Decabromodiphenyl ethane (DBDPE), as one of the most widely used new brominated flame retardants (NBFRs), can pose a potential threat to human health and the environment. An integrated transcriptome and proteome was performed for investigating the toxicological molecular mechanisms of Pleurotus ostreatus (P. ostreatus) during the biodegradation of DBDPE at the concentrations of 5 and 20 mg/L. A total of 1193/1018 and 92/126 differentially expressed genes/proteins (DEGs/DEPs) were found, respectively, with DBDPE exposure at 5 and 20 mg/L. These DEGs and DEPs were mainly involved in the cellular process as well as metabolic process. DEPs for oxidation-reduction process and hydrolase activity were up-regulated, and those for membrane, lipid metabolic process and transmembrane transport were down-regulated. The DEGs and DEPs related to some key enzymes were down-regulated, such as NADH dehydrogenase/oxidoreductase, succinate dehydrogenase, cytochrome C1 protein, cytochrome-c oxidase/reductase and ATP synthase, which indicated that DBDPE affected the oxidative phosphorylation as well as tricarboxylic acid (TCA) cycle. Cytochrome P450 enzymes (CYPs) might be involved in DBDPE degradation through hydroxylation and oxidation. Some stress proteins were induced to resist DBDPE toxicity, including major facilitator superfamily (MFS) transporter, superoxide dismutase (SOD), molecular chaperones, heat shock proteins (HSP20, HSP26, HSP42), 60S ribosomal protein and histone H4. The findings help revealing the toxicological molecular mechanisms of DBDPE on P. ostreatus, aiming to improve the removal of DBDPE.

Carbendazim (CBZ), a broad-spectrum pesticide frequently detected in fruits and vegetables, could trigger potential toxic risks to mammals. To facilitate the assessment of health risks, this study aimed to characterize the cytochrome P450 (CYPs)-mediated metabolism profiles of CBZ by a combined experimental and computational study. Our results demonstrated that CYPs-mediated region-selective hydroxylation was a major metabolism pathway for CBZ in liver microsomes from various species including rat, mouse, minipig, dog, rabbit, guinea pig, monkey, cow and human, and the metabolite was biosynthesized and well-characterized as 6-OH-CBZ. CYP1A displayed a predominant role in the region-selective hydroxylation of CBZ that could attenuate its toxicity through converting it into a less toxic metabolite. Meanwhile, five other common pesticides including chlorpyrifos-methyl, prochloraz, chlorfenapyr, chlorpyrifos, and chlorothalonil could significantly inhibit the region-selective hydroxylation of CBZ, and consequently remarkably increased CBZ exposure in vivo. Furthermore, computational study clarified the important contribution of the key amino acid residues Ser122, and Asp313 in CYP1A1, as well as Asp320 in CYP1A2 to the hydroxylation of CBZ through hydrogen bonds. These results would provide some useful information for the metabolic profiles of CBZ by mammalian CYPs, and shed new insights into CYP1A-mediated metabolic detoxification of CBZ and its health risk assessment.

In Lebanon, previous studies have indicated an onset of cardiovascular diseases 12 years earlier than in other parts of the world, suggesting the presence of additional risk factors specific to Lebanon. Measurements of airborne particles in Lebanon surpass the recommendations of the World Health Organization by over 150%. This study examined the association between obstructive coronary artery disease (CAD), assessed by a novel marker calculated from coronary catheterization, and markers of air pollution, specifically polycyclic aromatic hydrocarbons (PAHs), in a cohort of 258 patients seen at the American University of Beirut Medical Center since 2014. The concentrations of four types of hydroxylated polycyclic aromatic hydrocarbons (OHPAHs), 2-OHNAP, 2-OHFLU, 3-OHPHE, and 1-OHPYR, were measured in the urine samples of these patients using high performance liquid chromatography coupled with fluorescence detector. Results showed that the OHPAH concentrations were higher than what was reported in high-income countries and, most notably, the levels for non-smokers in this study were higher than those of smokers and some occupational workers in other countries. This implies that patients were exposed to high levels of PAHs, which originate from combustion sources. In particular, 1-OHPYR showed a significant association with presence of obstructive CAD, even after adjusting for covariates like age, sex, and diabetes. Smokers or not, this association has implications for public health and calls for urgent need to pass regulations to reduce the emissions of PAH sources, such as cars, diesel generators, and incinerators.

