Uptake, Accumulation, and Biomarkers of PM2.5-Associated Organophosphate Flame Retardants in C57BL/6 Mice after Chronic Exposure at Real Environmental Concentrations.

Although the bioaccumulation of organophosphate flame retardants (OPFRs) in aquatic organisms has been investigated, little information is available about their bioaccumulation in mammals following chronic inhalation exposure. To address this knowledge gap, C57BL/6 mice were exposed to 7 PM2.5-associated OPFRs via the trachea to study their bioaccumulation, tissue distribution, and urinary metabolites. Low (corresponding to the real PM2.5 concentrations occurring during winter in Guangzhou), medium, and high dosages were examined. After 72 days' exposure, ∑OPFR concentrations in tissues from mice in the medium dosage group decreased in the order of intestine > heart > stomach > testis > kidney > spleen > brain > liver > lung > muscle. Of the OPFRs detected in all three exposure groups, chlorinated alkyl OPFRs were most heavily accumulated in mice. We found a significant positive correlation between the bioaccumulation ratio and octanol-air partition coefficient (KOA) in mice tissues for low log KOW OPFR congeners (log KOW ≤ 4, p < 0.05). Three urinary metabolites (di-p-cresyl phosphate: DCrP, diphenyl phosphate: DPhP, dibutyl phosphate: DnBP) were detected from the high dosage group. These results provide important insights into the bioaccumulation potential of OPFRs in mammals and emphasize the health risk of chlorinated alkyl OPFRs.

Evaluation and optimization of sample pretreatment for GC/MS-based metabolomics in embryonic zebrafish.

Metabolomics tactics have been applied in the research associated with embryonic zebrafish. However, the report regarding the evaluation of impacts of sample pretreatment on metabolomics results from zebrafish embryos is limited. In the present study, different data normalization approaches, extraction solvents, and extraction strategies for off-line derivatization gas chromatography coupled with mass spectrometry-based metabolomics analysis of zebrafish eleutheroembryos were evaluated and optimized. The results showed that, when 4-chlorophenylalanine normalization, sample homogenization and pure methanol combined with ultrasonic extraction were conducted, better repeatabilities, higher signals and broader coverages of detected metabolites can be achieved. The recovery and standard deviation of most standards were in the range of 82%-121% and 6.6%-12%, respectively, while the relative standard deviation of major detected metabolites ranged from 5.4% to 19%, indicating good extraction efficiencies and method precision. Under the developed method, 87 important endogenous metabolites such as citric acid and hypoxanthine were identified by universal databases or standards among 270 extracted metabolites, which consisted of sugars, amines, amino acids, nucleotides, fatty acids, and sterols. Therefore, the results could provide a proper pretreatment protocol for the analysis of wide-coverage metabolome in embryonic zebrafish. In addition, this study highlights the impact of normalization and extraction methods on the data quality of metabolomics analysis.

Determination of HFRs and OPFRs in PM2.5 by ultrasonic-assisted extraction combined with multi-segment column purification and GC-MS/MS.

Toxic chemicals such as flame retardants are associated with atmospheric fine particles (PM2.5), which are an important pollutant in the world. In this study, a sensitive method using gas chromatography-tandem triple quadrupole mass spectrometry combined with ultrasonic-assisted extraction and multi-phase column purification was developed for simultaneously determination of 29 flame retardants including halogenated flame retardants (HFRs) and organophosphate flame retardants (OPFRs) in PM2.5 samples. Extraction time, as well as the type and volume of elution solvent were optimized. The recoveries of all target flame retardants from PM2.5 samples were in the range of 70%‒130%, with good repeatability and reproducibility (0.39%‒17.4%). The instrumental detection limits (IDLs) and method quantitation limits (MQLs) of HFRs were in the range of 0.004‒5.44 pg and 0.002‒2.52 pg m-3, while those of OPFRs were 0.003‒0.23 pg and 0.07‒5.41 pg m-3, respectively. The developed method has been successfully applied for analysis of target flame retardants in atmospheric PM2.5 collected from the cities of Guangzhou and Taiyuan, China. HFRs were found at concentrations of 45.7‒1230 pg m-3 and 51.2‒82.3 pg m-3 in Guangzhou and Taiyuan. The concentrations of HFRs were lower than those of OPFRs, which were detected at concentrations of 6004‒49,800 pg m-3 and 16,741‒34,346 pg m-3 in Guangzhou and Taiyuan. Accordingly, the analytical method is robust and useful for further elucidating the contamination profiles of flame retardants in PM2.5.

Analysis of transcriptional response in zebrafish eleutheroembryos exposed to climbazole: Signaling pathways and potential biomarkers.

Climbazole is an antifungal active ingredient used in personal care products. After application this chemical reaches the aquatic environment and may pose a risk to fish. In the present study, we measured the transcriptional effects of essential genes related to a wide range of signaling pathways on zebrafish eleutheroembryos exposed to climbazole at environmentally relevant and predicted worst-case environmental concentrations, and explored the potential biomarkers via partial least squares discriminant analysis. Transcription analysis covering up to 73 genes revealed significant down-regulation of circadian rhythm- and steroidogenesis-related genes in zebrafish embryos and larvae after exposure to environmentally relevant concentrations of climbazole. This topical antifungal agent also modulated the transcripts of genes involved in inflammation, oxidative stress, oocyte maturation, and sexual differentiation at predicted worst-case environmental concentrations. In addition, mprα, igf3, nr1d1, nr1d2b, cyp19a1a, vtg1, il-1ß, and il-8 were chosen as potential biomarkers in embryonic zebrafish following exposure to climbazole. These findings can help us understand the remarkable transcriptional response to climbazole in the early life stage of zebrafish. Future research should elucidate whether the transcriptional modulation translates into metabolic phenotypes associated with the corresponding signaling pathways. Environ Toxicol Chem 2019;38:794-805. © 2019 SETAC.

Contamination and risk profiles of triclosan and triclocarban in sediments from a less urbanized region in China.

Triclosan and triclocarban are priority environmental contaminants of increasing concern to environmental health. After application, the chemicals enter the aquatic environment and easily distribute in bed sediment due to their hydrophobicity, and thus pose potential ecological risks. This study investigated the distribution and risks of triclosan and triclocarban in the sediment environment of a less urbanized region in South China. The sampling sites with high levels of triclosan and triclocarban were found to locate in the tributaries. When compared to other monitoring results obtained from more densely populated regions, the residues of triclosan and triclocarban in the investigated region were low, suggesting that these two chemicals conservation in sediment is related to anthropic activities. The results of risk quotients showed that high risks to aquatic organisms were posed by triclosan residues in sediment, while the risks to benthic organisms were quite low. Triclocarban residues in sediment posed minimal to medium risks to aquatic and benthic organisms. In summary, using either of the calculation methods of risk quotients, medium risks posed by the antimicrobials can be found in certain sampling sites with low population densities. The results may be useful in the development of evidence-based policies for the government.