No abstract

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants (BFRs) and has been frequently detected in the environment and biota. Recent studies have found that derivatives of TBBPA, such as TBBPA bis(allyl) ether (TBBPA BAE) and TBBPA bis(2,3-dibromopropyl) ether (TBBPA BDBPE) are present in various environmental compartments. In this work, using liquid chromatography coupled with tandem mass spectrometry (LC−MS/MS) and liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC−Q-TOF-MS), TBBPA allyl ether (TBBPA AE) and TBBPA 2,3-dibromopropyl ether (TBBPA DBPE) were identified in environmental samples and further confirmed by synthesized standards. Soil, sediment, rice hull, and earthworm samples collected near a BFR manufacturing plant were found to contain these two compounds. In sediments, the concentrations of TBBPA AE and TBBPA DBPE ranged from 1.0 to 346.6 ng/g of dry weight (dw) and from 0.7 to 292.7 ng/g of dw, respectively. TBBPA AE and TBBPA DBPE in earthworm and rice hull samples were similar to soil samples, which ranged from below the method limit of detection (LOD, <0.002 ng/g of dw) to 0.064 ng/g of dw and from below the LOD (<0.008 ng/g of dw) to 0.58 ng/g of dw, respectively. Furthermore, mollusks collected from the Chinese Bohai Sea were used as a bioindicator to investigate the occurrence and distribution of these compounds in the coastal environment. The detection frequencies of TBBPA AE and TBBPA DBPE were 41 and 32%, respectively, and the concentrations ranged from below LOD (<0.003 ng/g of dw) to 0.54 ng/g of dw, with an average of 0.09 ng/g of dw, for TBBPA AE, and from below LOD (<0.008 ng/g of dw) to 1.41 ng/g of dw, with an average of 0.15 ng/g of dw, for TBBPA DBPE.

Short chain chlorinated paraffins (SCCPs) are high production volume chemicals in China and found to be widely present in the environment. In this study, fifty-one surface sediments and two sediment cores were collected from the East China Sea to study their occurrence, distribution patterns and potential transport in the marginal sea. SCCPs were found in all surface sediments and ranged from 5.8 to 64.8 ng/g (dry weight, d.w.) with an average value of 25.9 ng/g d.w. A general decreasing trend with distance from the coast was observed, but the highest value was found in a distal mud area far away from the land. The C10 homologue was the most predominant carbon chain group, followed by C11, C12, and C13 homologue groups. Significant linear relationship was found between total organic carbon (TOC) and total SCCP concentrations (R(2) = 0.51, p < 0.05). Spatial distributions and correlation analysis indicated that TOC, riverine input, ocean current, and atmospheric deposition played an important role in controlling SCCP accumulation in marine sediments. Vertical profiles of sediment cores showed that SCCP concentrations decreased from surface to the depth of 36 cm, and then slightly increased again with depth, which showed a significant positive correlation with TOC and chlorine contents (Cl%). The results suggest that SCCPs are being regionally or globally distributed by long-range atmospheric or ocean current transport.

Heavy-ion beam irradiation is one of the principal methods used to create mutants in plants. Research on mutagenic effects and molecular mechanisms of radiation is an important subject that is multi-disciplinary. Here, we re-sequenced 11 mutagenesis progeny (M3) Arabidopsis thaliana lines derived from carbon-ion beam (CIB) irradiation, and subsequently focused on substitutions and small insertion-deletion (INDELs). We found that CIB induced more substitutions (320) than INDELs (124). Meanwhile, the single base INDELs were more prevalent than those in large size (≥2 bp). In details, the detected substitutions showed an obvious bias of C > T transitions, by activating the formation of covalent linkages between neighboring pyrimidine residues in the DNA sequence. An A and T bias was observed among the single base INDELs, in which most of these were induced by replication slippage at either the homopolymer or polynucleotide repeat regions. The mutation rate of 200-Gy CIB irradiation was estimated as 3.37 × 10−7 per site. Different from previous researches which mainly focused on the phenotype, chromosome aberration, genetic polymorphism, or sequencing analysis of specific genes only, our study revealed genome-wide molecular profile and rate of mutations induced by CIB irradiation. We hope our data could provide valuable clues for explaining the potential mechanism of plant mutation breeding by CIB irradiation.

Sewage treatment plants (STP) are an important source of short chain chlorinated paraffins (SCCPs) to the ambient environment through discharge of effluent and application of sludge. In this work, a field study was conducted to determine the behavior and possible removal of SCCPs during the sewage treatment process in an advanced municipal STP in Beijing, China. SCCPs were detected in all sewage water and sludge samples, and 97% of the initial mass loading in raw sewage was found to be associated with suspended matter. The total concentrations in raw influent, tertiary effluent, and dewatered sludge were 184 ± 19 ng/L, 27 ± 6 ng/L, and 15.6 ± 1.4 μg/g dry weight (d.w.), respectively. The dissolved concentrations of total SCCPs (∑SCCPs) significantly decreased during mechanical, biological, and chemical treatments. SCCP homologue profiles in aqueous phase were distinctly different from those in solid phase. Along the treatment process, the relative abundance of shorter chain and lower chlorinated congeners gradually increased in sewage water, but no obvious variations of homologue profiles were found in sludge. Mass flow analysis indicated, the removal efficiency in aqueous phase for ∑SCCPs was 82.2%, and the congener-specific removal efficiencies were positively related to their solid−water partition coefficients (K d ). Mass balance results indicated that 0.8% and 72.6% of the initial SCCP mass loading were ultimately found in the effluents and dewatered sludge, respectively, while the remaining 26.6% was lost mainly due to biodegradation/ biotransformation. It was suggested that the activated sludge system including basic anaerobic−anoxic−aerobic processes played an effective role in removing SCCPs from the wastewater, while the sorption to sludge by hydrophobic interactions was an important fate of SCCPs during the sewage treatment.

