Effect of Dissolved Organic Matter on the Photodegradation of Decachlorobiphenyl (PCB-209) in Heterogeneous Systems: Experimental Analysis and Excited-State Theory Calculations.

Dissolved organic matter (DOM) can affect the transformation of pollutants through photosensitization, but most current research focuses on hydrophilic pollutants, making it such that less attention is paid to hydrophobic pollutants. In this paper, the effect and action mechanism of coexisting DOM on the photodegradation of decachlorobiphenyl (PCB-209) on suspended particles collected from the Yellow River were systematically investigated in a heterogeneous system using DOM standards and model compounds. Through molecular probe experiments, mass spectrometry analysis and theoretical calculations, we found that the excited triplet state of DOM (3DOM*) could excite PCB-209 to undergo dechlorination reaction. Due to the different modes of electron transition, the presence of carbonyl groups decreased the energy of 3DOM*, whereas the electron-donating groups made the energy of 3DOM* higher. DOM containing phenolic hydroxyl groups led to a higher steady-state concentration of •OH, and DOM containing phenyl ketone structures had a stronger ability to produce •O2-. Compared with aqueous •OH, •O2- produced from hydrophobic microregions could react more readily with PCB-209. This study deepens the understanding of the role of different functional groups of DOM in the photosensitized transformation of hydrophobic compounds.

Persistent and Bioaccumulative Halogenated Natural Products in Various Tropical Reef Fish Species from the Seychelles, Western Indian Ocean.

Gas chromatography with electron capture negative ion mass spectrometry (GC/ECNI-MS) was used to quantify and compare halogenated natural products (HNPs) and selected anthropogenic persistent organic pollutants (POPs) in individual samples of 17 fish species from the Seychelles (Western Indian Ocean). The sum-HNP amounts (9.5-1100 ng/g lipid mass (lm)) were between 1 and 2 orders of magnitude higher than those of the sum of seven abundant polychlorinated biphenyl (PCB) congeners (0.2-15 ng/g lm) and dichlorodiphenyltrichloroethane-related compounds (DDTs) (<1.1-43 ng/g lm). Within the group of HNPs, the two tetrabrominated phenoxyanisoles (aka methoxylated diphenyl ethers, MeO-BDEs), 2'-MeO-BDE 68 ≫ 6-MeO-BDE 47, were predominant in most cases. Pearson correlation analysis showed that MeO-BDE levels were positively correlated with less abundant HNPs (2,2'-diMeO-BB 80, 2',6-diMeO-BDE 68, and Br6-DBP) (p < 0.01). Accordingly, HNPs, rather than PCBs and DDTs, were the predominant polyhalogenated contaminants in the current species.

A microfluidic ratiometric electrochemical aptasensor for highly sensitive and selective detection of 3,3',4,4'-tetrachlorobiphenyl.

This study proposes a strategy using a microfluidic ratiometric electrochemical aptasensor to detect PCB77 with excellent sensitivity and specificity. This sensing platform combines a microfluidic chip, a wireless integrated circuit system for aptamer-based electrochemical detection, and a mobile phone control terminal for parameter configuration, identification, observation, and wireless data transfer. The sensing method utilizes a cDNA (MB-COOH-cDNA-SH) that is labelled with the redox probe Methylene Blue (MB) at the 5' end and has a thiol group at the 3' end. Additionally, it utilizes a single strand PCB aptamer that has been modified with ferrocenes at the 3' end (aptamer-Fc). Through gold-thiol binding, the labelled probe of MB-COOH-cDNA-SH was self-assembled onto the surface of an Au/Nb2CTx/GO modified electrode. On exposure to aptamer-Fc, it will hybridize with MB-COOH-cDNA-SH to form a stable double-stranded structure on the electrode surface. When PCB77 is present, aptamer-Fc binds specifically to the target, enabling the double-stranded DNA to unwind. Such variation caused changes in the differential pulse voltammetry (DPV) peak currents of both MB and Fc. A substantial improvement is observed in the ratio between the two DPV peaks. Under the optimum experimental conditions, this assay has a response that covers the 0.0001 to 1000 ng mL-1 PCB77 concentration range, and the detection limit is 1.56 × 10-5 ng mL-1. The integration of a ratiometric electrochemical aptasensor with designed microfluidic and integrated devices in this work is an innovative and promising approach that offers an efficient platform for on-site applications.

