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Microplastics (MPs) pollution has emerged as a global concern. To mitigate the potential threats by MPs, particularly to coastal regions, it is crucial to comprehend the environmental behavior of MPs and their affiliated chemicals. In the present study, we collected floating MPs using a Manta net (0.33 mm mesh size) in a one-year sampling event in 2022 from the eight major estuaries in the Pearl River Delta, China, and also from five coastal sites in August and December in the same year. Nineteen linear alkylbenzenes (∑ 19 LAB) and 16 polycyclic aromatic hydrocarbons (∑ 16 PAH) affiliated with MPs were measured. The mean concentrations of MPs-affiliated ∑ 19 LAB and ∑ 16 PAH were 6710 (range: 3400-12300) and 5310 (range: 817-19,600) ng g -1 , respectively, at the estuarine sites, and were 4920 (range: 2400-7600) and 2610 (range: 911-7890) ng g -1 , respectively, at the coastal sites. Significant correlations were found between logarithmic MPs-water partition coefficients (log K pw ) and logarithmic suspended particulate matter-water partition coefficients (log K d ) values for LABs and PAHs, indicating analogous partitioning dynamics for MPs and suspended particulate matter with water. The annual riverine outflows were 1170 and 414 g for ∑ 19 LAB and ∑ 16 PAH, respectively. Although the riverine outflows of LABs and PAHs carried by MPs remain negligible compared to those by suspended particulate matter, an upward trend was identified between 2018 and 2022. Notably, the riverine input of LABs and PAHs carried by suspended particulate matter to the coastal ocean decreased from 2005/2006 to 2022, due to a combination of improved technological processes and energy structures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Nanoplastics are ubiquitous in marine environments, exhibiting high bioavailability and potential toxicity to marine organisms. However, the impacts of nanoplastics with various surface modifications on marine microalgae remain largely unexplored. This study explored the toxicity mechanisms of two nanoplastic types-polystyrene (PS) and polymethyl methacrylate (PMMA)-with distinct surface modifications on Skeletonema costatum at cellular and molecular levels. Results showed that nanoplastics significantly impaired the growth of microalgae, particularly PS-NH 2 , which caused the most pronounced growth inhibition, reaching 56.99 % after a 96-h exposure at 50 mg/L. Transcriptomic profiling revealed that nanoplastics disrupted the expression of genes predominantly involved in ribosome biogenesis, aminoacyl-tRNA biosynthesis, amino acid metabolism, and carbohydrate metabolism pathways. The integrated biochemical and transcriptomic evidence highlighted that PS-NH 2 nanoplastics had the most adverse impact on microalgae, affecting fundamental pathways such as ribosome biogenesis, energy metabolism, photosynthesis, and oxidative stress. Our findings underscore the influence of surface-modified nanoplastics on algal growth and contribute new understanding to the toxicity mechanisms of these nanoplastics in marine microalgae, offering critical information for assessing the risks of emerging pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Due to the combined influences of marine and terrestrial disturbances, the sources of microplastics (MPs) in mangrove ecosystems are complex and diverse. Previous studies have inferred the possible involvement of mariculture activities as a potential source of mangrove MPs based on the characteristics of MPs. However, the direct contributions of mariculture-derived MPs to mangrove MPs remain largely unknown. In this study, we systematically investigated the fate of MPs in the discharge of mariculture wastewater by quantifying the source contributions of mariculture-derived MPs to rivers and mangroves. The majority of detected MPs were transparent fibers, with their composition primarily comprising materials commonly used in mariculture activities such as polyvinylpyrrolidone (PVP), polyethylene terephthalate (PET), and nylon. The partial least squares path model elucidated the relationships among the composition of MPs in ponds, rivers, and mangroves, indicating that ponds exert a substantial direct effect on mangroves, particularly significant in the sediments (63.68%). Water turbidity, sediment carbon content, and sediment particle size are key ecological factors influencing the abundance of mariculture-derived MPs. This study provides compelling evidence regarding the sources of mangrove MPs and novel insights into mitigating the dissemination of MPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Microplastics (MPs) and nanoplastics (NPs) are ubiquitous in the aquatic environment and have caused widespread concerns globally due to their potential hazards to humans. Especially, NPs have smaller sizes and higher penetrability, and therefore can penetrate the human barrier more easily and may pose potentially higher risks than MPs. Currently, most reviews have overlooked the differences between MPs and NPs and conflated them in the discussions. This review compared the differences in physicochemical properties and environmental behaviors of MPs and NPs. Commonly used techniques for removing MPs and NPs currently employed by wastewater treatment plants and drinking water treatment plants were summarized, and their weaknesses were analyzed. We further comprehensively reviewed the latest technological advances (e.g., emerging coagulants, new filters, novel membrane materials, photocatalysis, Fenton, ozone, and persulfate oxidation) for the separation and degradation of MPs and NPs. Microplastics are more easily removed than NPs through separation processes, while NPs are more easily degraded than MPs through advanced oxidation processes. The operational parameters, efficiency, and potential governing mechanisms of various technologies as well as their advantages and disadvantages were also analyzed in detail. Appropriate technology should be selected based on environmental conditions and plastic size and type. Finally, current challenges and prospects in the detection, toxicity assessment, and removal of MPs and NPs were proposed. This review intends to clarify the differences between MPs and NPs and provide guidance for removing MPs and NPs from urban water systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Commercial chemicals, such as synthetic musks, are of global concern, but data on their occurrence and spatial distribution in aquatic environments of large scale are scarce. Two sampling campaigns were conducted in the present study to measure freely dissolved synthetic musks in freshwaters across China using passive samplers, along with biological coexposure at selected sites. Polycyclic musks (PCMs) dominated synthetic musks, with a detection frequency of 95%. Higher concentrations of PCMs were observed in densely populated Mid, East, and South China compared to less populated regions, indicating the significance of anthropogenic activities for synthetic musks in water. The concentration ratios of galaxolide (HHCB)/tonalide (AHTN) were significantly higher in low-latitude areas than in high-latitude areas from June to September, suggesting that solar radiation played an important role in the degradation of HHCB/AHTN. Significant correlations were found between dissolved concentrations of HHCB and AHTN and their lipid-normalized concentrations in coexposed fish and clam. The estimated hazard quotients for HHCB and AHTN in freshwater fish consumed by humans were less than 0.01 at all sampling sites except the Yangtze River Basin. These results help to understand the environmental fate and ecological risks of synthetic musks on a large geographical scale.

Rivers are recognized as an important pathway for transport of microplastics (MPs) from land to sea, but limited information is available on the spatial distribution and seasonal variation of riverine MPs from upper reaches to estuaries. Such information is critical for source apportionment and development of effective management measures for riverine MPs. To fill the knowledge gap, we investigated the occurrence of MPs in surface water along an urban river in Guangzhou, southern China in wet and dry seasons. The abundances of MPs from 16 sampling sites in the wet and dry seasons varied from 0.123 to 1.84 particles m -3 and from 0.046 to 4.21 particles m -3 , respectively. The spatial distribution of MP abundances showed an increasing trend from upstream to midstream and a decreasing trend from midstream to downstream and estuaries. The abundances of MPs peaked at the midstream, which is surrounded by a highly urbanized region with high population density (∼2530 persons per km 2 ). The large surface water runoff during the wet season elevated the MP abundance in riverine water, except for that flowing through the central urban area where the abundance of MPs collected in the dry season was higher than that in the wet season. This was mainly ascribed to the large input from extensive anthropogenic activities and slow water flow rate in urban areas. The estimated monthly riverine MP fluxes from Humen, Hongqili, and Jiaomen were 7.42, 2.38, and 2.3 billion particles, respectively, in the wet season, and 0.86, 0.71, and 0.19 billion particles, respectively, in the dry season. An increase of riverine MP fluxes from Humen, Hongqili, and Jiaomen in the past three years was evident. The results from the present study provide valuable information for source apportionment of riverine MPs and support the initialization of possible MPs controlling measures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

