Revealing chemical release from plastic debris in animals' digestive systems using nontarget and suspect screening and simulating digestive fluids.

Plastic debris in the environment are not only pollutants but may also be important sources of a variety of contaminants. This work simulated kinetics and potential of chemical leaching from plastic debris in animals' digestive systems by incubating polyvinyl chloride (PVC) cord particles in artificial digestive fluids combined with nontarget and suspect screening based on UHPLC-Orbitrap HRMS. Impacts of particle size, aging, and digestive fluid were investigated to elucidate mechanisms of chemical leaching. Thousands of chemical features were screened in the leachates of PVC cord particles in the artificial digestive fluids, among which >60% were unknown. Bisphenol A (BPA) and bis(2-ethylhexyl) phthalate (DEHP) were the dominant identified CL1 compounds. Finer size and aging of the PVC particles and prolonged incubation time enhanced chemical release, resulting in greater numbers, higher levels, and more complexity in components of the released chemicals. The gastrointestinal fluid was more favorable for chemical leaching than the gastric fluid, with greater numbers and higher levels. Hundreds to thousands of chemical features were screened and filtered in the leachates of consumer plastic products, including food contact products (FCPs) in the artificial bird gastrointestinal fluid. In addition to BPA and DEHP, several novel bisphenol analogues were identified in the leachate of at least one FCP. The results revealed that once plastic debris are ingested by animals, hundreds to thousands of chemicals may be released into animals' digestive tracts in hours, posing potential synergistic risks of plastic debris and chemicals to plastic-ingesting animals. Future research should pay more attentions to identification, ecotoxicities, and environmental fate of vast amounts of unknown chemicals potentially released from plastics in order to gain full pictures of plastic pollution in the environment.

Profile, Tissue Distribution, and Time Trend of Bisphenol Plastic Additives in Freshwater Wildlife of the Pearl River Ecosystem, China.

Plastic-related contaminants in the environment have attracted increasing attention, with plastic pollution becoming a serious issue globally. The present study investigated the potential bioaccumulation and biotransfer of bisphenol (BP) compounds that are widely added in various products such as plastics and other products in a freshwater ecosystem, China. Among commonly applied 14 BP analogues, bisphenol A (BPA), bisphenol F (BPF), and bisphenol S (BPS) were predominant, representing 64%-100% of the total concentrations of BPs (ΣBPs) in freshwater wildlife. Both the concentrations and analogue profiles in the fish showed seasonal differences and species dependence. Higher BP concentrations were observed in fish collected during the dry season than the wet season. Higher percentages of non-BPA analogues (e.g., BPS and BPF) were observed in fish collected during the wet season. Pelagic species accumulated notably higher levels of BPs than midwater and bottom species. The liver generally contained the highest ΣBPs, followed successively by the swim bladder, belly fat, and dorsal muscle. The analogue profile also showed some differences among tissues, varying by species and season. Lower ΣBPs but higher percentages of non-BPA analogues were observed in female than male common carp. Time trends of the BPA concentration in fish varied by species, probably related to habitats and diets of the fish. Habitats, feeding behaviors, and trophic transfer may have significant impacts on exposure of wildlife to BPs in natural ecosystems. The BPs did not demonstrate strong potential for bioaccumulation. More research is warranted about metabolism and transgenerational transfer of BPs in wildlife to fully reveal the bioaccumulation and consequently ecological risks of these chemicals in the environment. Environ Toxicol Chem 2023;42:2130-2142. © 2023 SETAC.

Multi-residue determination of bisphenol analogues in organism tissues by ultra-high performance liquid chromatography-tandem mass spectrometry.

A reliable and sensitive analyzing method was developed and validated for determination of 13 novel bisphenol analogues (BPs) along with bisphenol A (BPA) in organism tissues. The complex organism tissues were treated by ultrasonic-assisted extraction using acetonitrile/formic acid (99:1, v/v), followed by successive purification using enhanced matrix removal-lipid sorbents and primary secondary amine sorbents. The BPs were finally determined by ultra-high performance liquid chromatography-tandem mass spectrometry after derivatization using pyridine-3-sulfonyl chloride. Satisfactory recoveries of 75 - 118% were obtained for the BPs, with good repeatability (RSD < 20%). Matrix interferences were efficiently diminished. The method quantification limits (MQLs) reached 0.003 - 0.1 ng g-1 dry weight (dw). The validated method was successfully applied to a preliminary investigation of the BPs in wild marine organisms collected from the nearshore waters along the coast of Guangdong, China. Besides BPA, novel BPs such as bisphenol F, bisphenol AF, and tetrabromobisphenol A were also detected at < MDL - 15.5 ng g-1 dw. This work laid a strong basis for further in-depth research on bioaccumulation of the novel BPs in the environment.