The catalytic hydro-dechlorination of 2, 4, 4' trichlorobiphenyl at mild temperatures and atmospheric pressure.

Polychlorinated biphenyls (PCBs), including all 209 congeners, are designated as persistent organic pollutants (POPs) due to their high toxicity and bioaccumulation in human bodies and the ecosystem. The need for PCB remediation still remains long after their production ban. In this study, a catalytic hydro-dechlorination (HDC) method was employed to dechlorinate 2,4,4'-trichlorobiphenyl (PCB 28), a congener found ubiquitously in multiple environmental media. The HDC of PCB 28 was experimentally studied at mild temperatures viz. ~20, 50, and ~77°C and atmospheric pressure. Et3N (triethylamine) was added as a co-catalyst. The dechlorination rates increased with temperature as well as Et3N dosage, and the HDC pathway was hypothesized based on the product and intermediates observed. The less chlorinated intermediates suggested that the position of the chlorine strongly impacted HDC rates, and the preference of HDC at para positions can be orders of magnitudes higher than the ortho. The activation energy was estimated in the range of 12.4-13.9 kJ/mole, indicating a diffusion-controlled HDC system.Implications: The remediation need for polychlorinated biphenyls (PCBs) still remains long after their production ban around the world. The development of low-cost methods is highly desirable, especially for developing countries, in response to the Stockholm Convention. In this study, the dechorination of a ubiquitously present PCB congener was studied using a catalytic hydro-dechlorination (HDC) method in low temperatures up to ~77°C and was able to achieve near 100% dechlorination in 6 hr. Results indicated that the HDC process can be performed under mild temperatures and atmospheric conditions and can be a potential solution to real world PCB contamination issues.

Optimization and validation of high throughput methods for the determination of 132 organic contaminants in green and roasted coffee using GC-QqQ-MS/MS and LC-QqQ-MS/MS.

Recently some major safety concerns have been raised on organic contaminants in widely consumed plants such as coffee. Hence, this study aimed to develop specifically optimized methods for determining organic contaminants, such as pesticides and polychlorinated biphenyls (PCBs), in coffee using GC-MS/MS and LC-MS/MS. QuEChERS method was used as a base extraction method, and 27 experiments were studied using design of experiments with categorical variables (extraction buffers, cleanup sorbents, and coffee roasting degree) to find the optimum method for each matrix type. The optimum method for green coffee was acetate buffer and chitosan for clean-up, while no-buffer extraction and the PSA + C18 method were ideal for light and dark-roasted coffee. The optimized methods were validated in accordance with SANTE/11312/2021. Furthermore, ten real samples (4 green, and 6 roasted) from the markets were analysed; ortho-phenylphenol was found in all the roasted coffee samples, and carbendazim was found in one green coffee sample.

Dioxin(-like)-Related Biological Effects through Integrated Chemical-wide and Metabolome-wide Analyses.

Dioxin(-like) exposures are linked to adverse health effects, including cancer. However, metabolic alterations induced by these chemicals remain largely unknown. Beyond known dioxin(-like) compounds, we leveraged a chemical-wide approach to assess chlorinated co-exposures and parent compound products [termed dioxin(-like)-related compounds] among 137 occupational workers. Endogenous metabolites were profiled by untargeted metabolomics, namely, reversed-phase chromatography with negative electrospray ionization (C18-negative) and hydrophilic interaction liquid chromatography with positive electrospray ionization (HILIC-positive). We performed a metabolome-wide association study to select dioxin(-like) associated metabolic features using a 20% false discovery rate threshold. Metabolic features were then characterized by pathway enrichment analyses. There are no significant features associated with polychlorinated dibenzo-p-dioxins (PCDDs), a subgroup of known dioxin(-like) compounds. However, 3,110 C18-negative and 2,894 HILIC-positive features were associated with at least one of the PCDD-related compounds. Abundant metabolic changes were also observed for polychlorinated dibenzofuran-related and polychlorinated biphenyl-related compounds. These metabolic features were primarily enriched in pathways of amino acids, lipid and fatty acids, carbohydrates, cofactors, and nucleotides. Our study highlights the potential of chemical-wide analysis for comprehensive exposure assessment beyond targeted chemicals. Coupled with advanced endogenous metabolomics, this approach allows for an in-depth exploration of metabolic alterations induced by environmental chemicals.