There is growing contamination of copper (Cu) in the marine environment, particularly after the ban of organotin compounds and the increase of the use of Cu-based antifouling paints. Although there are increasing research interests in temperature-dependent chemical toxicity to aquatic organisms, most existing studies focused on acute impacts of chemicals at high concentrations. This study aimed to investigate the interacting effect of temperature and copper exposure at environmentally relevant concentrations on survival and development in the marine copepod Tigriopus japonicus with a partial life-cycle toxicity test. Expressions of five stress response genes in the copepod, namely two glutathione S-transferases (GST-S and GST-O), two heat shock proteins (HSP70 and HSP90), and glutathione reductase (GR) were also investigated. The copepod's survival was significantly impaired at 15 °C after development to adult stage, while its developmental time reduced significantly with increasing temperature. Copper at the two environmentally relevant test concentrations had no significant impacts on these apical endpoints whereas the interaction between Cu and temperature was more significant in modulating gene expressions. GST-S, GST-O and HSP90 genes in copepods exposed to 100 µg Cu L -1 were significantly upregulated at 20 °C. At 32 °C, most genes were either insignificantly expressed or down-regulated, compared to the control, likely suggesting that thermal stress inhibited the copepod's antioxidative defense system. Overall, the results revealed that the joint Cu and thermal stresses have significantly elicited antioxidative system in the copepods. It clearly demonstrated the need for more fundamental studies about potential impacts of different environmental factors such as temperature on chemical toxicity under realistic scenario of marine pollution., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Activation of H 2 O 2 with metal-free catalysts is an efficient and environmentally benign alternative to electron-Fenton (EF) for organics degradation. In the present study, flexible nanocatalysts were synthesized with self-regulated metal oxide nanoparticles (FeOx NPs) for efficient removal of plasticizers from secondary wastewater effluent (SWE). Compared with NGr/EF and FeOx@Gr/EF systems, FeOx@NGr/EF could enhance the decay kinetics of plasticizers by 3.9-4.4 times and reduce 48-59% of the disposal cost. Reactive oxygen species tests and trapping experiments proved that the surface-catalyzed EF effectively broadened the range of solution pH. Density functional theory calculations coupled with electrochemical measurements indicated that the electron transfer rates between Fe-O-C atoms were enhanced with N-doping due to strong interactions between N-Fe bond. The synergistic effects of FeOx and N could improve the oxygen reduction activity for H 2 O 2 generation, and accelerate electron transfer between FeOx/NGr and H 2 O 2 for • OH generation, offering an alternative for wastewater treatment., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Marine ecosystems are currently subjected to dual stresses of chemical pollution and climate change. Through a series of laboratory experiments, this study investigated the impact of exposure to chemical contaminant such as DDT or copper (Cu), in combination with cold or warm temperature extremes on the marine medaka fish Oryzias melastigma. The results showed that extreme seawater temperatures (i.e., 15 and 32 °C in sub-tropical Hong Kong) exacerbated adverse chemical impacts on the growth performance of O. melastigma, in particular at the high thermal extreme. This was likely associated with an interruption of oxygen consumption and aerobic scope. Most importantly, the results of acclimation experiments, as reflected by thermal tolerance polygons, showed that chemical exposure substantially narrowed the thermal tolerance of the medaka, making them more vulnerable to temperature changes and extreme thermal events. Under dual stresses of thermal extremes and chemical exposure, the medaka switched their metabolic pathway to anaerobic respiration that might deplete their energy reserve for chemical detoxification. Although stress proteins such as heat shock proteins (HSP90) were up-regulated for cellular protection in the fish, such a defensive mechanism was repressed with intensifying dual stresses at high temperature and high chemical concentration. Bioconcentration of DDT or Cu generally increased with increasing temperature and its exposure concentration. Overall, these complex chemical-temperature interactions concomitantly exerted a concerted adverse impact to O. melastigma. The temperature-dependent toxicity of DDT or Cu shown in this study clearly demonstrated the potential challenge brought by the risk of chemical pollution under the impact of global climate change., (Copyright © 2022. Published by Elsevier B.V.)

Human brain has a complex structure and is able to perform powerful functions. Blood-brain barrier blocks the entry of foreign substances and maintains the homeostasis of the brain. However, some exogenous substances are still able to pass through the blood-brain barrier, with distribution patterns yet to be clarified. Perfluoroalkyl and polyfluoroalkyl substances (PFASs), including perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonic acids (PFSAs), a precursor (perfluorooctane sulfonamide that can be degraded to other substances), and emerging PFASs, were analyzed for the first time in living human brain glioma. The target compounds were detected and quantified in 25 out of 26 glioma samples. The concentration range of ∑PFAS was < RL-51 ng g -1 wet weight (applied to all reported concentrations), with a median of 2.9 ng g -1 . The most abundant compound was PFCAs (40%), followed by PFSAs (28%), emerging PFASs (22%), and perfluorooctane sulfonamide (10%). Abundant alternatives PFASs, including short-chain PFCAs, short-chain PFSAs, and emerging PFASs (52% of ∑PFAS), were found in the glioma samples, supporting the notion that low molecular weight exogenous compounds have high permeability to cross the blood-brain barrier and accumulate in brain tissue. Gender difference was not significant (p > 0.05) in the concentrations of PFASs in the glioma samples. Concentrations of PFASs increased with increasing age, from 0.61 ng g -1 (0-14 years old) to 1.6 ng g -1 (>48 years old), with no significant linear correlation with age. The present study suggested that glioma is an effective indicator for monitoring exogenous contaminants in brain tissues., (Copyright © 2021 Elsevier Inc. All rights reserved.)

While organic-diffusive gradients in thin films (o-DGT) passive samplers have been used to assess organic contaminants in water, the effects of biofouling on accurate analyte quantification by o-DGT are poorly understood. We evaluated the effects of biofouling on the uptake of six common perfluoroalkyl substances (PFAS) using a previously developed polyacrylamide-WAX (weak anion exchange) o-DGT without a filter membrane. Linear uptake ( R 2 > 0.91) over 21 days was observed in fouled samplers. The measured sampling rates ( R s ) and accumulated masses of PFAS in pre-fouled o-DGT were significantly lower ( p < 0.05, 20-39% relative error) than in control-fouled samplers. However, compared to clean o-DGT (no biofouling), the R s of most PFAS in control-fouled samplers ( i.e. , those with clean diffusive and binding gels initially) were not affected by biofouling. Under flowing (∼5.8 cm s -1 ) and static conditions, the measured diffusive boundary layer (DBL) thicknesses for clean o-DGT were 0.016 and 0.082 cm, respectively, whereas the effective in situ biofilm thicknesses for fouled o-DGT were 0.018 and 0.14 cm, respectively. These results suggest that biofilm growth does not have significant effects on target PFAS sampling by o-DGT under typical flowing conditions (≥2 cm s -1 ). However, rapid surface growth of biofilm on o-DGT deployed in quiescent waters over long periods of time may exacerbate the adverse effects of biofilms, necessitating the estimation of biofilm thickness in situ . This study provides new insights for evaluating the capability of o-DGT samplers when biofilm growth can be significant.

