Shift from legacy to emerging per- and polyfluoroalkyl substances for watershed management along the coast of China.

Per- and polyfluoroalkyl substances and their short-chain alternatives have attracted world-wide attention due to their widespread presence and persistence in the environment. However, the sources, environmental fate, and driving forces of PFAS in coastal ecosystems remain poorly understood. In this study, the spatial distribution, source apportionment, and driving mechanisms of PFAS were investigated through a comprehensive analysis of water samples collected along the China's coastline. The concentrations of Σ25PFAS in water samples followed a general pattern, with higher levels observed in northern coastal zones of China than the south, ranging from 0.72 to 1872.21 ng L-1. PFOA and PFBA were dominant. Emerging short-chain PFAS, such as PFBS, PFBA, F-53B and GenX, were frequently detected, with detection rates of 97%, 99%, 95% and 77%, respectively. This indicated a shift in coastal PFAS contamination from legacy compounds to emerging short-chain alternatives. Source apportionment using the Positive Matrix Factorization model identified key contributors to PFAS pollution, including textile production, volatile precursors, precious metal industries, aqueous film-forming foam, metal-plating, electrochemical fluorination, and fluoropolymer manufacturing. Additionally, PFAS concentrations were significantly positively correlated with cultivated land, urban area, and wastewater discharge, while negatively correlated with annual precipitation and woodland coverage (p<0.05). Socio-economic development was identified as a major driver of PFAS emissions, while the hydrological factors and vegetation coverage can significantly enhance watershed resilience against PFAS pollution.

Co-emissions of fluoride ion, fluorinated greenhouse gases, and per- and polyfluoroalkyl substances (PFAS) from different fluorochemical production processes.

Fluorochemical industry is an emerging industry leading to environmental emissions of fluoride ion, fluorinated greenhouse gases (GHGs) and per- and polyfluoroalkyl substances (PFASs) globally. Chlorofluorocarbon (CFCs) and hydrochlorofluorocarbon (HCFCs) are the primary causes of ozone layer depletion, and together with hydrofluorocarbons (HFCs), they contribute to global climate warming. PFAS are emerging persistent organic pollutants, comprising thousands of materials including perfluoroalkyl acids (PFAAs), perfluoroalkane sulfonamides (FASAs), and fluoropolymers.As the implementation of the Montreal Protocol and the Stockholm Convention makes progress, fluorochemical industry is searching for alternatives like HFCs, perfluoroalkyl ether carboxylic acids (PFECAs) and etc. Even though studies on chemical processes and environmental influences of the fluorochemical industry are plentiful, research on emissions of fluorine chemicals from different fluorochemical industry is still scarce. In this study, we conducted on-site sampling to analyze the distribution of fluorine chemicals in the surrounding environment of the fluorochemical industrial sites. The sampling sites represent different stages of fluorochemical industry production, including fluorite mining, synthesis of fluorochemical raw materials like fluorocarbons, and fine fluorine product processing which is mostly PFAS. Results show that at the fluorite mining stage, concurrent emissions of fluoride ion and CFC-12 contribute to the primary environmental issue. Perfluorooctanoic acid (PFOA) and some short-chain PFASs like perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluoroheptanoic acid (PFHpA), and perfluorobutanesulfonic acid (PFBS) are the main pollutants from fluocarbons production, accompanied by emissions of fluorinated GHGs such as HFC-32, and HCFC-22. At the fine fluorine product synthesis stage where produces fluoropolymers, perfluoropolyethers and fluorinated surfactants, PFAS especially for emerging alternatives PFECAs like hexafluoropropylene oxide dimer acid (HFPODA) and Perfluoro-4-oxapentanoic acid (PF4OPeA), as well as fluorinated GHGs like HFC-23 and HFC-227ea, require increasing attention.

Bioaccumulation and trophic transfer of per- and polyfluoroalkyl substances in a subtropical mangrove estuary food web.