Mammalian polychlorinated biphenyl (PCB) metabolism has not been systematically explored with nontarget high-resolution mass spectrometry (Nt-HRMS). Here we investigated the importance of the gut microbiome in PCB biotransformation by Nt-HRMS analysis of feces from conventional (CV) and germ-free (GF) adult female mice exposed to a single oral dose of an environmental PCB mixture (6 mg/kg or 30 mg/kg in corn oil). Feces were collected for 24 h after PCB administration, PCB metabolites were extracted from pooled samples, and the extracts were analyzed by Nt-HRMS. Twelve classes of PCB metabolites were detected in the feces from CV mice, including PCB sulfates, hydroxylated PCB sulfates (OH-PCB sulfates), PCB sulfonates, and hydroxylated methyl sulfone PCBs (OH-MeSO₂-PCBs) reported previously. We also observed eight additional PCB metabolite classes that were tentatively identified as hydroxylated PCBs (OH-PCBs), dihydroxylated PCBs (DiOH-PCBs), monomethoxylated dihydroxylated PCBs (MeO-OH-PCBs), methoxylated PCB sulfates (MeO-PCB sulfates), mono-to tetra-hydroxylated PCB quinones ((OH)ₓ-quinones, x = 1–4), and hydroxylated polychlorinated benzofurans (OH-PCDF). Most metabolite classes were also detected in the feces from GF mice, except for MeO-OH-PCBs, OH-MeSO₂-PCBs, and OH-PCDFs. Semi-quantitative analyses demonstrate that relative PCB metabolite levels increased with increasing dose and were higher in CV than GF mice, except for PCB sulfates and MeO-PCB sulfates, which were higher in GF mice. These findings demonstrate that the gut microbiome plays a direct or indirect role in the absorption, distribution, metabolism, or excretion of PCB metabolites, which in turn may affect toxic outcomes following PCB exposure.

Non-invasive human biomonitoring methods using hair and fingernails as matrices are widely used to assess the exposure of organic contaminants. In this work, a total of 72 human fingernails were collected from workers and near-by residents from a typical electronic waste (e-waste) dismantling site, and were analyzed for human exposure to polycyclic aromatic hydrocarbons (PAHs) and their mono-hydroxyl metabolites (OH-PAHs). The concentrations of PAHs and OH-PAHs were obtained as 7.97–551 and 39.5–3280 ng/g for e-waste workers (EW workers), 7.05–431 and 27.3–3320 ng/g for non-EW workers, 7.93–289 and 124–779 ng/g for adult residents, and 8.88–1280 and 181–293 ng/g for child residents, respectively. The composition profiles of PAHs in the human fingernails of the four groups were similar, with isomers of Phe, Pyr and Fluo being the predominated congeners, while 2-OH-Nap accounted for more than 70% of the total OH-PAHs. These contaminants were found most in the fingernails of EW workers, followed by non-EW workers, adult residents, and child residents, indicating e-waste dismantling activities are the major sources of PAH exposure. However, significantly higher levels of PAHs with 4–6 rings were observed only in workers as opposed to the residents, and a significant correlation between 3-OH-Flu (p < 0.05) and 2-OH-Phe (p < 0.01) in the fingernails and urine was observed, but no significant correlation was found between the concentration of OH-PAHs in matched hair and fingernail samples. In addition, the levels of PAHs in fingernails increased with the age of EW workers. This is the first study to explore the accumulation and distribution of PAHs and OH-PAHs in human fingernails, which would provide valuable insight into non-invasive biomonitoring and health risk assessment of PAHs.

Marine animals, plants or bacteria are a source of bioactive naturally-occurring halogenated compounds (NHCs) such as bromophenols (BPs), bromoanisoles (BAs) and hydroxylated or methoxylated analogues of polybrominated diphenyl ethers (HO-PBDEs, MeO-PBDEs) and bromobiphenyls (HO-BBs, MeO-BBs). This study applied a comprehensive screening approach using liquid chromatography high-resolution mass spectrometry and combining target, suspect and non-target screening with the aim to identify new hydroxylated NHCs which might be missed by commonly applied gas chromatographic methods. 24 alga samples, 4 sea sponge samples and 7 samples of other invertebrates were screened. Target screening was based on 19 available reference standards of BPs, (di)OH-BDEs and diOH-BBs and yielded seven unequivocally identified compounds. 6-OH-BDE47 was the most frequently detected compound with a detection frequency of 31%. Suspect screening yielded two additional compounds identified in alga samples as well as 17 and 8 compounds identified in sea sponge samples of Lamellodysidea sp. and Callyspongia sp., respectively. The suspect screening results presented here confirmed the findings of previous studies conducted on sea sponge samples of Lamellodysidea sp. and Callyspongia sp. Additionally, in Lamellodysidea sp. and Callyspongia sp. 13 and 4 newly identified NHCs are reported including heptabrominated diOH-BDE, monochlorinated pentabrominated diOH-BDE, hexabrominated OH–MeO-BDE and others. Non-target screening allowed the identification of 31 and 20 polyhalogenated compounds in Lamellodysidea sp. and Callyspongia sp. samples, respectively. Based on the obtained fragmentation spectra, polybrominated dihydroxylated diphenoxybenzenes (diOH-PBDPBs), such as hepta-, octa- and nonabrominated diOH-BDPBs, could be identified in both species. To our knowledge, this study is the first report on the environmental presence of OH-PBDPBs.