Microplastics (MPs) are ubiquitous in various environment compartments, including food. Here, we collected research reports of MPs in food published during 2010-2020, and summarized the analytical methods developed and utilized by researchers (e.g., digestion, separation and identification, as well as related QA/QC measures implemented), the occurrence, and the characteristics of MPs in six kinds of food. The potential effects on biota from exposure to MPs were also reviewed. The results showed that most researchers digested food samples using chemical solutions such as HNO 3 , H 2 O 2 , KOH, or NaOH. FT-IR and Raman spectroscopy were the main technique for identifying MPs, and microscopes were used to count MP particles. The abundances MPs were in the ranges of 0-5860, 2.00-1100, 0-698, 4.00-18.7, 0-5.68 × 10 4 and 900-3000 particles/kg in beverages, condiments, honey, meat, seafood and vegetables, respectively. The "maximum" annual human intake of MPs from these foods is approximately 1.42 × 10 5 -1.54 × 10 5 particles/capita, equivalent to the consumption of 50 plastic bags (size: 0.04 mm × 250 mm × 400 mm, density: 0.98 g/cm 3 ) each year. Blue-colored and fiber-shaped MP particles were the most commonly observed in food, predominated by PA, PE, PES, PET and PP types. Toxicity studies indicated that MPs, additives of MPs and adsorbents or microorganisms on the surfaces of MPs were all somewhat toxic to cells or biota. Exposure to MPs may induce oxidative stress, inflammation, neurotoxicity, and reproductive toxicity, and change the structure of intestinal microflora in cells or biota. Therefore, we call for more investigation into the residual, excretion and bioavailability of MPs or related absorbents/additives in biota and humans., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Tire-derived particles and polyethylene (PE) debris co-exist in estuaries and potentially deteriorate water quality. Chemicals can be emitted from tire-derived particles and resorb to PE debris. However, there was lack of information about the interaction (e.g., sorption and desorption) between tire-derived chemicals and PE debris. By combining batch sorption and desorption experiments along with in situ field deployment of PE sheets, we examined the utility of benzothiazoles (BTZs) sorbed in PE as suitable markers of tire-derived inputs. The sorptive characteristics and PE-water partition coefficients (often designated as K pew ) of selected tire-derived marker candidates, i.e., polycyclic aromatic hydrocarbons (PAHs), benzothiophenes (BTPs) and BTZs, were measured. Moderately polar BTPs and BTZs (except for 2-(4-morpholinyl) benzothiazole) reached equilibrium within 2-8 days, compared to 20 days for nonpolar PAHs. The measure K pew values and octanol-water partition coefficients of PAHs and BTZs were linearly correlated with each other (r 2  > 0.80; p < 0.05). The desorption potentiality of PAHs and BTZs from tire particles is consistent with the hydrophilic properties of the target chemicals, while desorption ratios of BTZs and PAHs are 25-87% and <20%, respectively. Samplers with PE sheets as the sorbent phase were deployed in Hailing Bay, an urbanized estuary in South China, to measure concentrations of PAHs, BTPs and BTZs. Benzothiazoles sorbed in PE samples were associated with the massive utilization of automobile tires, while PAHs were linked to the boat maintenance facilities and BTPs were not detected in any tire particle and field PE samples. Therefore sorbed BTZs in PE can potentially serve as chemical markers of tire-derived inputs to estuaries., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The presence of microcystins (MCs) in waterbodies requires a simple and reliable monitoring technique to characterize better their spatiotemporal distribution and ecological risks. An organic-diffusive gradients in thin films (o-DGT) passive sampler based on polyacrylamide diffusive gel and hydrophilic-lipophilic balance (HLB) binding gel was developed for MCs in water. The mass accumulation of three MCs (MC-LR, -RR, and -YR) was linear over 10 days (R 2  ≥ 0.98). Sampling rates (2.68-3.22 mL d -1 ) and diffusion coefficients (0.90-1.08 × 10 -6  cm 2  s -1 ) of three MCs were obtained at 20 °C. Two different passive samplers, o-DGT and the Solid Phase Adsorption Toxin Tracking device (SPATT), were co-deployed to estimate MC levels at three lakes in California, USA. Measured total MC concentrations were up to 10.9 μg L -1 , with MC-LR the primary variant at a measured maximum concentration of 2.74 μg L -1 . Time-weighted average MC concentrations by o-DGT were lower than grab water samples, probably because grab sampling measures both dissolved and particulate phases (i.e., MCs in cyanobacteria). Passive water samplers by design can only measure dissolved-phase MCs, which are considerably less during the cyanobacteria-laden periods observed. Both o-DGT and grab samples gave comparable results for three MC variants at low levels of MCs, e.g., <0.1 μg L -1 . o-DGT showed a higher correlation with grab sampling than SPATT did. This study demonstrates that o-DGT can be effectively used for monitoring and evaluation of dissolved MCs in waters., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Considerable efforts on exposure assessment of microplastics (MPs) as an agent in transport of toxic contaminants have been performed in organisms. However, chemical diffusion of inherent hydrophobic organic contaminants from MPs under simulated gut conditions is poorly examined. The present study examined the transfer kinetics of polybrominated diphenyl ethers (PBDEs) from polystyrene (PS), acrylonitrile butadiene styrene (ABS), and polypropylene (PP) MPs under gut surfactants (sodium taurocholate) at two relevant body temperatures of marine organisms, and evaluated the importance of MP ingestion in bioaccumulation of PBDEs in lugworm by a biodynamic model. Diffusion coefficients of PBDEs range from 5.82 × 10 -23 to 7.96 × 10 -20  m 2  s -1 in PS, 5.49 × 10 -23 to 3.45 × 10 -20  m 2  s -1 in ABS, and 5.58 × 10 -21 to 5.79 × 10 -17  m 2  s -1 in PP, with apparent activation energies in the range of 33-148 kJ mol -1 . The biota-plastic accumulation factors of PBDEs leached from these plastics range from 1.44 × 10 -8 to 7.15 × 10 -5 . Although ingestion of MPs with the common size (>0.5 mm) showed the negligible contribution to bioaccumulation of PBDEs in lugworm, their contribution in PBDEs transfer can be increased with gradual breakdown of MPs., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Accumulation of microplastics (MPs) data on a global scale is key to supporting plastic waste management for protecting ecosystems. To respond this call, a sampling campaign was conducted in the summer and winter seasons of 2018 to collect beach and mangrove sediment samples from 32 sites along the coastline of South China. The MPs concentrations in the intertidal zone along the coast of South China were comparable to those in other regions around the world. Polystyrene foams and fibers were the most abundant debris in the 0.2-5 mm and 0.02-2 mm MPs, respectively. Principal component and correlation analyses indicated that the abundances of MPs were related to wind direction, wastewater discharge amount, and tourist and fishing activities. Risk assessments suggested that potential ecological risks induced by MPs on beaches and mangrove forest along the coast of South China should not be overlooked., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Low yields of H 2 O 2 and a narrow range of appropriate pH values have been two major drawbacks for electro-Fenton (EF) process. Herein, metal-free electrochemical advanced oxidation processes (EAOPs) were developed with nitrogen and sulfur co-doped electrochemically exfoliated graphene (N, S-EEGr) electrocatalysts, which was confirmed as an outstanding bifunctional catalyst for synchronous generation and activation of H 2 O 2 via (2 + 1) e - consecutive reduction reactions. Specifically, two elements (N, S) in metal-free N, S-EEGr-CF cathode synergize to promote the formation of H 2 O 2 followed by its activation. With N, S-EEGr-CF cathode, phenol of initial 50 mg L -1 could be effectively removed within pH 3-11 and 6.25 mA cm -2 , and 100% removal efficiency could be achieved within 15-min even at neutral pH. The pseudo-first-order rate constant for phenol removal in metal-free EAOPs with N,S-EEGr-CF at neutral pH was 10 times higher than that with EF process. Detection of active species, coupled with decay kinetics with specific trapping agents, confirmed that OH was the dominant oxidizing species promoting removal efficiencies of organics (phenol, antibiotics and dyes) at pH 3 and pH 7. In the actual wastewater treatment, the synergistic effect of bifunctional catalyst would also be used for improving the degradation efficiency of organics. Thus, the metal-free EAOPs with N,S-EEGr-CF cathode may serve as an alternative in wastewater treatment with a broadened range of solution pH values and avoiding Fe 2+ (catalyst) addition., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Micro- and nanoplastics (MNPs) are ubiquitous in aquatic and terrestrial environments, and detrimental biological effects have been observed on a variety of organisms, from bacteria and alga to plants and animals. A fast-growing number of toxicological studies report diverse responses and wide species-dependent sensitivity upon MNP exposure. While studies are dominated by in vivo animal tests, our understanding of cellular toxicity and the corresponding toxicity mechanisms is still limited. This challenges the proper assessment of environmental hazards and health risks of MNPs. In this review, we gathered and analyzed the up-to-date studies on humans, animals, plants, alga, and bacteria, and identified the similarities and differences in key toxicity mechanisms of MNPs across different taxonomic groups. Particularly, human cell-based studies at the cellular level provide fundamental and valuable information on the key toxicity mechanisms, which are essential to answer the question of whether and how MNPs pose health threats. In general, toxicity mechanisms of MNPs depend on their size, surface characteristics, polymer type, as well as cell type. Plausible toxicity mechanisms mainly include membrane disruption, extracellular polymeric substance disruption, reactive oxygen species generation, DNA damage, cell pore blockage, lysosome destabilization, and mitochondrial depolarization. A deeper understanding of these key mechanisms in different taxonomic groups can also improve both in vivo and in vitro models useful for predictive impact assessments of plastic pollution on the environment and human health., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The partition coefficient (K pew ) of an analyte between low-density polyethylene (LDPE) film and water is a critical parameter for measuring freely dissolved concentrations of the analyte with PE passive sampling devices. Measuring log K pew for super hydrophobic organic chemicals (HOCs) have been proven extremely difficult. The present study developed a large volume model for measuring log K pew of super HOCs, i.e., novel halogenated flame retardants (NHFRs). Results showed that the measured log K pew values of selected PAHs and PCBs obtained by the large volume model were in line with those from the co-solvent model and the literature data within less 0.3 log units of difference, while those of NHFRs (6.27-7.34) except for hexachlorocyclopentadienyldibromocyclooctane (HCDBCO) and Decabromodiphenyl ethane (DBDPE) were significantly lower than those (6.51-8.89) from the co-solvent model. A curvilinear relationship was observed between log K pew and log K ow of all target compounds, with the turning point at log K ow  = ∼8.0 in the large volume model, but that was not found for the co-solvent model. These can be attributed to the large molecular volumes (> 450 Å 3 ) for NHFRs, which require high Gibbs free energy to penetrate into the inside structures of LDPE in the large volume model. However, the solvent swelling effects in the co-solvent model needs to be investigated. Therefore, the large volume model is robust to determine the K pew values of super HOCs for facilitating the application of aquatic passive sampling techniques., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Riverine runoff is a significant transport pathway for microplastics (MPs) discharged from land-based sources to marine environments where MPs accumulate. Knowledge of riverine MP-associated biofilms will improve the understanding of the fate and potential effects of MPs in marine environments. This study aimed to characterize the microbial biofilms colonizing MPs in the riverine water of the Pearl River Delta, China, and identify the seasonal, geographical and environmental influences on MP-associated communities. We sampled MPs and the surrounding surface water from eight outlets in three seasons and analyzed their microbial communities by Illumina sequencing of the 16S rRNA gene libraries. Across all sampling seasons and locations, abundant MP-colonizing taxa belonged to the phylum Proteobacteria, which suggested initial biofilm development on those MPs. The structure and composition of MP-attached microbial communities varied with respect to season and location, and the microbial diversity of the MP-associated biofilm communities decreased in June compared with that in the April and November sampling events. Opportunistic pathogens of the genus Acinetobacter were significantly enriched on the MP surfaces for all sampling events. Among the 15 environmental variables examined, the main drivers of MP-associated biofilm community composition included IC, alkalinity, TOC, TDS, Cl - , NO 3 - , NO 2 - and pH. This study provides an insight into the environmental factors that shape microbial biofilm colonization on MPs in estuary environments and a further understanding of the structure, diversity and ecological roles of MP-associated communities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Microplastics (MPs) contain high levels of polybrominated diphenyl ethers (PBDEs), which can leach to organism tissues upon ingestion, thereby leading to increased chemical exposure. However, leaching kinetics of inherent contaminants from ingested MPs are poorly studied. The present study characterized the leaching kinetics of PBDEs from sub-millimeter sized MPs in fish oil at relevant body temperatures for marine organisms and assessed exposure risk of MPs for cod fish by a biodynamic model. Diffusion coefficients (D p ) of PBDEs are in the ranges of 1.98 × 10 -19 -2.35 × 10 -16 m 2 ·s -1 in polystyrene, 1.89 × 10 -20 -2.07 × 10 -18 m 2 ·s -1 in acrylonitrile butadiene styrene, and 4.26 × 10 -18 -1.72 × 10 -15 m 2 ·s -1 in polypropylene. A linear function obtained between log D p of BDE-209 and glass-transition temperature of MPs allows estimation of D p of BDE-209 contained in other common types of MPs present in the gastrointestinal lipid. The biota-plastic accumulation factors of PBDEs for three plastics were in the range of 4.77 × 10 -14 -4.03 × 10 -7 . Although bioaccumulation of MPs-affiliated PBDEs is accelerated by oil in the gastrointestinal tract, the modeled steady-state concentrations of PBDEs in cod tissue lipid through ingestion of MPs under the most likely conditions were below the lower end of the global PBDE concentration, implicating that ingestion of MPs by organisms remains a negligible pathway in general., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Global rivers act as a dominant transport pathway for land-based plastic debris to the marine environment. Organic pollutants (OPs) affiliated with riverine plastics can also enter the global oceans, but their amounts remain unknown. Microplastic (MP) samples were collected in a one-year sampling event from the surface water of the eight main riverine outlets in the Pearl River Delta (PRD), China, and analyzed for OPs affiliated with MPs, including 16 polycyclic aromatic hydrocarbons (PAHs), eight polybrominated diphenyl ethers (PBDEs), and 14 polychlorinated biphenyls (PCBs). The mean concentrations of MP-affiliated ∑ 16 PAH, ∑ 8 PBDE, and ∑ 14 PCB were 2010 (range: 25-40,100), 412 (range: 0.84-14,800), and 67.7 (range: 1.86-456) ng g -1 , respectively. Based on these and previous results, the annual riverine outflows of MP-affiliated OPs were 148, 83, and 8.03 g for ∑ 16 PAH, ∑ 8 PBDE, and ∑ 14 PCB, respectively. Assuming that plastic debris of different sizes contained the same concentrations of the target pollutants as MPs, the mean riverine outflows of plastic-bound ∑ 16 PAH, ∑ 8 PBDE, and ∑ 14 PCB were 6.75, 3.77, and 0.37 kg year -1 , respectively, which were insignificant compared with the riverine outflows of OPs through riverine water discharge (up to hundred tons per year). Apparently, plastics are an insignificant carrier of riverine OPs to the coastal oceans.