Mangrove estuaries are an important land-sea transitional ecosystem that is currently under various pollution pressures, while there is a lack of research on per- and polyfluoroalkyl substances (PFAS) in the organisms of mangrove estuaries. In this study, we investigated the distribution and seasonal variation of PFAS in the tissues of organisms from a mangrove estuary. The PFAS concentrations in fish tissues varied from 0.45 ng/g ww to 17.67 ng/g ww and followed the order of viscera > head > carcass > muscle, with the highest tissue burden found in the fish carcass (39.59 ng). The log BAF values of PFDoDA, PFUnDA, and PFDA in the whole fish exceeded 3.70, indicating significant bioaccumulation. The trophic transfer of PFAS in the mangrove estuary food web showed a dilution effect, which was mainly influenced by the spatial heterogeneity of PFAS distribution in the estuarine environment, and demonstrated that the gradient dilution of PFAS in the estuary habitat environment can disguise the PFAS bio-magnification in estuarine organisms, and the larger the swimming ranges of organisms, the more pronounced the bio-dilution effect. The PFOA-equivalent HRs of category A and B fish were 3.48-5.17 and 2.59-4.01, respectively, indicating that mangrove estuarine residents had a high PFAS exposure risk through the intake of estuarine fish.

Differentiable Logic Policy for Interpretable Deep Reinforcement Learning: A Study From an Optimization Perspective.

The interpretability of policies remains an important challenge in Deep Reinforcement Learning (DRL). This paper explores interpretable DRL via representing policy by Differentiable Inductive Logic Programming (DILP) and provides a theoretical and empirical study of DILP-based policy learning from an optimization perspective. We first identified a fundamental fact that DILP-based policy learning should be solved as a constrained policy optimization problem. We then proposed to use Mirror Descent for policy optimization (MDPO) to deal with the constraints of DILP-based policies. We derived the closed-form regret bound of MDPO with function approximation, which is helpful to the design of DRL frameworks. Moreover, we studied the convexity of DILP-based policy to further verify the benefits gained from MDPO. Empirically, we experimented MDPO, its on-policy variant, and 3 mainstream policy learning methods, and the results verified our theoretical analysis.

Per- and polyfluoroalkyl substances (PFASs) in water and sediment from a temperate watershed in China: Occurrence, sources, and ecological risks.

Per- and polyfluoroalkyl substances (PFASs) are a class of synthetic organic fluorides that have been widely used in various industrial and consumer applications. However, their potential ecological risks have raised concerns. In this study, PFASs were investigated in different environmental media in the Jiulong River and Xiamen Bay regions of China, revealing widespread contamination of PFASs in the watershed. PFBA, PFPeA, PFOA, and PFOS were detected in all 56 sites, with short-chain PFASs dominating (72 % of the total). Novel PFAS alternatives, including F53B, HFPO-DA, and NaDONA, were detected in >90 % of the water samples. Seasonal and spatial variations in PFAS concentrations were observed in the Jiulong River estuary, while Xiamen Bay was not significantly affected by seasonal changes. In sediment, PFSAs were dominant with long-chains while PFCAs with short-chains, and the occurrence was influenced by water depth and salinity. PFSAs were more inclined to be adsorbed in sediments than PFCAs, and log Kd of PFCAs increased with the numbers of -CF2-. Paper packaging, machinery manufacturing, WWTP discharge, airport and dock activities were the dominant sources of PFASs. Risk quotient showed that PFOS or PFOA may pose high toxicity to Danio rerio and Chironomus riparius. Although the overall ecological risk in the catchment is still low, the hazard of bio-concentration under long-term exposure and multi-pollutant synergistic toxicity cannot be ignored.

Per- and polyfluoroalkyl substances in marine organisms along the coast of China.

Per- and polyfluoroalkyl substances (PFASs) are a large and complex class of synthetic chemicals widely used in industrial and domestic products. This study compiled and analyzed the distribution and composition of PFASs in marine organisms sampled along the coast of China from 2002 to 2020. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were dominant in bivalves, cephalopods, crustaceans, bony fish and mammals. PFOA in bivalves, crustaceans, bony fish and mammals gradually decreased from north to south along the coast of China, and the PFOA contents of bivalves and gastropods in the Bohai Sea (BS) and the Yellow Sea (YS) were higher than those of PFOS. The increased production and use of PFOA have been detected by biomonitoring temporal treads in mammals. For the organisms in the East China Sea (ECS) and the South China Sea (SCS), which were less polluted by PFOA compared to BS and YS, PFOS was universally higher than PFOA. The PFOS of mammals with high trophic levels was significantly higher than that of other taxa. This study is conducive to better understanding the monitoring information of PFASs of marine organisms in China and is of great significance for PFAS pollution control and management.

