Observation-Based Diagnostics of Reactive Nitrogen Recycling through HONO Heterogenous Production: Divergent Implications for Ozone Production and Emission Control.

Understanding of nitrous acid (HONO) production is crucial to photochemical studies, especially in polluted environments like eastern China. In-situ measurements of gaseous and particulate compositions were conducted at a rural coastal site during the 2018 spring Ozone Photochemistry and Export from China Experiment (OPECE). This data set was applied to investigate the recycling of reactive nitrogen through daytime heterogeneous HONO production. Although HONO levels increase during agricultural burning, analysis of the observation data does not indicate more efficient HONO production by agricultural burning aerosols than other anthropogenic aerosols. Box and 1-D modeling analyses reveal the intrinsic relationships between nitrogen dioxide (NO2), particulate nitrate (pNO3), and nitric acid (HNO3), resulting in comparable agreement between observed and simulated HONO concentrations with any one of the three heterogeneous HONO production mechanisms, photosensitized NO2 conversion on aerosols, photolysis of pNO3, and conversion from HNO3. This finding underscores the uncertainties in the mechanistic understanding and quantitative parametrizations of daytime heterogeneous HONO production pathways. Furthermore, the implications for reactive nitrogen recycling, ozone (O3) production, and O3 control strategies vary greatly depending on the HONO production mechanism. On a regional scale, the conversion of HONO from pNO3 can drastically enhance O3 production, while the conversion from NO2 can reduce O3 sensitivity to NOx changes in polluted eastern China.

Species-specific and habitat-dependent bioaccumulation of halogenated flame retardants in marine organisms from estuary to coastal seas.

Halogenated flame retardants (HFRs) have attracted global attention owing to their adverse effects on ecosystems and humans. The Shandong Peninsula is the largest manufacturing base for HFRs in East Asia, yet its impacts on marine ecosystems are unclear. Seventeen HFRs were analyzed in organisms captured from the Xiaoqing River estuary, Bohai Sea (BS), Yellow Sea and Northern East China Sea to investigate the distribution and bioaccumulation of HFRs on a broad scale. The results showed a downward trend in ΣHFR concentrations from the estuary (37.7 ng/g lw on average) to Laizhou Bay (192 ng/g lw) and to coastal seas (3.13 ng/g lw). The concentrations of ΣHFRs were significantly higher in demersal fish (0.71-198 ng/g lw) and benthic invertebrates (0.81-3340 ng/g lw) than in pelagic fish (0.30-27.6 ng/g lw), reflecting a habitat dependence. The concentrations of higher-brominated homologs were greater in benthic invertebrates, whereas a greater level of lower-brominated PBDE congeners was observed in fish, suggesting different profiles between species. Furthermore, the analogue composition of HFRs in fish was similar to that in the dissolved phase of seawater, whereas the HFR pattern in benthic invertebrates was consistent with the profile in sediment. The concentrations of HFRs in organisms vary widely depending on emissions from anthropogenic activities, whereas bioaccumulation patterns are strongly influenced by species and habitat.

Effect of hydrodynamic and ecosystem conditions on persistent organic pollutant temporal-spatial variations in the Yellow Sea.

Coastal seas are important pools of persistent organic pollutants (POPs) discharged from land. Considering the complex conditions in coastal seas and various biochemical features of POPs, special temporal-spatial variations in POPs have been reported. To understand these variations, we developed a three-dimensional hydrodynamic-ecosystem-POP coupled model and applied it to the Yellow Sea. We selected two POP species (polychlorinated biphenyl congener 153 (PCB-153) and decabromodiphenyl ether (BDE-209)), which have different biochemical properties, as target materials. The dissolved PCB-153 simulated concentration was high in late spring and low in autumn, whereas that of BDE-209 was high in summer and low in winter. Both PCB-153 and BDE-209 showed high particle-bound concentrations in early spring. In summer, dissolved PCB-153 accumulated at the sea bottom, whereas dissolved BDE-209 accumulated at the sea surface. Seasonal and spatial variation differences in the two POPs are likely caused by greater Henry's Law Constant (H') and bioconcentration factor (BCF) of PCB-153 than that of BDE-209, which leads to higher volatilization and stronger absorption by the particles for PCB-153 than BDE-209. As a component of such differences, the "biological pump" of PCB-153 in the central Yellow Sea is more apparent than that of BDE-209.

