfen to aquatic organism has not been well explored. In this work, the bioaccumulation, metabolic profile and toxicity of pyriproxyfen and its metabolites to zebrafish were studied, and the enantioselectivity of pyriproxyfen and the major chiral metabolites were also determined. Sixteen metabolites of pyriproxyfen in zebrafish were identified. Hydroxylation, ether linkage cleavage and oxidation in phase I metabolism, followed by sulfate and glucuronic acid conjugation. The bioconcentration factors ranged from 1175 to 1246. Hydroxylation metabolites of pyriproxyfen showed enantioselective behavior in zebrafish with enantiomer fractions (EFs) of 4'-OH- pyriproxyfen and 5″-OH- pyriproxyfen ranged from 0.50 to 0.71. Toxicological indexes including acute toxicity, joint toxicity and oxidative stress were tested. Among all the metabolites, 4'-OH- pyriproxyfen was found 2 folds more toxic to zebrafish than pyriproxyfen. (-)-Pyriproxyfen was found 2 folds more toxic than rac- and (+)-pyriproxyfen. Antagonistic effects were found in binary joint toxicity of pyriproxyfen and its hydroxylated metabolites. Pyriproxyfen and its metabolites also showed oxidative stress damage by inhibiting the activity of CAT and SOD and increasing MDA. This work provided deep insight into the metabolism and the potential risks of pyriproxyfen to aquatic organisms.

Effects of antibiotic norfloxacin on the degradation and enantioselectivity of the herbicides in aquatic environment.

Antibiotics are currently extensively used in human medicine, animal farming, agriculture and aquaculture, and their residue has become a global environmental problem. However, the effects of antibiotic on other pollutants in aquatic environment are still poorly understood. In this study, the influences of norfloxacin on the residue, degradation and distribution of the herbicides (simazine, atrazine, terbuthylazine, acetochlor and metolachlor) and the enantioselectivity of acetochlor in sediment and water-sediment microcosm system were investigated. Sediment was spiked with norfloxacin and water was contaminated by herbicides to simulate environmental pollution. The amounts of herbicides in water and sediment samples were analyzed within 30 days of cultivation. The results showed that norfloxacin could significantly inhibit the dissipation, lengthen the half-lives and enhance the residues of herbicides in sediment. Take simazine as an example, its half-life significantly increased from 16.1 days to 19.3 days and its residual percentage grew from 24.2% to 30.4% when sediment was contaminated with 5 mg·kg-1 norfloxacin. However, only acetochlor degradation was significantly inhibited by norfloxacin in water-sediment microcosm and the distribution of the herbicides were not affected. Enantioselective degradation of acetochlor was observed both in control and norfloxacin-treated water-sediment system, with R-acetochlor preferential elimination, suggesting the co-existence of norfloxacin had very limited influence on the enantioselectivity. The findings indicated that co-contamination with norfloxacin could increase the persistence of herbicides in aquatic environment, thus increasing the environmental risks to aquatic organisms.

Coexisting antibiotic changes the persistence and metabolic profile of atrazine in the environment.

Pesticides are widely used in agriculture to control weeds, pests and plant diseases. Antibiotics may be introduced to the agricultural environment by manure fertilizer or wastewater irrigation. Co-existence of antibiotics in field may lead to profound impacts on pesticide residue. In this study, the impacts of oxytetracycline on the environmental fate and metabolic profile of atrazine was investigated, and the disturbance of oxytetracycline on functional genes related to atrazine degradation in soils was also studied. Oxytetracycline could inhibit the degradation of atrazine significantly and prolong the half-life to 1.27 and 1.59 times longer at 5 mg/kg and 50 mg/kg. Also, oxytetracycline altered the composition of atrazine metabolites, including three chloro-s-triazine metabolites (DEA, DIA, DDA) and three hydroxyl metabolites (OH-ATZ, OH-DEA, OH-DIA). Oxytetracycline decreased the ratio of hydroxyl metabolites, while increased the chloro-s-triazine metabolites which had higher toxicity and were easily leached in soil. Atrazine hydrolase genes atzA and trzN were down-regulated by oxytetracycline, which might decrease the hydroxyl metabolite formation and detoxification of atrazine. Oxytetracycline changed the degradation of atrazine and the composition of the metabolites probably by altering the soil microorganisms. The increased persistence and the percentage of the chloro-s-triazine metabolites induced by oxytetracycline might result in increased environmental problems.

The influence of polyethylene microplastics on pesticide residue and degradation in the aquatic environment.