Nontarget analysis and comprehensive characterization of halogenated organic pollutants by GC-Q-Orbitrap-HRMS in association with chromatogram segmentation and Cl/Br-specific screening algorithms.

Nontarget analysis enables high-efficiency screening and identification of halogenated organic pollutants (HOPs) in complex matrices irrespective of lacking authentic standards, particularly for novel and emerging species, thereby realizing comprehensive component characterization of HOPs. Notwithstanding, nontarget analysis and comprehensive characterization of HOPs remain on the way to improvement. In this study, we implemented nontarget analysis of HOPs in fly ash, egg and sediment using gas chromatography quadrupole-orbitrap high-resolution mass spectrometry with the aid of chromatogram segmentation and Cl/Br-specific screening algorithms, and further performed comprehensive characterization of components and distribution of HOPs. In total, 122 HOP formulas were identified and tentatively assigned with structures, of which 28 were found in ≥ two matrices. Taking isomers into account, in total 1059 HOP congeners were found. Based on the identification and semiquantification results, the chemical components and concentration profiles of HOPs were preliminarily clarified, and accordingly the overall pollution signatures of HOPs were sketched. The total concentrations of HOPs in the fly ash, egg and sediment were 4.7, 41.2 and 750.8 µg g-1, respectively. Organochlorines were the most abundant among the categories classified by halogen types, and halogenated benzenes, halogenated dioxins, halogenated biphenyls/terphenyls and halogenated polycyclic aromatic hydrocarbons (H-PAHs) were the predominant of the structurally classified categories. Moreover, dozens of formulas of novel/little-known HOPs such as mix-chlorinated/brominated PAHs with ≥4 aromatic rings and polychlorinated terphenyls were identified. This study presents an accurate and high-performance nontarget analysis method for HOPs in complex matrices, and yields new cognitions on the pollution status of HOPs from an overall perspective.

High-performance nontarget analysis of halogenated organic compounds in tap water, fly ash, soil and sediment using ultrahigh resolution mass spectrometry and scripting approaches based on Cl/Br-specific search algorithms.

Halogenated organic compounds (HOCs) are a huge group of pollutants, which have caused severe environmental pollution worldwide. This study developed a nontarget analysis method for characterization of known and unknown HOCs in tap water, fly ash, soil and sediment using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with aid of scripting data-processing approaches. The FT-ICR-MS was equipped with an electrospray ionization source operated in negative ion mode, and full scan at a mass resolution around 200,000 was applied. Data screening scripts were developed based on exact mass differences and abundance ratios between neighboring chlorine/bromine isotopologues. Cosine similarity analysis was applied to evaluating similarity between measured and simulated isotopologue distributions which were constituted by abundance ratios between neighboring isotopologues for identification of polychlorinated and polybrominated compounds. From huge amount of peaks in raw mass spectra, thousands of MS features of HOCs were screened out. In total 824 HOC formulae were finally identified, including 702 organochlorines, 108 organobromines, and 14 mix-chlorine/bromine-containing organic compounds (OClBrs), mainly being monochlorinated/monobrominated compounds (∼90%) whose abundances were also the most prominent. Dozens of HOCs were tentatively structurally elucidated, including halogenated phenols, carboxylic acids, benzenesulfonic acids, etc. Three novel OClBrs were structurally identified, i.e., bromochlorobenzoic acid, bromodichlorophenol and bromotrichlorophenol. The data-processing scripts and strategies can facilitate accurate and high-throughput nontarget analysis of both common and novel/emerging halogenated organic pollutants in complex matrices. The research results provide informative insights into pollution profiles of HOCs in the environment, suggesting that halogenated organic pollutants remain to be seriously concerned.

Lifetime bioaccumulation, gender difference, tissue distribution, and parental transfer of organophosphorus plastic additives in freshwater fish.