Distribution, sources, and eco-risk of Current-Use Pesticides (CUPs) in the coastal waters of the northern Shandong Peninsula, China.

This study investigated the spatial distributions and seasonal variations of 19 CUPs in the coastal areas of the Shandong Peninsula and its surrounding rivers and assessed their ecological risk. In freshwater and seawater, insecticides (chlorpyrifos, methoxychlor, and pyridaben), as well as fungicides (fenarimol) and herbicides (dichlobenil) were the main pollutants (Detection Frequency: 100 %). Spatially, during winter, the regional pollution levels of Σ19CUPs in seawater showed a trend of Laizhou Bay (LZB, mean:4.13 ng L-1) > Yellow River Estuary (YRE, mean:2.57 ngL-1) > Bohai Bay (BHB, mean:2.21 ng L-1) > Yanwei Area (YWA, mean:1.94 ng L-1). The similarities of major substances between rivers and the marine environment suggest that river discharge is the main source of CUPs pollution in coastal areas. In summer, CUPs in rivers posed a high risk. In winter, the risk significantly decreased, indicating a moderate overall risk. Seawater exhibited a low risk in winter.

Molecular signatures and formation mechanisms of water-soluble chromophores in particulate matter from Karachi in Pakistan.

Excitation-emission matrix (EEM) fluorescence spectroscopy is a widely-used method for characterizing the chemical components of brown carbon (BrC). However, the molecular basics and formation mechanisms of chromophores, which are decomposed by parallel factor (PARAFAC) analysis, are not yet fully understood. In this study, we characterized the water-soluble organic carbon (WSOC) in aerosols collected from Karachi, Pakistan, using EEM spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We identified three PARAFAC components, including two humic-like components (C1 and C2) and one phenolic-like species (C3). We determined the molecular families associated with each component by performing Spearman correlation analysis between FT-ICR MS peaks and PARAFAC component intensities. We found that the C1 and C2 components were associated with nitrogen-enriched compounds, where C2 with the longest emission wavelength exhibited a higher level of aromaticity, N content, and oxygenation than C1. The C3 associated formulas have fewer nitrogen-containing species, a lower unsaturation degree, and a lower oxidation state. An oxidation pathway was identified as an important process in the formation of C1 and C2 components at the molecular level, particularly for the assigned CHON compounds associated with the gas-phase oxidation process, despite their diverse precursor types. Numerous C2 formulas were found in the "potential BrC" region and overlapped with the BrC-associated formulas. It can be inferred that the compounds that fluoresce C2 contributed considerably to the light absorption of BrC. These findings are essential for future studies utilizing the EEM-PARAFAC method to explore the sources, processes, and compositions of atmospheric BrC.

Comprehensive Assessment of Exposure Pathways for Perfluoroalkyl Ether Carboxylic Acids (PFECAs) in Residents Near a Fluorochemical Industrial Park: The Unanticipated Role of Cereal Consumption.

With the replacement of perfluorooctanoic acid (PFOA) with perfluorinated ether carboxylic acids (PFECAs), residents living near fluorochemical industrial parks (FIPs) are exposed to various novel PFECAs. Despite expectations of low accumulation, short-chain PFECAs, such as perfluoro-2-methoxyacetic acid (PFMOAA), previously displayed a considerably high body burden, although the main exposure routes and health risks remain uncertain. Here, we explored the distribution of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in diverse environmental media surrounding a FIP in Shandong Province, China. PFECAs were found at elevated concentrations in all tested matrices, including vegetables, cereals, air, and dust. Among residents, 99.3% of the ∑36PFAS exposure, with a 43.9% contribution from PFECAs, was due to gastrointestinal uptake. Dermal and respiratory exposures were negligible at 0.1 and 0.6%, respectively. The estimated daily intake (EDI) of PFMOAA reached 114.0 ng/kg body weight (bw)/day, ranking first among all detected PFECAs. Cereals emerged as the dominant contributor to PFMOAA body burden, representing over 80% of the overall EDI. The median EDI of hexafluoropropylene oxide dimer acid (HFPO-DA) was 17.9 ng/kg bw/day, markedly higher than the USEPA reference doses (3.0 ng/kg bw/day). The absence of established threshold values for other PFECAs constrains a comprehensive risk assessment.

