Comprehensive exploration of the anaerobic biotransformation of polychlorinated biphenyls in Dehalococcoides mccartyi CG1: Kinetics, enantioselectivity, and isotope fractionation.

Anaerobic microbial transformation is a key pathway in the natural attenuation of polychlorinated biphenyls (PCBs). Much less is known about the transformation behaviors induced by pure organohalide-respiring bacteria, especially kinetic isotope effects. Therefore, the kinetics, pathways, enantioselectivity, and carbon and chlorine isotope fractionation of PCBs transformation by Dehalococcoides mccartyi CG1 were comprehensively explored. The results indicated that the PCBs were mainly dechlorinated via removing their double-flanked meta-chlorine, with their first-order kinetic constants following the order of PCB132 > PCB174 > PCB85 > PCB183 > PCB138. However, PCBs occurred great loss of stoichiometric mass balance during microbial transformation, suggesting the generation of other non-dehalogenation products and/or stable intermediates. The preferential transformation of (-)-atropisomers and generation of (+)-atropisomers were observed during PCB132 and PCB174 biotransformation with the enantiomeric enrichment factors of -0.8609 ± 0.1077 and -0.4503 ± 0.1334 (first half incubation times)/-0.1888 ± 0.1354 (second half incubation times), respectively, whereas no enantioselectivity occurred during PCB183 biotransformation. More importantly, although there was no carbon and chlorine isotope fractionation occurring for studied substrates, the δ13C values of dechlorination products, including PCB47 (-28.15 ± 0.35‰ âˆ¼ -27.77 ± 0.20‰), PCB91 (-36.36 ± 0.09‰ âˆ¼ -34.71 ± 0.49‰), and PCB149 (-28.08 ± 0.26‰ âˆ¼ -26.83 ± 0.10‰), were all significantly different from those of their corresponding substrates (PCB85: -30.81 ± 0.02‰ âˆ¼ -30.22 ± 0.21‰, PCB132: -33.57 ± 0.15‰ âˆ¼ -33.13 ± 0.14‰, and PCB174: -26.30 ± 0.09‰ âˆ¼ -26.01 ± 0.07‰), which further supported the generation of other non-dehalogenation products and/or stable intermediates with enrichment or depletion of 13C. These findings provide deeper insights into the anaerobic microbial transformation behaviors of PCBs.

Trophic Transfer of Halogenated Organic Pollutants in a Wetland Food Web: Insights from Compound-Specific Nitrogen Isotope of Amino Acids and Food Source Analysis.

A trophic position (TP) model (TPmix model) that simultaneously considered trophic discrimination factor and ßGlu/Phe variations was developed in this study and was first applied to investigate the trophic transfer of halogenated organic pollutants (HOPs) in wetland food webs. The TPmix model characterized the structure of the wetland food web more accurately and significantly improved the reliability of TMF compared to the TPbulk, TPAAs, and TPsimmr models, which were calculated based on the methods of stable nitrogen isotope analysis of bulk, traditional AAs-N-CSIA, and weighted ßGlu/Phe, respectively. Food source analysis revealed three interlocking food webs (kingfisher, crab, and frogs) in this wetland. The highest HOP biomagnification capacities (TMFmix) were found in the kingfisher food web (0.24-82.0), followed by the frog (0.08-34.0) and crab (0.56-11.7) food webs. The parabolic trends of TMFmix across combinations of log KOW in the frog food web were distinct from those of aquatic food webs (kingfisher and crab), which may be related to differences in food web composition and HOP bioaccumulation behaviors between aquatic and terrestrial organisms. This study provides a new tool to accurately study the trophic transfer of contaminants in wetlands and terrestrial food webs with diverse species and complex feeding relationships.

Anaerobic biotransformation of two novel brominated flame retardants: Kinetics, isotope fractionation and reaction mechanisms.

1,2,5,6-tetrabromocyclooctane (TBCO) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), as safer alternatives to traditional brominated flame retardants, have been extensively detected in various environmental media and pose emerging risks. However, much less is known about their fate in the environment. Anaerobic microbial transformation is a key pathway for the natural attenuation of contaminants. This study investigated, for the first time, the microbial transformation behaviors of ß-TBCO and DPTE by Dehalococcoides mccartyi strain CG1. The results indicated that both ß-TBCO and DPTE could be easily transformed by D. mccartyi CG1 with kobs values of 0.0218 ± 0.0015 h-1 and 0.0089 ± 0.0003 h-1, respectively. In particular, ß-TBCO seemed to undergo dibromo-elimination and then epoxidation to form 4,5-dibromo-9-oxabicyclo[6.1.0]nonane, while DPTE experienced debromination at the benzene ring (ortho-bromine being removed prior to para-bromine) rather than at the carbon chain. Additionally, pronounced carbon and bromine isotope fractionations were observed during biotransformation of ß-TBCO and DPTE, suggesting that C-Br bond breaking is the rate-limiting step of their biotransformation. Finally, coupled with identified products and isotope fractionation patterns, ß-elimination (E2) and Sn2-nucleophilic substitution were considered the most likely microbial transformation mechanisms for ß-TBCO and DPTE, respectively. This work provides important information for assessing the potential of natural attenuation and environmental risks of ß-TBCO and DPTE.