Plastic pollution has been a growing global issue. Various plastic additives may enter the environment with plastic debris, which could also become contaminants. Lifetime bioaccumulation, gender difference, tissue distribution, and parental transfer potential of commonly applied organophosphorus plastic additives (OPPAs) were investigated in wildlife fish of the Pearl River system, China. The OPPAs were widely detected in 7 consumable fish species. Tris (2-chloropropyl) phosphate was the predominant compound, with a median concentration of 18.8 ng/g lipid weight. The total OPPA concentrations (ΣOPPAs) were higher in the livers and swimming bladders, suggesting important roles of lipophilicity on the OPPAs accumulation in the fish. Besides, the livers were more abundant in the non-chlorinated OPPAs relative to the other tissues, indicating potentially stronger metabolism of the chlorinated OPPAs in the livers. Redbelly tilapia contained obviously lower ΣOPPAs than the other species. On the other hand, proportions of the chlorinated OPPAs were obviously lower in barbel chub and Guangdong black bream. For an individual species, higher ΣOPPAs were usually detected in the female than in the male fish. Furthermore, the females contained higher proportions of the non-chlorinated OPPAs. These results suggested potentially more accumulation of the OPPAs, particularly the non-chlorinated OPPAs in the female than in the male fish. Body weight dependence of the OPPAs accumulation showed varied patterns depending on species, tissue, and compound. Species-specific characteristics affected by both ecology and organisms' physiology should be considered in combination in assessing bioaccumulation of the OPPAs. The OPPAs were slightly bioaccumulative with LogBAFs of 1.2-3.3. The OPPAs did not show obvious inclination to be partitioned to biota from sediment. Omnipresence of the OPPAs in both egg/ovary and testis of the fish suggested potential transgenerational transfer of these chemicals, which can be a serious ecological issue and warrants further research.

Tissue Distribution, Growth Dilution, and Species-Specific Bioaccumulation of Organic Ultraviolet Absorbents in Wildlife Freshwater Fish in the Pearl River Catchment, China.

Tissue distributions and body-size dependent and species-specific bioaccumulation of 12 organic ultraviolet absorbents (UVAs) were investigated in 9 species of wildlife freshwater fish from the Pearl River catchment, South China. The concentrations of the 12 UVAs were from 109 to 2320 ng/g lipid weight in the fish tissue samples. The UVAs 2-hydroxy-4-methoxybenzophenone (BP-3), octocrylene (OCR), UV531, and 5 benzotriazole UV stabilizers (UVP, UV329, UV234, UV328, and UV327) were detected in more than half of the fish tissue samples. The UVA UV531 showed an obvious potential for bioaccumulation in the wild freshwater fish, with an estimated bioaccumulation factor (log BAF) and a biota-sediment accumulation factor (BSAF) of 4.54 ± 0.55 and 4.88 ± 6.78, respectively. Generally, liver (989 ± 464 ng/g lipid wt) contained the highest level of UVAs, followed in decreasing order by belly fat (599 ± 318 ng/g lipid wt), swimming bladder (494 ± 282 ng/g lipid wt), dorsal muscle (470 ± 240 ng/g lipid wt), and egg (442 ± 238 ng/g lipid wt). The bioaccumulation of UVAs in the freshwater wild fish was species specific and compound dependent. Bottom-dwelling detritus-ingesting omnivorous fish contained obviously higher UVA concentrations, suggesting that detritus/sediment ingestion is a significant pathway for exposure of the wild freshwater fish to the UVAs. The UVAs UV531 and BP-3 demonstrated a potential for growth dilution. Metabolism might play a significant role in elimination of the UVAs in the fish tissues, with the highest rate of metabolism in the liver. The UVAs did not demonstrate obvious trophic magnification in the freshwater ecosystem of the Pearl River catchment. More research is warranted to elucidate maternal transfer of the UVAs. Environ Toxicol Chem 2020;39:343-351. © 2019 SETAC.

Distribution, sedimentary record, and persistence of microplastics in the Pearl River catchment, China.