Antibiotics and current-use pesticides are ubiquitous in the environment. It is important to figure out their spatial distribution under the influences of anthropogenic activities and transport from rivers to coastal oceans. To address this knowledge gap, the present study conducted quarterly sampling in eight main runoff outlets of the Pearl River, South China, and obtained total concentrations of antibiotics and current-use pesticides at 24-296 ng L -1 . Higher total concentrations of these chemicals occurred in summer, attributed to seasonal consumption patterns and washout by rainfalls, respectively. The spatial distributions of target analytes were not significantly different between the eastern and western outlets with high and moderate urbanization levels, respectively. Approximately 16.4, 17.7, and 12.5 tons of antibiotics, organophosphorus pesticides, and neonicotinoids were discharged annually from the outlets to the South China Sea. These results suggested that usage amount and hydrology exhibited positive effects on the riverine inputs of the target chemicals. In addition, most target chemicals exhibited low risks to green algae, but erythromycin and parathion posed high ecological risks to aquatic organism (Daphnid and fish)., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Microplastic (MP) pollution has become an area of increasing concern because MPs accumulate various types of pollutants. Many previous studies have explored the interactions between MPs and hydrophobic pollutants. However, little research has been conducted on hydrophilic pollutants, which are of much higher concentration and ubiquitous in environment. Surfactants cause hydrophobic MPs to become hydrophilic, which may significantly enhance their capacities to adsorb hydrophilic pollutants. This study explored the influence of co-existing surfactants on the adsorption of ionic organic pollutants by MPs, and found that the presence of an ionic surfactant could significantly enhance the capacity of polyvinyl chloride (PVC, 0.2 mm) MPs to adsorb pollutants with opposite charges. The Langmuir methylene blue adsorption capacity of PVC could be increased from 172 to 4417 ppm in the presence of a sodium dodecyl benzene sulfonate surfactant. Nonionic surfactants impeded the adsorption of both cationic and anionic pollutants due to the steric resistance of the hydrophilic polyethelene glycol chains. The electrostatic interaction mechanism dominated the interfacial behaviors of ionic pollutants on surfactant-adsorbed MP interfaces. The effects of the surfactants were further verified using four different model pollutants and six surfactants. The adsorption capacities of real environmental MPs, including PVC, polyethylene (PE), polypropylene (PP), and polystyrene (PS), increased by three to twenty-six times. The adsorption properties of MPs may be determined by the presence of co-existing surfactants, rather than their polymer species or additives., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Passive sampling techniques have been widely used to determine the dissolved concentration profiles of hydrophobic organic compounds (HOCs) in sediment porewater. However, the effects of having a protection for the passive sampler on profiling HOCs concentrations in sediment porewater, especially in deep sediment, have remained unclear. To address this issue, low density polyethylene passive samplers with and without protectors, which consisted of glass fiber filter and porous stainless steel shield, were simultaneously deployed in sediment of the Dongjiang River, South China. The results showed that the protectors retarded the dissipation of performance reference compounds (PRCs) from the sampler by a factor of 2-9. The protectors seemed to exert a negligible effect on the measured concentrations of PAHs, BDE-47, and BDE-99 in surficial sediment porewater (0-14 cm depth) from both samplers. However, the sediment porewater concentration profiles of PAHs and BDE-47 from the sampler with protectors were in agreement with those normalized by dry weight in deep sediment (16-34 cm depth), indicating that a diffusion layer established by the protectors may minimize the probability of local depletion of the target analytes in deep sediment. In addition, the log K oc values of PAHs, BDE-47, and BDE-99 exhibited a slight increasing trend with sediment depth. This finding suggested that in situ passive sampling techniques could be a feasible tool in determining the site-specific log K oc values of HOCs at different sediment depths., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Cyclic volatile methylsiloxanes (cVMS) are widely used in consumer products and commonly detected in the environment. There are challenges in the analysis of cVMS because of their ubiquitous use which can introduce high background contamination. The current study introduces a sample preparation method based on headspace of solid-phase microextraction (SPME) for monitoring the cVMS in waters. Efforts were made to reduce the background contamination during sample preparation and instrument analysis. A laboratory prepared MIL-101 coating was prepared using polysulfone instead of polydimethylsiloxane as adhesive to avoid the contamination. The extraction performance of the MIL-101 fiber was optimized and evaluated. The optimized extraction time and temperature were 60 min and 40 °C, respectively. The method quantification limits of the MIL-101 fiber for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) in water were 0.15 ng mL -1 , 0.14 ng mL -1 , and 0.27 ng mL -1 , respectively. The extraction efficiency of the proposed MIL-101 fiber was comparable to the commercial polydimethylsiloxane/divinylbenzene fiber. The developed method was applied to analyze the cVMS in wastewater treatment plant and the concentrations in the barscreen and in the aeration tank ranged from 0.73 to 3.3 ng mL -1 and 7.74-85.1 ng mL -1 , respectively. The MIL-101 fiber was also applied to study the photodegradation of the cVMS in water under simulated sunlight. Approximately 25%, 20%, and 45% of D4, D5, and D6, respectively, were degraded after 10 h exposure., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The ubiquity of microplastics in aquatic and terrestrial environments and related ecological impacts have gained global attention. Microplastics have been detected in table salt, drinking water, and air, posing inevitable human exposure risk. However, rigorous analytical methods for detection and characterization of microplastics remain scarce. Knowledge about the potential adverse effects on human health via dietary and respiratory exposures is also limited. To address these issues, we reviewed 46 publications concerning abundances, potential sources, and analytical methods of microplastics in table salt, drinking water, and air. We also summarized probable translocation and accumulation pathways of microplastics within human body. Human body burdens of microplastics through table salt, drinking water, and inhalation were estimated to be (0-7.3)×10 4 , (0-4.7)×10 3 , and (0-3.0)×10 7 items per person per year, respectively. The intake of microplastics via inhalation, especially via indoor air, was much higher than those via other exposure routes. Moreover, microplastics in the air impose threats to both respiratory and digestive systems through breathing and ingestion. Given the lifetime inevitable exposure to microplastics, we urgently call for a better understanding of the potential hazards of microplastics to human health.