In this work, we prepared nanocomposites of nickel-decorated manganese oxynitride on graphene nanosheets and demonstrated them as photocatalysts for degradation of acetylsalicylic acid (ASA). The catalyst exhibited a high degradation efficiency over ASA under visible light irradiation and an excellent structural stability after multiple uses. Compared to manganese oxide (MnO) and manganese oxynitride (MnON) nanoparticles, larger specific surface area and smaller band gap were observed for the nanocomposite accounting for the enhanced photocatalytic efficiency. Besides the compositional effect of the catalyst, we also examined the influence of various experimental parameters on the degradation of ASA such as initial concentration, catalyst dose, initial pH and additives. The best performance was obtained for the nanocomposite when the catalyst dose was 10 mg/mL and the initial pH 3. Detection of intermediates during photocatalysis showed that ASA undergoes hydroxylation, demethylation, aromatization, ring opening, and finally complete mineralization into CO₂ and H₂O by reactive species. For practical applications as a photocatalyst, cytotoxicity of the nanocomposite was also evaluated, which revealed its insignificant impact on the cell viability. These results suggest the nanocomposite of nickel-decorated manganese oxynitride on graphene nanosheets as a promising photocatalyst for the remediation of ASA-contaminated water.

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.

Atrazine contamination is of great concern due to its widespread occurrence in shallow lakes. Here, the distribution and degradation of atrazine in acidic and alkaline lake systems were investigated. Meanwhile, the bacterial communities in different sediments and the effects of environmental factors on atrazine-degrading bacteria were evaluated. In the lake systems without plants, atrazine levels in sediment interstitial water reached peak concentrations on the 4th d. More than 90% of atrazine was then degraded in all sediment interstitial water by day 30. Meanwhile, the degradation rate of atrazine in alkaline sediments was faster than that in acidic sediments. Values of hydroxylated metabolites in the acidic lake sediments tended to be greater. Moreover, the amounts of Proteobacteria, Actinobacteria, Firmicute, Nitrospinae, Aminicenantes, Ignavibacteriae and Saccharibacteria in acidic Tangxunhu Lake sediments were significantly different from alkaline Honghu Lake sediments, while the amounts of Cyanobacteria and Saccharibacteria in sediments treated with atrazine were significantly greater than those in sediments without atrazine (P < 0.05). Notably, pH was the most relevant environmental factor in the quantitative variation of atrazine-degrading bacteria, including in Clostridium-sensu-stricto, Pseudomonas, Comamonas and Rhodobacter. The Mantel test results indicated that the degradation of atrazine in different sediments was mainly affected by the sediment physicochemical properties rather than by the addition of atrazine and the cultivation of hydrophytes.

In this study, the degradation of eight bromophenols (BPs), including monobromophenols (2-BP, 3-BP, and 4-BP), dibromophenols (2,4-DBP, 2,6-DBP, and 3,5-DBP), a tribromophenol (2,4,6-TBP) and a pentabromophenol (PBP), by a Fe(VI) reaction process at a pH of 8.0 was systematically studied. It was concluded that their degradation rates increased with increasing Fe(VI) concentrations in solution. The removal of 2,4,6-TBP, 2-BP, and 2,6-DBP was faster than that of the other five BPs, which could be attributed to the position of the substituting Br atom. Moreover, the direct oxidation and coupling reactions greatly influenced the reactivity of the bromophenols with Fe(VI). The electron paramagnetic resonance (EPR) analysis confirmed the presence of hydroxyl radicals in present system. The oxidation reaction products of PBP and 2-BP were recognized by an electrospray time-of-flight mass spectrometer; hydroxylation, hydroxyl substitution, the cleavage of the C–C bond, direct oxidation and polymerization via an end linking mechanism were noticeably found in the reaction process, resulting in the formation of polymerization products and causing hydroxylation to occur. Theoretical calculations further determined the possible oxidation sites of 2-BP and PBP. This study may provide comprehensive and important information on the remediation of BPs by Fe(VI).