Microplastics (MPs) in the environment have become an issue worldwide. However, data about MPs in freshwater systems are still limited so far. This study investigated sources, fate, and seasonal and spatial distribution of MPs in the main stream Pearl River and its tributaries, as well as in the Pearl River Estuary (PRE), China. MPs were widely detected in the river water, river bed sediment, and estuarine sediment, with abundances of 0.57 ±â€¯0.71 items L-1, 685 ±â€¯342 items kg-1 dry weight (dw), and 258 ±â€¯133 items kg-1 dw, respectively. Sheet, fragmental, and fibrous polyethylene, polypropylene, and ethylene-propylene copolymers were predominant, suggesting that MPs in the Pearl River catchment be mainly derived from fragmentation of discarded plastic wastes. In addition, municipal wastewater was also an important MPs source, especially for polyethylene terephthalate (PET) fibers. Polymers of higher density, such as PET and polyvinyl alcohol were relatively more abundant in the sediment than in the river water, especially in the estuarine sediment. Upward increase of the MP abundance was observed in the sedimentary core, probably indicating increasing release of plastic wastes due to growing production and uses of plastic products. On the other hand, percentage of finer MPs increased with increasing depth. The results revealed persistence and potential downward dispersion of the fine MPs. The MPs abundance was positively related with population density and gross domestic product, demonstrating impacts of human activities and economic development on the MPs contamination. Higher MPs abundance was detected in dry season than in wet season in the river water, suggesting dilution effect of precipitation. It's estimated that 15963 tons of MPs could be released annually into the PRE from the main stream Pearl River and its tributaries.

Occurrence and Species-Specific Distribution of Plastic Debris in Wild Freshwater Fish from the Pearl River Catchment, China.

Freshwater systems are an important source and vector of plastic debris found in oceans. However, plastic debris in freshwater organisms has not been well studied. The occurrence, characterization, polymer composition, and seasonal and spatial distribution of plastic debris were investigated in 9 species of wild freshwater fish from the Pearl River catchment, south China. Approximately 50% of the total fish (n = 279) belonging to 9 species were found to ingest plastic debris with an average abundance of 7.0 ± 23.8 items/individual, indicating wide plastic contamination in the Pearl River catchment. Plastic debris were predominantly transparent or white in color, fibers or fragments in shape, and polyethylene, polypropylene, ethylene-propylene copolymer (PE-PP), and polyethylene terephthalate (PET) in polymer composition. A species-specific distribution of the plastic debris was observed in terms of abundance, shape, and polymer composition. Redbelly tilapia had the highest (27.4 ± 54.0 items/individual), whereas common carp had the lowest (0.2 ± 0.4 items/individual) abundance of the plastic debris in their gastrointestinal tracts. Fibers of PET were predominant in the freshwater species except in barbel chubs, which had mostly PE-PP fragments. Omnivores and bottom-dwellers were more likely to ingest plastic debris. Seasonal variation was observed, with generally higher abundance of plastic debris in fish collected in the dry season than in the wet season. Environ Toxicol Chem 2019;38:1504-1513. © 2019 SETAC.

Anaerobic Ammonium Oxidation in Acidic Red Soils.

Anaerobic ammonium oxidation (anammox) has been proven to be an important nitrogen removal process in terrestrial ecosystems, particularly paddy soils. However, the contribution of anammox in acidic red soils to nitrogen loss has not been well-documented to date. Here, we investigated the activity, abundance, and distribution of anammox bacteria in red soils collected from nine provinces of Southern China. High-throughput sequencing analysis showed that Candidatus Brocadia dominates the anammox bacterial community (93.03% of sequence reads). Quantification of the hydrazine synthase gene (hzsB) and anammox 16S rRNA gene indicated that the abundance of anammox bacteria ranged from 6.20 × 106 to 1.81 × 109 and 4.81 × 106 to 4.54 × 108 copies per gram of dry weight, respectively. Contributions to nitrogen removal by anammox were measured by a 15N isotope-pairing assay. Anammox rates in red soil ranged from 0.01 to 0.59 nmol N g-1 h-1, contributing 16.67-53.27% to N2 production in the studied area, and the total amount of removed nitrogen by anammox was estimated at 2.33 Tg N per year in the natural red soils of southern China. Pearson correlation analyses revealed that the distribution of anammox bacteria significantly correlated with the concentration of nitrate and pH, whereas the abundance and activity of anammox bacteria were significantly influenced by the nitrate and total nitrogen concentrations. Our findings demonstrate that Candidatus Brocadia dominates anammox bacterial communities in acidic red soils and plays an important role in nitrogen loss of the red soil in Southern China.