Research has already demonstrated the toxic effects of microplastics (MPs) on different biota. However, the underlying toxic mechanism of MPs remains to be elucidated, especially the effect of particle size and the presence of dissolved organic matter in water. This study investigated the impact on Scenedesmus obliquus exposed in five types of polystyrene particle suspensions with different sizes and surface charges, in the presence and absence of humic acid (HA). Results indicated that the 50% growth inhibition rate of S. obliquus showed no significant difference between the five types of MPs, but the toxic mechanism varied with particle size. Larger size MPs caused adverse effects by blocking the light transport and affecting photosynthesis, while smaller ones destroyed the cell wall by adsorbing onto the algae surface. Also, the addition of HA significantly alleviated the toxicity of smaller size MPs, but not of the larger ones. Scanning electron microscopy images and the reactive oxygen species assay demonstrated that the HA could form a corona on the surface of MPs, reduce the affinity to microalgae, and minimize the adverse effect. Together, these findings identified important factors in determining the toxicity of MPs, providing valuable data for risk assessment of MPs.

Plastic pollution has caused increasing global concern. Currently, model estimates of the riverine plastic inputs to the global oceans based on the concept of Mismanaged Plastic Waste (MPW) varied substantially, and no field measurements of riverine inputs were available. We conducted sampling at the eight major river outlets of the Pearl River Delta, South China with rapid economic growth and urbanization to provide field measured data for fine-tuning modeling results. Floating microplastics (MPs) were collected with a Manta net (mesh size of 0.33 mm) five times during 2018. Microplastic particles (0.3-5.0 mm) widely occurred in all sampling sites. The number and mass concentrations of MPs were in the ranges of 0.005-0.7 particles m -3 and 0.004-1.28 mg m -3 and were positively correlated with water discharges. The annual riverine input of MPs from the Pearl River Delta was estimated at 39 billion particles or 66 tons, which converts to 2400-3800 tons of plastic debris based on calculations described in Text S2. These values were substantially below the MPW-based model estimates (91,000-170,000 tons). The large difference between measured and modeling results may have derived from the large uncertainty in the MPW values assigned to the world's countries/regions.

The kinetics of mercuric ion (Hg 2+ ) binding with heterogeneous naturally dissolved organic matter (DOM) has been hypothesized to result from competitive interactions among different organic ligands and functional groups of DOM for Hg 2+ . However, an experimental protocol is lacking to determine Hg 2+ binding with various competitive ligands and DOM, their binding strengths, and their dynamic exchange reactions. In this study, a stepwise reduction approach using ascorbic acid (AA) and stannous tin [Sn(II)] was devised to differentiate Hg(II) species in the presence of two major functional groups in DOM: the carboxylate-bound Hg(II) is reducible by both AA and Sn(II), whereas the thiolate-bound Hg(II) is reducible only by Sn(II). Using this operational approach, the relative binding strength of Hg 2+ with selected organic ligands was found in the order dimercaptopropanesulfonate (DMPS) > glutathione (GSH) > penicillamine (PEN) > cysteine (CYS) > ethylenediaminetetraacetate > citrate, acetate, and glycine at the ligand-to-Hg molar ratio < 2. Dynamic, competitive ligand exchanges for Hg 2+ from weak carboxylate to strong thiolate functional groups were observed among these ligands and within DOM, and the reaction depended on the relative binding strength and abundance of thiols and carboxylates, as well as reaction time. These results provide additional insights into dynamic exchange reactions of Hg 2+ within multicompositional DOM in controlling the transformation and bioavailability of Hg(II) in natural aquatic environments.