Development of a trace quantitative method to investigate caffeine distribution in the Yellow and Bohai Seas, China, and assessment of its potential neurotoxic effect on fish larvae.

Caffeine is an emerging contaminant in aquatic environments. The study utilized a validated method to investigate the presence and distribution of caffeine in the surface water of the Yellow and Bohai Seas, urban rivers, and the Yantai estuary area. The analytical method conforms to EPA guidelines and exhibits a limit of quantification that is 200 times lower than that of prior investigations. The study revealed that the highest concentration of 1436.4 ng/L was found in convergence of ocean currents in the Yellow and Bohai Seas. The presence of larger populations and the process of urban industrialization have been observed to result in elevated levels of caffeine in offshore regions, confirming that caffeine can serve as a potential indicator of anthropogenic contamination. Fish larvae exhibited hypoactivity in response to caffeine exposure at environmentally relevant concentrations. The study revealed that caffeine pollution can have adverse effects on marine and offshore ecosystems. This emphasizes the importance of decreasing neurotoxic pollution in the aquatic environment.

Spatiotemporal distribution and particle-water partitioning of polycyclic aromatic hydrocarbons in Bohai Sea, China.

The Bohai Sea is one of the most polluted marine areas in China with polycyclic aromatic hydrocarbons (PAHs) due to its unique hydrological and geographical environment. To investigate differences in PAH concentrations, composition, and particle-water partitioning before and after the rainy reason, water samples were collected during two surveying voyages covering most of the area of the Bohai Sea. Total and dissolved PAH concentrations were higher during the June voyage (total PAHs: 32.29 ± 15.18 ng/L, dissolved PAHs: 31.25 ± 15.26 ng/L) than the August voyage (total PAHs: 15.98 ± 6.39 ng/L, dissolved PAHs: 11.21 ± 5.59 ng/L). The opposite trend was observed for particulate PAHs (June: 1.04 ± 1.01 ng/L, August: 4.78 ± 2.96 ng/L). Among particulate PAHs, an unusually high proportion (65.07%) of low-molecular-weight (LMW) PAHs was observed during the August voyage, which was significantly higher than the proportion during the June voyage (21.86%). This high proportion was inconsistent with the general distribution of PAHs in the aquatic environment according to their physicochemical properties. The excess LMW PAHs adsorbed on suspended particulate matter arose mainly from soil affected by the petrochemical industry of the Bohai Economic Rim, and were carried with particles on runoff into the Bohai Sea during the rainy season. An estimated 5.49 t of LMW PAHs transitioned from the particulate phase to the dissolved phase during the rainy season. This transfer of LMW PAHs from coastal soil to the water column may be an important source of PAHs in the Bohai Sea.

Riverine microbial communities impacted by per- and polyfluoroalkyl substances (PFAS) emissions from a fluoropolymer-manufacturing plant.

Per- and polyfluoroalkyl substances (PFAS) are widespread pollutants that can influence microorganisms. To unveil the effects of PFAS in natural microecosystems, a study that focused on the bacterial, fungal, and microeukaryotic communities around the PFAS point source was conducted in China. A total of 255 specific taxa were significantly different between the upstream and downstream samples, 54 of which were directly correlated with PFAS concentration. Stenotrophomonas (99.2 %), Ralstonia (90.7 %), Phoma (21.9 %), and Alternaria (97.6 %) were the dominant genera in sediment samples from the downstream communities. In addition, most of the dominant taxa were significantly correlated with PFAS concentration. Furthermore, the type of microorganism (bacteria, fungi, and microeukaryotes) and habitat (sediment or pelagic) also influence the microbial community responses to PFAS exposure. Pelagic microorganisms featured more PFAS-correlated biomarker taxa (36 pelagic microeukaryotic biomarkers and 8 pelagic bacteria biomarkers) than the sediments (9 sediment fungi biomarkers and 5 sediment bacteria biomarker). In general, around the factory, the microbial community was more variable in pelagic, summer, and microeukaryotic conditions than in other types. Attention needs to be paid to these variables in the future effect of PFAS on microorganisms.

Influence of hydrodynamic conditions on the fate of halogenated flame retardants along salinity gradients in a highly polluted micro-tidal estuary.