Biomagnification and elimination effects of persistent organic pollutants in a typical wetland food web from South China.

This study investigated the quantitative sources of persistent organic pollutants (POPs), their biomagnification factors, and their effect on POP biomagnification in a typical waterbird (common kingfisher, Alcedo atthis) food web in South China. The median concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in kingfishers were 32,500 ng/g lw and 130 ng/g lw, respectively. The congener profiles of PBDEs and PCBs showed significant temporal changes because of the restriction time points and biomagnification potential of different contaminants. The concentrations of most bioaccumulative POPs, such as CBs 138 and 180 and BDEs 153 and 154, decreased at lower rates than those of other POPs. Pelagic fish (metzia lineata) and benthic fish (common carp) were the primary prey of kingfishers, as indicated by quantitative fatty acid signature analysis (QFASA) results. Pelagic and benthic prey species were the primary sources of low and high hydrophobic contaminants for kingfishers, respectively. Biomagnification factors (BMFs) and trophic magnification factors (TMFs) had parabolic relationships with log KOW, with peak values of approximately 7. Significant negative correlations were found between the whole-body elimination rates of POPs in waterbirds and the log-transformed TMFs and BMFs, indicating that the strong metabolism of waterbirds could potentially affect POP biomagnification.

LDER: a classification framework based on ERP enhancement in RSVP task.

Objective.Rapid serial visual presentation (RSVP) based on electroencephalography (EEG) has been widely used in the target detection field, which distinguishes target and non-target by detecting event-related potential (ERP) components. However, the classification performance of the RSVP task is limited by the variability of ERP components, which is a great challenge in developing RSVP for real-life applications.Approach.To tackle this issue, a classification framework based on the ERP feature enhancement to offset the negative impact of the variability of ERP components for RSVP task classification named latency detection and EEG reconstruction was proposed in this paper. First, a spatial-temporal similarity measurement approach was proposed for latency detection. Subsequently, we constructed a single-trial EEG signal model containing ERP latency information. Then, according to the latency information detected in the first step, the model can be solved to obtain the corrected ERP signal and realize the enhancement of ERP features. Finally, the EEG signal after ERP enhancement can be processed by most of the existing feature extraction and classification methods of the RSVP task in this framework.Main results.Nine subjects were recruited to participate in the RSVP experiment on vehicle detection. Four popular algorithms (spatially weighted Fisher linear discrimination-principal component analysis (PCA), hierarchical discriminant PCA, hierarchical discriminant component analysis, and spatial-temporal hybrid common spatial pattern-PCA) in RSVP-based brain-computer interface for feature extraction were selected to verify the performance of our proposed framework. Experimental results showed that our proposed framework significantly outperforms the conventional classification framework in terms of area under curve, balanced accuracy, true positive rate, and false positive rate in four feature extraction methods. Additionally, statistical results showed that our proposed framework enables better performance with fewer training samples, channel numbers, and shorter temporal window sizes.Significance.As a result, the classification performance of the RSVP task was significantly improved by using our proposed framework. Our proposed classification framework will significantly promote the practical application of the RSVP task.

Application of amino acids nitrogen stable isotopic analysis in bioaccumulation studies of pollutants: A review.

Accurately quantifying trophic positions (TP) to describe food web structure is an important element in studying pollutant bioaccumulation. In recent years, compound-specific nitrogen isotopic analysis of amino acids (AAs-N-CSIA) has been progressively applied as a potentially reliable tool for quantifying TP, facilitating a better understanding of pollutant food web transfer. Therefore, this review provides an overview of the analytical procedures, applications, and limitations of AAs-N-CSIA in pollutant (halogenated organic pollutants (HOPs) and heavy metals) bioaccumulation studies. We first summarize studies on the analytical techniques of AAs-N-CSIA, including derivatization, instrumental analysis, and data processing methods. The N-pivaloyl-i-propyl-amino acid ester method is a more suitable AAs derivatization method for quantifying TP. The AAs-N-CSIA application in pollutant bioaccumulation studies (e.g., Hg, MeHg, and HOPs) is discussed, and its application in conjunction with various techniques (e.g., spatial analysis, food source analysis, and compound tracking techniques, etc.) to research the influence of pollutant levels on organisms is summarized. Finally, the limitations of AAs-N-CSIA in pollutant bioaccumulation studies are discussed, including the use of single empirical values of ßglu/phe and TDFglu/phe that result in large errors in TP quantification. The weighted ßglu/phe and the multi-TDFglu/phe models are still challenging to solve for accurate TP quantification of omnivores; however, factors affecting the variation of ßglu/phe and TDFglu/phe are unclear, especially the effect of pollutant bioaccumulation in organisms on internal AA metabolic processes.