The impacts of microplastics on aquatic ecosystems and biota are gaining attention globally. Although microplastics have been widely detected in biota, there currently are few standardized detection and identification methods. The present study developed a novel one-step digestion method which was evaluated with mussel and fish samples. This method employed nitric acid and hydrogen peroxide (HNO 3 :H 2 O 2 = 4:1 by volume) as digestion reagents, which completely digested biota samples <5 g weight within 30 min at 50 °C. A density separation step was subsequently used to remove organic residues as necessary. The efficiency and suitability of this method were tested by spiking microplastics of 7 different types and of various sizes (1000, 900, 675, 300, 250, and 150 μm) into mussel and gastrointestinal tracts of fish. The recoveries of microplastics ranged from 90 to 100%. No significant changes in weight, surface area, and particle size (t test, p > 0.05) were observed for all tested polymers. Fourier transform infrared spectral analyses demonstrated that the method did not degrade any of the polymers except for polyethylene terephthalate. The method was demonstrated with mussel and fish samples collected from the Pearl River delta, south China, and was able to recover microplastics effectively. Overall, the present method is time-saving and easy to operate, with low procedural cross-contamination. The properties of microplastics recovered by the present method remained largely intact, greatly benefiting subsequent qualitative and quantitative analyses. Environ Toxicol Chem 2019;38:1400-1408. © 2019 SETAC., (© 2019 SETAC.)

Influence of sediment particle size on the desorption, bioavailability, and bioaccumulation potential of cypermethrin was investigated in the present study using two biomimetic techniques (Tenax extraction and solid-phase microextraction (SPME)) and bioaccumulation testing with Lumbriculus variegatus. A field-collected sediment was wet sieved to obtain five particle-size fractions (<20, 20-63, 63-180, 180-500, and >500 μm) and used for cypermethrin spiking. The finest sediment (<20 μm) had the highest rapid desorption fraction (F r ) and rate (k r ) when compared to coarser sediments. Elimination rate constants of cypermethrin determined by SPME (k e-SPME ) and L. variegatus (k e-L.v. ) for various fractions of sediments followed the same trend, suggesting SPME fiber acts as a good surrogate for benthic organisms considering passive partitioning. Finally, biota-sediment accumulation factors (BSAFs) of cypermethrin in worms were almost the same among the sediments with different particle sizes (0.425 ± 0.07-0.445 ± 0.07 g OC g -1 lipid), suggesting that the differences in desorption and freely dissolved concentrations of cypermethrin did not significantly influence its bioaccumulation potential in worms. Selective ingestion of fine sediment particles may be one of the contributing reasons for no differences in BSAFs observed in the treatments as would have been expected. The different desorption and freely dissolved concentrations of cypermethrin in sediments with different particle sizes observed in this study highlights the need for further work to better understand the influence of particle size on the toxicity of highly toxic insecticides, such as cypermethrin, to sensitive benthic species., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Microplastics (MPs) sized between 0.33 and 5 mm were collected using Manta trawls from ten surface seawater sites in Bohai and Huanghai Seas, China. A total of 1024 (Bohai Sea) and 132 (Huanghai Sea) microplastic pieces were classified, including polystyrene foams, polyethylene films and lines, and other plastic pellets, with concentrations of MPs ranging from 3 to 162 particles per 100 m 3 (0.012-2.96 mg m -3 ). A pretreatment of MPs with 30% H 2 O 2 in water did not significantly lower polycyclic aromatic hydrocarbon (PAH) concentrations on MPs compared to no H 2 O 2 pretreatment. Measurements of PAHs carried on the collected MPs indicated that the concentrations of the sum of 16 PAHs were in the range of 3400-119,000 ng g -1 . The sources of PAHs in Bohai and Huanghai Seas were highly similar, with petroleum and gasoline probably as the dominant sources. The present study shows the relative importance of MPs in regards to chemical transport in the marine environment. The combination of high concentrations of PAHs affiliated with MPs and the increasing magnitude of plastic pollution in the world's oceans demonstrates the considerable importance of MPs to the fate of PAHs in marine environments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Sludge disposal such as land application is suspected as a significant source of microplastic (MP) pollution in the environment. To examine such a hypothesis, the present study was conducted to investigate the occurrence of MPs in sludge by analyzing 79 sewage sludge samples collected from 28 wastewater treatment plants (WWTPs) in 11 Chinese provinces. MP concentrations in the sludge samples ranged from 1.60-56.4 × 10 3 particles per kilogram of dry sludge, with an average of 22.7 ± 12.1 × 10 3 particles per kilogram of dry sludge. Thereinto, the sludge-based MP contents were greater in eastern China than in western China and varied during different months. Their colors and types were mainly white (59.6%) and fibers (63%), respectively. Microscope Fourier Transform infrared spectroscopy revealed that most of MPs belonged to polyolefin, acrylic fibers, polyethylene and polyamide. Some WWTP parameters, such as servicing area, proportion of industrial wastewater, secondary treatment and sludge dewatering may have affected MP concentrations in sludge. Based on the total sludge production in China, the average amount of sludge-based MPs entering into natural environmental was estimated to be 1.56 × 10 14 particles per year. The findings confirmed that sewage sludge discharge is an important source of MP pollution in the environment. Further evaluation of the associated environmental hazards with MPs is deemed necessary., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Occurrence of microplastics (MPs) in the environment has attracted great attention as it has become a global concern. This review aims to systematically demonstrate the role of marine microplastic as a novel medium for environmental partitioning of chemicals in the ocean, which can cause toxic effects in the ecological environment. This review assimilated and analyzed available data published between 1972 and 2017 on the interaction between MPs and selected chemicals. Firstly, the review analyzes the occurrence of chemicals in MPs and outlines their distribution patterns. Then possible mechanisms of the interaction between MPs and organic chemicals and potential controlling factors were critically studied. Finally, the hazards of MPs and affiliated organic chemicals to marine organisms were shortly summarized., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

To examine the distributional patterns of persistent organic pollutants in the wild fish of Hong Kong and assess the health risks associated with consuming them, two typical kinds of persistent organic pollutants, such as dichlorodiphenyltrichloroethane (DDTs) and polychlorinated biphenyls (PCBs), were determined in 31 kinds of fishes caught from the coastal areas of Hong Kong. The results indicate that the concentrations of DDTs and PCBs in the wild fishes were in the ranges of 0.44-17 ng·g -1 and 0.028-6.3 ng·g -1 , respectively, which were at the low end of the global ranges. Spatially, the lowest concentrations of DDTs and PCBs were found in the fishes occurring in the west of Lantau Island and Tolo Harbor. Furthermore, the feeding habits and living environments of the fishes could have some influence on the accumulation of DDTs and PCBs in them. Source diagnostics indicated that DDTs in these fishes mainly originated from historical residues, but the fishes which migrate for relatively longer distances may be subject to DDT contamination in the estuaries. Finally, human health risk assessments suggested that the increased potential lifetime cancer risk of local adolescences and adults exposed to DDTs and PCBs via wild fish consumption was high. Therefore, the local residents in Hong Kong should reduce their daily intake of wild fish caught from the surrounding coastal regions.

An increasing number of reports have been published concerning microplastic (MP) pollution in aquatic environments. Methods used in these studies continue to be updated and lack standardization, so that an up-to-date review pertaining methods for MP research is needed. This critical review examines the analytical methods, including sampling, identification, and quantitation, for MP research. Samples are generally collected from water, sediment, and biota gastrointestinal tract. Manta nets or trawls are prevalently used in surface water sampling, while direct shoveling or box-corer grab are commonly applied in sediment sampling. Microplastics in biota are generally obtained by dissecting organisms and separating livers, gills, and guts. Density separation is frequently chosen to separate MPs from sample matrices. Chemical digestion can dissolve other organic materials and isolate MPs for further identification. Visual sorting should be combined with chemical composition analysis to better identify the polymer type. Pyrolysis or thermal decomposition gas chromatography coupled with mass spectrometry, Fourier transform infrared spectroscopy, and Raman spectroscopy are currently the main technologies for MP identification. Units prevalently used to express MP abundance in water, sediment, and biota are "particles per m 3 ," "particles per m 2 ," and "particles per individual," respectively. As MP abundances often varied with the methods used, we recommend that analytical protocols of MPs should better be standardized and optimized. Despite the important progress in analysis of MPs, detection technologies for identifying nano-sized plastic particles are still lacking, and therefore should be developed swiftly.