Halogenated flame retardants (HFRs) have properties similar to those of hydrophobic organic pollutants (HOPs). However, the understanding of their environmental fate in tidal estuaries remains limited. This study aims to bridge knowledge gaps regarding the land-sea transport of HFRs through riverine discharge into coastal waters. HFR levels were significantly influenced by tidal movement, and decabromodiphenyl ethane (DBDPE) was the predominant compound with a median concentration of 3340 pg L-1 in the Xiaoqing River estuary (XRE), whereas BDE209 had a median concentration of 1370 pg L-1. The Mihe River tributary plays a key role in transporting pollution to the downstream estuary of the XRE in summer, and the increasing suspended particulate matter (SPM) by resuspension in winter significantly affects HFR levels. These concentrations were inversely proportional to diurnal tidal oscillations. Tidal asymmetry caused an increase in SPM during an ebb tide, which increased HFR levels in a micro-tidal estuary such as the Xiaoqing River. The location of the point source and flow velocity influences the HFR concentrations during tidal fluctuations. Tidal asymmetry increases the likelihood of some HFRs being adsorbed by particles exported to the adjacent coast, and some settled down in areas with low hydrodynamic conditions, hindering their flow to the ocean.

Trophic behaviors of PFOA and its alternatives perfluoroalkyl ether carboxylic acids (PFECAs) in a coastal food web.

With the increasing restrictions and concerns about legacy poly- and perfluoroalkyl substances (PFAS), the production and usage of alternatives, i.e., perfluoroalkyl ether carboxylic acids (PFECAs), have risen recently. However, there is a knowledge gap regarding the bioaccumulation and trophic behaviors of emerging PFECAs in coastal ecosystems. The bioaccumulation and trophodynamics of perfluorooctanoic acid (PFOA) and its substitutes (PFECAs) were investigated in Laizhou Bay, which is located downstream of a fluorochemical industrial park in China. Hexafluoropropylene oxide trimer acid (HFPO-TrA), perfluoro-2-methoxyacetic acid (PFMOAA) and PFOA constituted the dominant compounds in the ecosystem of Laizhou Bay. PFMOAA was dominant in invertebrates, whereas the long-chain PFECAs preferred to accumulate in fishes. The PFAS concentrations in carnivorous invertebrates were higher than those in filter-feeding species. Considering migration behaviors, the ∑PFAS concentrations followed the order oceanodromous fish < diadromous fish < non-migratory fish. The trophic magnification factors (TMFs) of long-chain PFECAs (HFPO-TrA, HFPO-TeA and PFO5DoA) were >1, suggesting trophic magnification potential, while biodilution for short-chain PFECAs (PFMOAA) was observed. The intake of PFOA in seafood may constitute a great threat to human health. More attention should be given to the impact of emerging hazardous PFAS on organisms for the health of ecosystems and human beings.

Microcosm experiment to test bacterial responses to perfluorooctanoate exposure.

The impact of perfluoroalkyl and polyfluoroalkyl substances on microbial communities is challenging to investigate in situ because of the complexity and dynamics of natural ecosystems. In the present study, four microcosms were established to explore the impact of perfluorooctanoate (PFOA) on bacterial communities in riverine and marine settings. PFOA distribution between the aqueous and sedimentary phases fluctuated in both PFOA-amended and unamended control systems. PFOA was more rapidly partitioned into the sediment in marine than in riverine microcosms. Differences in iron concentration and salinity may influence PFOA exchange between water and sediment. In marine microcosms, the alpha diversity of bacterial communities was significantly correlated to PFOA concentration. PFOA tended to correlate more strongly with bacterial community composition in water than in sediment. At the whole system level, Lefse's analysis indicated Algoriphagus halophilus as biomarkers for PFOA exposure in both riverine and marine systems, and the family Flavobacteriaceae were also more abundant in the exposed systems. In terms of temporal variation (comparison between three time points in the systems), metastat analysis showed great variability of potential PFOA-sensitive bacteria at the genus level. As such, most PFOA-sensitive genera were transitory and variable and existed for a short term in different systems (river, sea, blank, and experiment) and phases. Compared with other PFOA-sensitive genera, we suggest that further research is carried out to explore the use of Limnobacter as a bioindicator for temporal monitoring of PFOA pollution.