Urbanization affects spatial variation and species similarity of bird diversity distribution.

Although cities are human-dominated systems, they provide habitat for many other species. Because of the lack of long-term observation data, it is challenging to assess the impacts of rapid urbanization on biodiversity in Global South countries. Using multisource data, we provided the first analysis of the impacts of urbanization on bird distribution at the continental scale and found that the distributional hot spots of threatened birds overlapped greatly with urbanized areas, with only 3.90% of the threatened birds' preferred land cover type in urban built-up areas. Bird ranges are being reshaped differently because of their different adaptations to urbanization. While green infrastructure can improve local bird diversity, the homogeneous urban environment also leads to species compositions being more similar across regions. More attention should be paid to narrow-range species for the formulation of biodiversity conservation strategies, and conservation actions should be further coordinated among cities from a global perspective.

[Seasonal Variation and Source Analysis of Water-soluble Inorganic Ions in Fine Particulate Matter in Zhengzhou].

In order to explore the characteristics of PM2.5 concentration and water-soluble inorganic ions in Zhengzhou City, a total of 170 PM2.5 samples were collected in the spring, summer, autumn, and winter seasons of 2016, with 30 days continuous sampling during each season. The mass concentration of PM2.5 was analyzed gravimetrically, water-soluble inorganic ions were determined by ion chromatography, and principle component analysis was employed for source apportionment. The results showed that the mass concentration of PM2.5 was 150.72µg·m-3 during the sampling period. The mass concentration was highest in winter and lowest in summer, and that of autumn is higher was higher than that of spring. The ions SO42-, NO3-, and NH4+ were the major WSIs found in PM2.5, accounting for 92.55%, 92.94%, 93.06%, and 93.15% of the total amount of the seven ions found in spring, summer, autumn, and winter, respectively. The anion-to-cation ratio was 0.886, which indicated that PM2.5 was slightly alkaline in Zhengzhou. Secondary inorganic species, including NH4+, NO3-, and SO42- were the major components of the water-soluble ions. These ions most likely existed in the form of NH4NO3 and (NH4)2SO4 during spring and summer, while they were present as NH4NO3, (NH4)2SO4 and NH4HSO4 in autumn. In addition to these three forms, NH4Cl or other forms may exist in winter. Industrial emissions, combustion, secondary transformation, soil, and construction dust were the major sources of the water-soluble ions in PM2.5.

[Interannual Variation of Metal Elements and Water-Soluble Ions in PM2.5 During Wintertime in Xinxiang and Their Source Apportionment].

To study the interannual variations of chemical composition and source apportionment, a field campaign was carried out to collect the PM2.5 temperance sample during the winter of 2015 and the winter of 2016 in Xinxiang urban areas. PM2.5 mass concentration, metal elements, and the water-soluble ions were determined and meteorological factors were recorded simultaneously. The results showed that the daily mean concentrations of PM2.5 indicated serious pollution with values of 226 µg·m-3 and 224 µg·m-3 in 2015 and 2016, respectively. The Cd and Pb elements in PM2.5 were significantly enriched, with EF more than 1000. However, compared with 2015, the enrichment effect of most metal elements showed a trend of decrease in 2016. The water-soluble ions were mainly composed of SO42-, NO3-, and NH4+. The results showed a trade-off effect between metal elements and water-soluble ions in the two study periods. The results of PCA and PMF analyses show that there were four main emission sources in Xinxiang city in winter, namely dust, secondary source, industrial source, and fossil fuel combustion source. Moreover, the main sources of PM2.5 was the mixed source of soil and building dust and secondary aerosol pollution, with contributions of 37.46% and 34.94% in the winters of 2015 and 2016, respectively.