Microplastics pollution has become a global concern in recent years. In this work, the potential influences of polyethylene (PE) microplastics on the residue, degradation and distribution behaviors of eight pesticides (epoxiconazole, tebuconazole, myclobutanil, azoxystrobin, simazine, terbuthylazine, atrazine and metolachlor) in the aquatic environment were investigated. The results showed that the presence of 2-50 g L-1 microplastics could decrease the pesticide residues in water. The adsorption isotherms were linear, indicating the process was dominated by partitioning into the bulk polymer. The desorption kinetics data implied the desorption process obeyed a pseudo-second-order kinetic model, with R2 above 0.99 in most cases. Aging treatment of microplastics had no significant effects on the interaction with the pesticides. The presence of PE microplastics could significantly prolong the degradation half-lives of pesticides in water, especially for those with moderate degradation half-lives and high log Kow values. Take terbuthylazine as an example, its half-life significantly increased from 31.8 days to 45.2 days in the presence of 10 g L-1 microplastics. Besides, PE microplastics had little impact on the behavior of the pesticides in the water-sediment system. The findings of this study indicated that PE could adsorb pesticides through partitioning, thus influencing the persistence of the pesticides in water.

The enantioselective enrichment, metabolism, and toxicity of fenoxaprop-ethyl and its metabolites in zebrafish.

To investigate the impacts of the widely used chiral herbicide fenoxaprop-ethyl (FE) on aquatic organisms, the enrichment, metabolism, acute toxicity, and oxidative stress of fenoxaprop-ethyl and its main metabolites fenoxaprop (FA), ethyl-2-(4-hydroxyphenoxy)propanoate (EHPP), 2-(4-hydroxyphenoxy)propanoic acid (HPPA), and 6-chloro-2,3-dihydrobenzoxazol-2-one (CDHB) in zebrafish were studied. The enantioselectivity of fenoxaprop-ethyl and its chiral metabolites was also determined. Fenoxaprop-ethyl quickly degraded in zebrafish by aquatic exposure. FA, HPPA, and CDHB were the main metabolites that were enriched in the zebrafish. In the metabolism experiment, the half-lives of the metabolites were 0.92-1.72 days in zebrafish. The R-enantiomers of FA and HPPA were preferentially enriched and metabolized with enantiomeric fractions (EFs) of 0.65-0.85. According to the 96-h acute toxicity, FA, HPPA, EHPP, and CDHB were less toxic to zebrafish than FE, following the order of FE > CDHB > EHPP > FA > HPPA. The S-enantiomers of FE, FA, CDHB, and EHPP were more toxic than the R-enantiomers. FE and its metabolites could significantly increase catalase (CAT) and superoxide dismutase (SOD) activity and the malondialdehyde (MDA) content in gill and liver tissues, indicating their oxidative stress, and these effects were also enantioselective. This work could supply more information for evaluating the risks of fenoxaprop-ethyl on aquatic organisms concerning their metabolites and enantiomers.

Bioaccumulation and Metabolism of Carbosulfan in Zebrafish (Danio rerio) and the Toxic Effects of Its Metabolites.

Carbosulfan is a carbamate insecticide that has been widely used in agriculture. However, studies showed that carbosulfan could be highly toxic to aquatic organisms. The metabolism of carbosulfan in adult zebrafish is still largely unexplored, and the metabolites in individual or in combination may pose a potential threat to zebrafish. In the present study, the bioaccumulation and metabolism of carbosulfan in zebrafish (Danio rerio) were assessed, and the main metabolites, including carbofuran and 3-hydroxycarbofuran, were determined. The toxicity of carbosulfan and its metabolites individually or in combination to zebrafish was also investigated. The bioaccumulation and metabolism experiment indicated that carbosulfan was not highly accumulated in zebrafish, with a bioaccumulation factor of 18 after being exposed to carbosulfan for 15 days, and the metabolism was fast, with a half-life of 1.63 d. The two main metabolites were relatively persistent, with half-lives of 3.33 and 5.68 d for carbofuran and 3-hydroxycarbofuran, respectively. The acute toxicity assay showed that carbofuran and 3-hydroxycarbofuran had 96-h LC50 values of 0.15 and 0.36 mg/L, showing them to be more toxic than carbosulfan (96-h LC50 = 0.53 mg/L). Combinations of binary or ternary mixtures of carbosulfan and its metabolites displayed coincident synergistic effects on acute toxicity, with additive index (AI) values of 1.9-14.3. In the livers and gills of zebrafish exposed to carbosulfan, carbofuran, and 3-hydroxycarbofuran, activities of catalase, superoxide dismutase, and glutathione-S-transferase were significantly changed in most cases, and the content of malondialdehyde was greatly increased, indicating that carbosulfan and its metabolites induced varying degrees of oxidative stress. The metabolites were more persistent and toxic to zebrafish and exhibit coincident synergistic effects in combination. These results can provide evidence for the potential risk of pesticides and highlight the importance of a systematic assessment for the combination of the precursor and its metabolites.

The influence of oxytetracycline on the degradation and enantioselectivity of the chiral pesticide beta-cypermethrin in soil.