Diffusive gradients in thin films (DGT) probe for effectively sampling of per- and polyfluoroalkyl substances in waters and sediments.

The passive sampling technique, diffusive gradients in thin films (DGT) has attracted increasing interests as an in-situ sampler for organic contaminants including per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been questioned because of the small effective sampling area (3.1 cm2). In this study, we developed a DGT probe for rapid sampling of eight PFAS in waters and applied it to a water-sediment system. It has a much larger sampling area (27 cm2) and as a result lower method quantification limits (0.15 - 0.21 ng/L for one-day deployment and 0.02 - 0.03 ng/L for one-week deployment) and much higher (by > 10 factors) sampling rate (100 mL/day) compared to the standard DGT (piston configuration). The sampler could linearly accumulate PFAS from wastewater, was sensitive enough even for a 24 hr deployment with performance comparable to grab sampling (500 mL). The DGT probe provided homogeneous sampling performance along the large exposure area. The use of the probe to investigate distributions of dissolved PFAS around the sediment-water interface was demonstrated. This work, for the first time, demonstrated that the DGT probe is a promising monitoring tool for trace levels of PFAS and a research tool for studying their distribution, migration, and fate in aquatic environments including the sediment-water interface.

Beyond the Tip of the Iceberg: Suspect Screening Reveals Point Source-Specific Patterns of Emerging and Novel Per- and Polyfluoroalkyl Substances in German and Chinese Rivers.

Only a few dozens of the several thousand existing per- and polyfluoroalkyl substances (PFAS) are monitored using conventional target analysis. This study employed suspect screening to examine patterns of emerging and novel PFAS in German and Chinese river water affected by industrial point sources. In total, 86 PFAS were (tentatively) identified and grouped into 18 structure categories. Homologue patterns revealed distinct differences between fluoropolymer production sites of the two countries. In the Chinese Xiaoqing River Basin, the C8 homologue was the most prevalent compound of the emerging series of chlorinated perfluoroalkyl carboxylic acids (Cl-PFCAs) and perfluoroalkylether carboxylic acids (PFECAs). In contrast, C6 and shorter homologues were dominant in the German Alz River. This indicates that the phaseout of long-chain compounds in Europe and their ongoing production in Asian countries also apply to unregulated emerging PFAS classes. Additional characteristics to differentiate the point sources were the peak area ratio of perfluorobutane sulfonic acid (PFBS) versus the emerging compound hydro-substituted PFBS (H-PFBS) as well as the occurrence of byproducts of the sulfonated tetrafluoroethylene-based polymer Nafion. The large number of identified unregulated PFAS underlines the importance of a grouping approach on a regulatory level, whereas the revealed contamination patterns can be used to estimate, prioritize, and minimize contributions of specific sources.

Habitat-dependent trophic transfer of legacy and emerging halogenated flame retardants in estuarine and coastal food webs near a source region.

With the phase-out of legacy halogenated flame retardants (HFRs), such as decabromodiphenyl ether (BDE-209), emerging ones, such as decabromodiphenyl ethane (DBDPE), are being widely produced. We conducted field campaigns to assess the trophic transfer of legacy and emerging HFRs in estuarine and coastal food webs of Laizhou Bay, which are located near the largest HFR manufacturing base in China. Seawater, sediment, plankton, invertebrates, and fish were collected from both sites. BDE-209 was the predominant compound in the estuary, whereas DBDPE was the main contributor to HFRs in the bay, followed by BDE-209. Invertebrates, especially bivalves and sea cucumbers, showed higher levels of BDE-209 and DBDPE than fish. The HFR levels in the organisms of the two coastal zones were comparable to each other, although their concentrations in the estuarine water were one order of magnitude higher than those in the bay. The HFR profiles in benthic organisms were similar to those in the sediments, indicating that the bioaccumulation of HFRs in coastal food webs depended on the habitat. The ΣHFR concentrations followed the order filter-feeding > carnivorous for invertebrates, and demersal non-migratory fish showed higher HFR levels than oceanodromous fish. The trophic magnification factors estimated for BDE-209, dechlorane plus, and DBDPE were lower than 1, suggesting biodilution potential in both food webs, whereas several PBDE congeners exhibited biomagnification capacity. Feeding habits, habitats, hydrophobicity, bioavailability, and metabolism may be the main factors impacting the bioaccumulation of HFRs in organisms in estuarine-coastal ecosystems of northern China.