Identification of novel brominated contaminants in the environment, especially the derivatives and byproducts of brominated flame retardants (BFRs), has become a wide concern because of their adverse effects on human health. Herein, we qualitatively and quantitatively identified three byproducts of tetrabromobisphenol-S bis(2,3-dibromopropyl ether) (TBBPS-BDBPE), including TBBPS mono(allyl ether) (TBBPS-MAE), TBBPS mono(2-bromoallyl ether) (TBBPS-MBAE) and TBBPS mono(2,3-dibromopropyl ether) (TBBPS-MDBPE) as novel brominated contaminants. Meanwhile, the mass spectra and analytical method for determination of TBBPS-BDBPE byproducts were presented for the first time. The detectable concentrations (dry weight) of TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE were in the ranges 28–394 μg/g in technical TBBPS-BDBPE and 0.1–4.1 ng/g in mollusks collected from the Chinese Bohai Sea. The detection frequencies in mollusk samples were 5%, 39%, 95% for TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE, respectively, indicating their prevailing in the environment. The results showed that they could be co-produced and leaked into the environment with production process, and might be more bioaccumulative and toxic than TBBPS-BDBPE. Therefore, the production and use of TBBPS derivatives lead to unexpected contamination to the surrounding environment. This study also provided an effective approach for identification of novel contaminants in the environment with synthesized standards and Orbitrap high resolution mass spectrometry.

BackgroundPolychlorinated biphenyls (PCBs) are a family of structurally related chlorinated aromatic hydrocarbons. Numerous studies have documented a wide spectrum of biological effects of PCBs on human health, such as immunotoxicity, neurotoxocity, estrogenic or antiestrogenic activity, and carcinogensis. The role of PCBs as etiologic agents for breast cancer has been intensively explored in a variety of in vivo, animal and epidemiologic studies. A number of investigations indicated that higher levels of PCBs in mammary tissues or sera correlated to breast cancer risk, and PCBs might be implicated in advancing breast cancer progression.Methodology/Principal FindingsIn the current study, we for the first time report that PCBs greatly promote the ROCK activity and therefore increase cell motility for both non-metastatic and metastatic human breast cancer cells in vitro. In the in vivo study, PCBs significantly advance disease progression, leading to enhanced capability of metastatic breast cancer cells to metastasize to bone, lung and liver. Additionally, PCBs robustly induce the production of intracellular reactive oxygen species (ROS) in breast cancer cells; ROS mechanistically elevate ROCK activity.Conclusions/SignificancePCBs enhance the metastatic propensity of breast cancer cells by activating the ROCK signaling, which is dependent on ROS induced by PCBs. Inhibition of ROCK may stand for a unique way to restrain metastases in breast cancer upon PCB exposure.

Chemokine stromal cell-derived factor-1 (SDF-1) is a potent chemoattractant involved in leukocyte trafficking and metastasis. Heparan sulfate on the cell surface binds SDF-1 and may modulate its function as a coreceptor of this chemokine. A major effect of the glycosaminoglycan binding may be on the quaternary structure of SDF-1, which has been controversially reported as a monomer or a dimer. We have investigated the effect of sulfated oligosaccharides on the oligomerization of SDF-1 and of its mutated form SDF-1 (3/6), using affinity capillary electrophoresis (ACE) hyphenated to mass spectrometry (MS). Coupled to MS, ACE allowed the study for the first time of the effect of size-defined oligosaccharides on the quaternary organization of SDF-1 in muM range concentrations, i.e., lower values than the mM values previously reported in NMR, light scattering, and ultracentrifugation experiments. Our results showed that in the absence of sulfated oligosaccharides, SDF-1 is mostly monomeric in solution. However, dimer formation was observed upon interaction with heparin-sulfated oligosaccharides despite the mM Kd values for dimerization. A SDF-1/oligosaccharide 2/1 complex was detected, indicating that oligosaccharide binding promoted the dimerization of SDF-1. Heparin tetrasaccharide but not disaccharide promoted dimer formation, suggesting that the dimer required to be stabilized by a long enough bound oligosaccharide. The SDF-1/oligosaccharide 1/1 complex was only observed with heparin disaccharide and fucoidan pentasaccharide, pointing out the role of specific structural determinants in promoting dimer formation. These results underline the importance of dimerization induced by glycosaminoglycans for chemokine functionality.