Pesticide residues most likely coexist with antibiotics due to the application of animal-based fertilizers in agriculture. In this study, the degradation and enantioselectivity of beta-cypermethrin in soil and chicken manure-amended soil were investigated. The effects of oxytetracycline on the soil microbial community were also estimated. The results showed that the half-life of beta-cypermethrin in the soil was 16.9 days and that the (+)-enantiomer was degraded preferentially in both pairs of enantiomers. The metabolites cis/trans-DCCA(3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid) and 3-PBA (3-Phenoxybenzoic acid) were detected. The trans-DCCA concentrations ranged from 0.094 to 0.120 mg/kg, which were higher than the concentrations of cis-DCCA (0.091-0.120 mg/kg) and 3-PBA (0.022-0.061 mg/kg). In the presence of oxytetracycline, beta-cypermethrin degradation was inhibited slightly, while the enantioselectivity was not affected. Oxytetracycline increased the enrichment and persistence of the metabolites. Addition of chicken manure decreased the cis-DCCA residue levels in the soil and alleviated the effect of oxytetracycline; however, chicken manure increased the accumulation and persistence of 3-PBA. In addition, oxytetracycline perturbed the structure of the soil microbial community. The abundance of Proteobacteria increased, while the abundances of Firmicutes and Actinobacteria decreased. These changes might affect the biodegradation of beta-cypermethrin and its metabolites. Combined pollution with antibiotics should be considered for its potential impact on pesticide residues.

Pectin reduces environmental pollutant-induced obesity in mice through regulating gut microbiota: A case study of p,p'-DDE.

BACKGROUND: The prevalence of obesity has raised global concerns. Environmental pollutants are one of the main causes of obesity. Many studies have demonstrated that dietary fiber could reduce obesity induced by high-fat diets, but whether environmental pollutant-induced obesity can be reversed is still unknown. OBJECTIVES: This study aimed to investigate the effects of pectin on obesity induced by a typical environmental pollutant p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and explore the underlying mechanism by which pectin reversed p,p'-DDE-induced obesity. METHODS: p,p'-DDE was used to induce obesity in C57BL/6J mice and pectin was supplied during and after cessation of p,p'-DDE exposure. Body and fat weight gain, plasma lipid profile and insulin resistance of mice were assessed. Gut microbiota composition and the levels of short-chain fatty acids (SCFAs) as well as the receptor proteins and hormones in the SCFAs-related signaling pathway were analyzed. Moreover, p,p'-DDE levels in various tissues of mice were detected. RESULTS: Pectin supplementation reversed body and fat weight gain, dyslipidemia, hyperglycemia and insulin resistance in p,p'-DDE-exposed mice. Furthermore, pectin apparently altered the p,p'-DDE-induced microbial composition and then promoted the levels of SCFAs in colonic feces as well as the expression of G-protein coupled receptors and the concentration of hormone peptide YY (PYY) and glucagon like peptide-1 (GLP-1). Pectin treatment also significantly reduced p,p'-DDE accumulation in mice tissues during p,p'-DDE exposure but did not change p,p'-DDE metabolism after termination of p,p'-DDE exposure. CONCLUSIONS: Pectin had a good effect on reducing p,p'-DDE-induced obesity through regulating gut microbiota and provided a potential strategy for the treatment of environmental pollutant-caused health problems.

The biological activities of prothioconazole enantiomers and their toxicity assessment on aquatic organisms.

Chiral fungicide prothioconazole has a wide range of antifungal spectrum; however, little research has been conducted to evaluate prothioconazole on an enantiomeric level. Five target pathogens and three common aquatic organisms were tested for the enantioselective bioactivity and toxicity of prothioconazole in this work. The antifungal activity of the enantiomers against wheat phytoalexin, rice blast fungus, exserohilum turcicum, Alternaria triticina, and Fusarium avenaceum was determined, and it was found that (-)-prothioconazole were 85 to 2768 times more active than (+)-prothioconazole toward these target organisms. In order to reflect the risk to aquatic ecosystem, the acute toxicity of the enantiomers to Daphnia magna, Chlorella pyrenoidosa, and Lemna minor L. was assessed. It was observed that the toxicity of (-)-prothioconazole to D. magna was 2.2 times higher than (+)-prothioconazole, but it was lower to C. pyrenoidosa and L. minor L. The toxicities of (+)-enantiomer and (-)-enantiomer to D. magna and C. pyrenoidosa were synergy, indicating that the racemate had higher threat to the organisms. It could be concluded that the effects of prothioconazole on target organisms and the acute toxicity to nontarget species were enantioselective with (-)-enantiomer possessing higher efficiency and lower toxicity. Such enantiomeric differences should be taken into consideration when assessing the performance of prothioconazole.