First Report on the Bioaccumulation and Trophic Transfer of Perfluoroalkyl Ether Carboxylic Acids in Estuarine Food Web.

As novel alternatives to legacy poly- and perfluoroalkyl substances (PFAS), perfluoroalkyl ether carboxylic acids (PFECAs) have been widely detected in the environment; however, there is limited information and knowledge regarding their bioaccumulation and trophic transfer behavior along the food chain. This research presents the first known published data on the bioaccumulation and trophic transfer characteristics of PFECAs in a source-impacted estuary. Elevated PFECA concentrations were observed in organisms (for instance, conch, with perfluoro-2-methoxyacetic acid (PFMOAA) concentration reaches up to 16 700 ng/g dry weight (dw)), indicating exposure risks to the consumers. Conch can be acted as a potential environmental bioindicator of PFMOAA. PFMOAA, hexafluoropropylene oxide trimer acid (HFPO-TrA) and PFOA were predominant detected in biotas. On the basis of trophic magnification factors (TMFs), PFECAs with ≥6 perfluorinated carbons (HFPO-TrA, hexafluoropropylene oxide tetramer acid (HFPO-TeA) and perfluoro (3, 5, 7, 9, 11-pentaoxadodecanoic) acid (PFO5DoA)) could be biomagnified along the food chain (TMF > 1), while PFMOAA with the least perfluorinated carbons undergone biodilution (TMF < 1). As seafood is an important dietary source of protein to human, there is a potential health risk related to the consuming polluted aquatic products.

Exploring source footprint of Organophosphate esters in the Bohai Sea, China: Insight from temporal and spatial variabilities in the atmosphere from June 2014 to May 2019.

Organophosphate esters (OPEs) are still produced and used in large quantities in the world-wide, and the environmental burden and behavior have generated widespread concern, especially in some large-scale waterbodies. This study conducted a comprehensive assessment on the temporal and spatial variabilities and budget of OPEs to trace the source for the Bohai Sea (BS), based on a 5-year seasonal monitoring campaign (June 2014 to May 2019) of 12 atmospheric sites around the BS and our previous studies. The average concentration of Σ10OPEs in atmosphere during the sampling period was 7.65 ± 6.42 ng m-3, and chlorinated OPEs were the major compounds. The Seasonal-Trend decomposition procedure based on Loess (STL) analyzed that during the 5-year sampling period, the atmospheric concentrations of Σ10OPEs had a slightly increasing trend with a rate of + 0.092 ng m-3 yr-1, and the seasonal concentrations had a distinct seasonal distribution. The highest concentration of Σ10OPEs was observed at the sampling site of Dalian, followed by Tianjin, Yantai, and Beihuangcheng. The estimation of the fugacity ratios and air-water gas exchange fluxes established that the concentration levels of two major components of chlorinated OPEs (tris-(2-chloroethyl) phosphate (TCEP) and tris-(1-chloro-2-propyl) phosphate (TCPP)) in the atmosphere were dominated by their volatilization from BS's seawater (1.24 ± 0.46 t yr-1 for TCEP and 5.15 ± 2.15 t yr-1 for TCPP), with 73% deriving from the coastal seawater. The budget assessment suggested that the volatile fluxes of TCEP and TCPP accounted for 8% and 29% of their storages (15.6 ± 5.32 t for TCEP and 17.6 ± 6.70 t for TCPP) in the BS seawater, which were mainly contributed by continental river input (20% for TCEP and 42% for TCPP). The efforts indicated that river inputs of TCEP and TCPP needed to be paid more attention for the improvement of environmental quality of the BS.

Occurrence and ecological risk assessment of neonicotinoids and related insecticides in the Bohai Sea and its surrounding rivers, China.