Little is known about the occurrences, distributions, sources, and potential risks of organophosphate (OP) triesters and diester degradation products in municipal sludge from wastewater treatment plants (WWTPs). In this study, we conducted the first nationwide survey to simultaneously determine a suite of 11 OP triesters and six diester degradation products in sludge from WWTPs across China. All OP triesters were detected and three diesters were identified for the first time in sludge samples. Total concentrations of OP triesters and diester degradation products were in the ranges of 43.9-2160 and 17.0-1300 ng (g of dry weight) -1 , respectively, indicating relatively low pollution levels in China compared with those of several developed countries. A distinct geographical variation of higher concentrations of OP triesters and diesters in East China than in Central and West China was observed, suggesting that regional levels of organophosphate esters are associated with the magnitudes of regional economic development. Source analysis revealed nonchlorinated OP diesters are mainly derived from degradation in WWTPs, while chlorinated OP diesters were largely sourced from outside WWTPs. The estimated total emission fluxes of OP triesters and diesters via land-application sludge in China were approximately 330 and 134 kg/year, respectively. Further risk assessment based on risk quotient values in sludge-applied soils indicated low to medium risks for most OP triesters and diesters except tris(methylphenyl) phosphate. The significant accumulation of OP triesters and widespread occurrence of diester degradation products in sludge raise environmental concerns about these contaminants.

Extensive use of neonicotinoid insecticides has raised great concerns about their ecological risk. A reliable method to measure trace neonicotinoids in complicated aquatic environment is a premise for assessing their aquatic risk. To effectively remove matrix interfering substances from field water samples before instrumental analysis with HPLC/MS/MS, a multi-sorbent solid phase extraction method was developed using Box-Behnken design. The optimized method employed 200mg HLB/GCB (w/w, 8/2) as the sorbents and 6mL of 20% acetone in acetonitrile as the elution solution. The method was applied for measuring neonicotinoids in water at a wide range of concentrations (0.03-100μg/L) containing various amounts of matrix components. The recoveries of acetamiprid, imidacloprid, thiacloprid and thiamethoxam from the spiked samples ranged from 76.3% to 107% while clothianidin and dinotefuran had relatively lower recoveries. The recoveries of neonicotinoids in water with various amounts of matrix interfering substances were comparable and the matrix removal rates were approximately 50%. The method was sensitive with method detection limits in the range of 1.8-6.8ng/L for all target neonicotinoids. Finally, the developed method was validated by measurement of trace neonicotinoids in natural water., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Assessment of surface water pollution by organic pollutants is a top priority in many parts of the world, as it provides critical information for implementing effective measures to ensure drinking water safety. This is particularly important in China, where insufficient data of national scale have been acquired on the occurrence of any organic pollutants in the country's water bodies. To fill the knowledge gap, we employed passive samplers to survey polycyclic aromatic hydrocarbons (PAHs) in 42 freshwaters throughout the country. The dissolved Σ 24 PAH concentrations ranged from 0.28 to 538 ng L -1 , with the highest and lowest values obtained in Southern Lake in Wuhan and in the Nam Co Lake in Tibet, respectively. Average Σ 24 PAH concentrations in West, Central, and East China correlated well with the population densities in these regions. The composition profiles of PAHs showed a mixed PAH source of coal combustion, fossil fuel combustion, and oil spills. In addition, all dissolved PAH concentrations were below the water guidelines developed by the U.S. Environmental Protection Agency, the European Union, and the Canadian government, except for anthracene in Southern Lake. Our results also demonstrated the feasibility of establishing a global network of monitoring organic pollutants in the aquatic environment with passive sampling techniques.

Identifying key toxicants in sediment is a great challenge, particularly if nontarget toxicants are involved. To identify the contaminants responsible for sediment toxicity to Chironomus dilutus in Guangzhou reach of the Pearl River in South China, passive dosing and in vivo toxicity testing were incorporated into effect-directed analysis (EDA) to account for bioavailability. Fractionation of sediment extracts was performed with gel permeation chromatography and reverse phase liquid chromatography sequentially. Polydimethylsiloxane served as passive dosing matrix for midge bioassays. The fractions showing abnormal enzymatic response were subject to a nontarget analysis, which screened out 15 candidate toxicants. The concentrations of the screened contaminants (log-based organic carbon normalized) in sediments of 10 sites were compared to sediment toxicity (10 and 20 day mortality and 10 day enzymatic response) to C. dilutus using correlation analyses. The results suggested that oxidative stress induced by cypermethrin, dimethomorph, pebulate and thenylchlor may have in part caused the observed toxicity to C. dilutus. The present study shows that EDA procedures coupled with passive dosing and in vivo toxicity testing can be effective in identifying sediment-bound toxicants, which may pose high risk to benthic organisms but are not routinely monitored and/or regulated. The findings of the present study highlight the importance of incorporating environmentally relevant approaches in assessing sediment heavily impacted by a multitude of contaminants, which is often the case in many developing countries.

The present study examined the bioacessibility of DDTs and PBDEs in cooked fish (yellow grouper; Epinephelus awoara) with and without heating using the colon extended physiologically based extraction test. The bioaccessibility of DDTs and PBDEs increased from 60 and 26% in raw fish to 83 and 63%, respectively, after the addition of oil to raw fish. However, they decreased from 83 to 66% and from 63 to 40%, respectively, when oil-added fish were cooked. Human health risk assessment based on bioaccessible concentrations of DDTs and PBDEs in fish showed that the maximum allowable daily fish consumption rates decreased from 25, 59, and 86 g day -1 to 22, 53, and 77 g day -1 for children, youths, and adults, respectively, after fish were cooked with oil. These findings indicated that the significance of cooking oil to the bioaccessibility of DDTs and PBDEs in food should be considered in assessments of human health risk.

Organic contaminants, in particular persistent organic pollutants (POPs), adversely affect water quality and aquatic food webs across the globe. As of now, there is no globally consistent information available on concentrations of dissolved POPs in water bodies. The advance of passive sampling techniques has made it possible to establish a global monitoring program for these compounds in the waters of the world, which we call the Aquatic Global Passive Sampling (AQUA-GAPS) network. A recent expert meeting discussed the background, motivations, and strategic approaches of AQUA-GAPS, and its implementation as a network of networks for monitoring organic contaminants (e.g., POPs and others contaminants of concern). Initially, AQUA-GAPS will demonstrate its operating principle via two proof-of-concept studies focused on the detection of legacy and emerging POPs in freshwater and coastal marine sites using both polyethylene and silicone passive samplers. AQUA-GAPS is set up as a decentralized network, which is open to other participants from around the world to participate in deployments and to initiate new studies. In particular, participants are sought to initiate deployments and studies investigating the presence of legacy and emerging POPs in Africa, Central, and South America.

Persistent organic pollutants (POPs) present in water may be bioconcentrated in phytoplankton and further transferred into higher trophic levels. In the present study, seawater, sediment, phytoplankton and macroalgae (Ulva lactuca L.) samples were collected from two estuarine bays in South China and analyzed for 24 polybrominated diphenyl ethers (PBDEs) and 22 organochlorine pesticides (OCPs). The concentrations of PBDE congeners except BDE-209 were low in both phytoplankton and Ulva. BDE-209 was the predominant congener in phytoplankton and Ulva, accounting for 89.5% and 86.6% of the total average concentrations of PBDEs (48.5 and 4.1ngg -1 dw), respectively. The average concentrations of DDTs, HCHs and 1-chloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDMU) in phytoplankton were 398, 241 and 11.3ngg -1 dw, respectively, while those of DDTs and HCHs in Ulva were 8.4 and 33.1ngg -1 dw. The levels of both PBDEs and OCPs were an order of magnitude higher in phytoplankton than in Ulva, indicating that phytoplankton with larger surface areas have higher uptake efficiency for POPs than Ulva. Bioconcentration factors (BCFs) of DDT and PBDE in phytoplankton from the two bays were in the range of 10 5 -10 6 , suggesting that bioconcentration may be one of the key sources of POPs and algae can be an important route for POPs to move toward higher trophic levels., (Copyright © 2016. Published by Elsevier B.V.)