Systemic insecticides like neonicotinoids and the phenylpyrazole insecticide fipronil are the most widely applied insecticides around the world. Multiple studies analyzed insecticide residues in freshwater systems, but data on seawater contamination levels are scarce. This study investigates the spatiotemporal distribution and ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected transformation products (TPs) in the Chinese Bohai Sea and its surrounding rivers. Well-established neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) and TPs of fipronil and imidacloprid were frequently detected (detection frequency (DF): 42-100%) in freshwater. The median total insecticide concentration in freshwater was significantly higher in summer (72.4 ng•L-1) than in fall (23.4 ng•L-1), with major contributions from neonicotinoids, suggesting that pollution originates mostly from diffuse sources. In 2018, acetamiprid, desnitro-imidacloprid, fipronil-desulfinyl and thiacloprid were abundant in seawater (DF: 47-100%), indicating a high stability of acetamiprid and thiacloprid and a rapid photodegradation of fipronil and imidacloprid in surface waters. These results indicate that the continued use of these parent compounds may lead to their accumulation and/or of their TPs in shallow coastal seas. Consequently, this may lead to their transport to open seas, increasing their potential risk to marine organisms. Similarities between contaminant fingerprints in freshwater and seawater strongly suggest riverine discharges as main pollution source of adjacent coastal areas. This is the first study to perform an ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected TPs on marine ecosystems. Fipronil and its TPs demonstrated to be environmentally relevant with potential high risks for aquatic species. Our study provides novel insights into the fate and ecological risk of fipronil, neonicotinoids, sulfoxaflor and their TPs to marine species in shallow coastal seas.

Organophosphate flame retardants, tetrabromobisphenol A, and their transformation products in sediment of e-waste dismantling areas and the flame-retardant production base.

Due to the prohibition of polybrominated diphenyl ethers, organophosphate flame retardants (OPFRs) and tetrabromobisphenol A (TBBPA) have become emerging flame retardants. However, knowledge about their occurrence, especially their transformation products, is still limited. This study collected sediment samples from two rivers, i.e., Lianjiang River (located at an e-waste dismantling area) and Xiaoqing River (situated at a flame retardant production base), to investigate the occurrence, composition, and spatiality distribution of OPFRs, TBBPA, and their transformation products. Both targets were detected in the Lianjiang River in the range of 220-1.4 × 104 and 108-3.1 × 103 ng/g dw (dry weight) for OPFRs and TBBPA, and 0.11-2.35 and 4.8-414 ng/g dw for their respective transformation products, respectively. The concentrations of OPFRs and TBBPA in the Xiaoqing River ranged from 4.15 to 31.5 and 0.76-2.51 ng/g dw, respectively, and no transformation products were detected. Different compositional characteristics of OPFRs and distinct spatial distribution from mainstream and tributary observed between the two rivers are attributed to the difference in the local industries. Spatial distribution and principal component analysis indicated that e-waste dismantling activities could be a vital source of local pollution. Besides, the confluence of tributaries seemed to determine the contaminant levels in the Xiaoqing River. Also, concentration ratios and Spearman's correlation between metabolites and parent chemicals were analyzed. Low concentration ratios (3.6 ×10-4 to 0.16) indicated a low transformation degree, and Spearman's correlation analysis suggested transformation products were partly stemming from commercial products. Considering the limited study of these transformation products, more studies on their sources, transform mechanism, and toxicity are required.

Tetrabromobisphenol A induced reproductive endocrine-disrupting effects in mussel Mytilus galloprovincialis.

Tetrabromobisphenol A (TBBPA) pollution in marine environmental media poses great risks to marine organisms due to its potential endocrine-disrupting effects. However, limited attention of TBBPA's endocrine-disrupting effects has been paid on marine invertebrates. In this work, the reproductive endocrine-disrupting effects of TBBPA were evaluated by observing the gametes development, quantifying the gender-specific gene expression, and determining vertebrate sex hormones in mussels Mytilus galloprovincialis treated with TBBPA for 30 days. Additionally, transcriptomic profiling and enzymes activities were conducted to investigate the potential mechanisms of reproductive endocrine-disrupting effects. We found that promotion of gametogenesis and alterations of vertebrate sex hormones occurred in TBBPA-treated mussels of both sexes. Meanwhile, estrogen sulfotransferase (SULT1E1) and steroid sulfatase (STS) were up-regulated at transcript level as a result of TBBPA treatments, suggesting that TBBPA disrupted the steroidogenesis in mussels through promoting steroids sulfonation and hydrolysis of sulfate steroids. The induction of SULTs for TBBPA biotransformation might be responsible for the dysregulation of steroidogenesis and steroids metabolism. Overall, these findings provide a new insight into assessing impact of TBBPA as well as TBBPA biomonitoring in marine environment.