The fate of hydrophobic organic compounds in aquatic environment are largely determined by their exchange at sediment-water interface, which is highly dynamic and subject to rapidly evolving environmental conditions. In turn, environmental conditions may be governed by both physicochemical parameters and anthropogenic events. To examine the importance of various impact factors, passive sampling devices were deployed at the seafloor of Hailing Bay, an urbanized estuarine bay in Guangdong Province of South China to measure the sediment-water diffusion fluxes of several metabolites of dichlorodiphenyltrichloroethane (DDT), p,p'-DDE, p,p'-DDD and o,p'-DDD. The physicochemical properties of water (temperature, pH, salinity and dissolved oxygen) and surface sediment (sediment organic matter, physical composition, pH, water content, colony forming unit and catalase activity) were also measured. The results showed that the diffusion fluxes of o,p'-DDD, p,p'-DDD and p,p'-DDE at sites A1 and A2 near a fishing boat maintenance facility ranged from 0.42 to 4.73 ng m -2 d -1 (from sediment to overlying water), whereas those at offshore sites varied between -0.03 and -3.02 ng m -2 d -1 (from overlying water to sediment), implicating A1 and A2 as the sources of the target compounds. The distribution patterns of the diffusion fluxes of the target compounds were different from those of water and sediment parameters (water temperature, salinity, sediment texture, pH, colony forming unit and catalase activity) at six sampling sites. This finding suggested that none of these parameters were critical in dictating the sediment-water diffusion fluxes. Besides, decreases in the contents of kerogen and black carbon by 6.7% and 11% would enhance the diffusion fluxes of the target compounds by 11-14% and 12-23%, respectively, at site A1, indicating that kerogen and black carbon were the key factors in mediating the sediment-water diffusion fluxes of DDT-related compounds in field environments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Mass transfer of hydrophobic organic contaminants (HOCs) across the air-water interface is an important geochemical process controlling the fate and transport of HOCs at the regional and global scales. However, few studies have characterized concentration or fugacity profiles of HOCs near both sides of the air-water interface, which is the driving force for the inter-compartmental mass transfer of HOCs. Herein, we introduce a novel passive sampling device which is capable of measuring concentration (and therefore fugacity) gradients of HOCs across the air-water interface. Laboratory studies indicated that the escaping fugacity values of polycyclic aromatic hydrocarbons (PAHs) from water to air were negatively correlated to their volatilization half-lives. Results for field deployment were consistent between the passive sampler and an active method, i.e., a combination of grab sampling and liquid-liquid extraction. In general, the fugacity profiles of detected PAHs were indicative of an accumulation mechanism in the surface microlayer of the study regions (Haizhu Lake and Hailing Bay of Guangdong Province, China), while p,p'-DDD tended to volatilize from water to the atmosphere in Hailing Bay. Furthermore, the fugacity profiles of the target analytes increased towards the air-water interface, reflecting the complexity of environmental behavior of the target analytes near the air-water interface. Overall, the passive sampling device provides a novel means to better characterize the air-water diffusive transfer of HOCs, facilitating the understanding of the global cycling of HOCs., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Natural organic matter and grain size are considered as important parameters dictating the transport and fate of organic compounds in sediment. However, increasing evidence suggested that manufactured debris may alter the underlying mechanisms for biogeochemical cycling of organic compounds. To examine this assumption, estuarine sediment and embedded debris were collected from a fishery base in Guangdong Province of South China and analyzed for organophosphorus flame retardants (OPFRs), phthalates (PAEs), organotin compounds (OTs) and dichlorodiphenyltrichloroethanes (DDTs). Coarse-size debris (>200μm) were heterogeneously distributed in sediment, and most abundant near the boat maintenance facilities, aquaculture zone and shipping channel. The median concentrations of OPFRs, OTs, PAEs and DDTs in debris were 11, 0.2, 11 and 3.9μgg(-1) dry sample weight(-1), respectively, 1 to 3 orders of magnitude greater than those in bulk sediment (19, 60, 240 and 570ngg(-1) dry sample weight(-1), respectively). Furthermore, OPFRs, OTs and PAEs were mostly (>99%) enriched in coarse-size (63-2000μm) sediment, and there was no significant correlation (p>0.05) between the concentrations of OPFRs, OTs and PAEs in bulk and size-fractioned sediment samples and total organic carbon or grain size, similar to the distribution pattern of DDTs reported previously. When distinct debris were removed from the light-density (<1.7gcm(-3)) fraction of coarse-size (200-2000μm) sediment, the concentration levels of OPFRs, OTs, PAEs and DDTs declined by 84%, 59%, 55% and 7%, respectively. Obviously, debris irregularly distributed in sediment can alter the sediment sorption capacity for OPFRs, OTs and PAEs, and thus may undermine the significance of organic matter and grain size to the distribution of organic chemicals in sediment. Finally, commonly used procedures for preparing sediment samples and screening of debris may disturb the grain size distribution or underestimate the abundance of heavy-density debris, resulting in flawed sediment quality assessment., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Anthropogenic impacts have continuously intensified in mega urban centers with increasing urbanization and growing population. The spatial distribution pattern of such impacts can be assessed with soil halogenated flame retardants (HFRs) as HFRs are mostly derived from the production and use of various consumer products. In the present study, soil samples were collected from the Pearl River Delta (PRD), a large urbanized region in southern China, and its surrounding areas and analyzed for a group of HFRs, i.e., polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane, bis(hexachlorocyclopentadieno)cyclooctane (DP) and hexabromobenzene. The sum concentrations of HFRs and PBDEs were in the ranges of 0.66-6500 and 0.37-5700 (mean: 290 and 250) ng g(-1) dry weight, respectively, around the middle level of the global range. BDE-209 was the predominant compound likely due to the huge amounts of usage and its persistence. The concentrations of HFRs were greater in the land-use types of residency, industry and landfill than in agriculture, forestry and drinking water source, and were also greater in the central PRD than in its surrounding areas. The concentrations of HFRs were moderately significantly (r(2) = 0.32-0.57; p < 0.05) correlated with urbanization levels, population densities and gross domestic productions in fifteen administrative districts. The spatial distribution of DP isomers appeared to be stereoselective as indicated by the similarity in the spatial patterns for the ratio of anti-DP versus the sum of DP isomers (fanti-DP) and DP concentrations. Finally, the concentrations of HFRs sharply decreased with increasing distance from an e-waste recycling site, indicating that e-waste derived HFRs largely remained in local soil., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

An overlooked issue for field application of in situ performance reference compound (PRC) calibration methods is the validity of the assumption that both the sorption of a target compound and desorption of its corresponding PRC follow the first-order kinetics with the same rate constants under stagnant conditions. In the present study, disposable polydimethylsiloxane fibers of 2 sizes (7 and 35 µm) impregnated with 8 (13) C-labeled or deuterated PRCs were statically deployed into different marine sediments, from which the kinetics for sorption of the target compounds and desorption of the PRCs were characterized. Nonsymmetrical profiles were observed for exchange of the target analytes and their corresponding PRCs in sediment under stagnant conditions. The hysteretic desorption of PRCs in the kinetic regime may be ascribed to the low chemical potential between the fiber and sediment porewater, which reflects the inability of water molecules to rapidly diffuse through sediment to solvate the PRCs in the aqueous layer around the fiber surface. A moderate correlation (r = 0.77 and r = 0.57, p < 0.05 for both regressions) between the PRC-calibrated equilibrium concentrations of 1,1-dichloro-2,2-bis-(chlorophenyl) ethylene (p,p'-DDE) and polychlorinated biphenyl (PCB)-153 and the lipid normalized levels in worms (Neanthes arenaceodentata) was obtained in co-exposure tests under simulating field conditions, probably resulting from slightly overestimated bioavailability because of the hysteretic desorption of PRCs and toxic effects. Environ Toxicol Chem 2016;35:1978-1985. © 2015 SETAC., (© 2015 SETAC.)