First report of perfluoroalkyl acids (PFAAs) in the Indus Drainage System: Occurrence, source and environmental risk.

Perfluoroalkyl acids (PFAAs) are of global interest due to their persistence in the aquatic environment. This study assessed the occurrence of PFAAs in the Indus Drainage System and discerned their potential sources and environmental risks for the first time in Pakistan. 13 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkyl sulfonates (PFSAs) were analyzed to verify the dominant prevalence of short-chain PFAAs in the environment since the phase-out of long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). A significant variation (p ≤ 0.05) of individual PFAAs between the monitoring sites was confirmed by data normality tests Kolmogorov-Smirnov and Shapiro-Wilk, suggesting that different locations contribute differently to individual PFAAs concentrations. ΣPFAAs concentrations in riverine water and sediments ranged from 2.28 to 221.75 ng/L and 0.78-29.19 ng/g dw, respectively. PFBA, PFPeA, and PFHxA were the most abundant PFAAs, and on average accounted for 14.64, 13.75, and 12.97 ng/L of ∑PFAAs in riverine water and 0.34, 0.64, and 0.79 ng/g dw of ∑PFAAs in sediments. ΣPFAAs mean contamination in the drainage was significantly (p < 0.05) high in River Chenab followed by River Indus > Soan > Ravi > Kabul > Swat with more prevalence of short-chain (C4-C7) PFCAs followed by PFOA, PFBS, PFOS, PFNA, PFDA, PFHxS, PFUnDA, and PFDoDA. The correlation analysis determined the PFAAs' fate and distribution along the drainage, indicating that PFAAs with carbon chains C4-C12, except for PFSAs with carbon chains C6-C8, were most likely contaminated by the same source, the values of Kd and Koc increased linearly with the length of the perfluoroalkyl carbon chain, better understand the transport and partitioning of individual PFAAs between riverine water and sediments, where the HCA and PCA discerned industrial/municipal wastewater discharge, agricultural and surface runoff from nearby fields, and urban localities as potential sources of PFAAs contamination. The collective mass flux of short-chain (C4-C7) PFCAs was 5x higher than that of PFOS + PFOA, suggesting a continuous shift in the production and usage of fluorinated replacements for long-chain PFAAs with short-chain homologs. In terms of risk, individual PFAAs pollution in the drainage was within the world's risk thresholds for human health, with the exception of PFBA, PFPeA, PFHpA, PFHxA, PFOA, PFNA, and PFBS, whereas for ecology, the concentrations of individual PFAAs did not exceed the ecological risk thresholds of the United States of America, Canada, European Union (EU), Italy, Australia, and New Zealand, with the exception of PFSAs, whose detected individual concentrations were significantly higher than the EU, Australian and New Zealander PFSAs guidelines of 0.002 µg/L, 0.00047 µg/L, 0.00065 µg/L, 0.00013 µg/L, and 0.00023 µg/L, respectively, which may pose chronic risks to the regional ecosystem and population.

Occurrence, Spatial Distribution and Health Risk of Hexabromocyclododecane (HBCD) in Source Water in the Lower Yangtze River, China.

The occurrence and health risk of hexabromocyclododecane (HBCD), a brominated flame retardant with its three diastereoisomers, in drinking water sources in the lower Yangtze River in China was investigated. Its concentration ranged from 0.58 to 3.71 ng/L and averaged at 1.18 ng/L. Among the three diastereoisomers of α-, ß- and γ-HBCD, γ-HBCD was the dominant one accounting for 44% (ranging 27-82%) to the total concentration. Source of HBCD in the contaminated site was discussed according to its spatial distribution and diastereoisomer profile. The margin of exposure (MOE) approach was applied to evaluate the health risk of HBCD through drinking water by estimated exposure and derived reference dose. The MOE was 17 for adults and 12 for children in the worst-case scenario, suggesting a trivial health concern.

Transport and environmental risks of perfluoroalkyl acids in a large irrigation and drainage system for agricultural production.

The quality of irrigation water and drainage water is essential for local ecosystem and human health in agricultural regions. In this study, the transport analysis, source identification, and environmental risk assessment of perfluoroalkyl acids (PFAAs) were conducted in the largest irrigation area in northern China. The concentrations of the total PFAAs (ΣPFAA) ranged from 41.5 to 263 ng/L in surface water, and the short-chain perfluoroalkyl carboxylic acids (PFCAs) and perfluorooctanoic acid (PFOA), were dominant with a total contribution of 94%. Generally, the ΣPFAA levels increased from irrigation waters to drainage and receiving lake waters. PFOA showed the highest increase, with potential emission sources located in the catchment of the sub main drainage ditch D5. More PFOA (36.8 kg/y) was outflowed from Ulansuhai Lake to the Yellow River than that inflowed from the Yellow River to the irrigation district (6.15 kg/y). The results of a risk assessment indicated that avian wildlife living in Ulansuhai Lake were threatened by the PFOA and perfluorobutane sulfonate (PFBS) pollution. The estimated daily intakes (EDIs) of the sum of the PFOA, perfluorononanoic acid (PFNA), perfluorohexane sulfonic acid (PFHxS), and perfluorooctane sulfonic acid (PFOS) through aquatic food consumption for people with the different aquatic food preferences accounted for 6-42% (urban) and 4-27% (rural) of the strictest tolerant daily intake (TDI) value. The results of this study highlight the impact of local emissions of PFAS on massive irrigation and drainage systems, and ultimately, the ecosystem and human health.

Endocrine disrupting compounds, pharmaceuticals and personal care products in the aquatic environment of China: Which chemicals are the prioritized ones?

Endocrine disrupting compounds (EDCs), pharmaceuticals and personal care products (PPCPs) have been of great concern as emerging contaminants of aquatic environment. Therefore, there is an urgent need to identify top contaminants so as to allocate better management measures. A list of 77 pharmaceuticals, 20 personal care products (PCPs) and 36 EDCs that were frequently detected in Chinese surface waters was examined in this study. The reported chemicals were concentrated in the highly populated and industrialized areas of China (e.g. the Bohai region, Yangtze River Delta and Pearl River Delta). The concentrations of EDCs and PPCPs were closely related to human domestic sewage and industrial wastewater discharge, and they were generally higher than or at least comparable to most of global rivers. Based on the proximity between the medians of reported exposure concentrations and effect concentrations, the risk ranking results showed that EDCs, e.g. estrone (E1), estriol (E3), 17α-ethynylestradiol (EE2), and PCPs, e.g. triclocarban (TCC), triclosan (TCS), were deemed to represent higher risks to aquatic organisms across China, as well as the Northern rivers (including the Bohai region), Yangtze River Basin, and Pearl River Basin. Pharmaceuticals posed relatively lower risks to organisms owing to their higher effect concentrations. By comparison, the Northern rivers were hotspots where many chemicals were identified as posing greater risks than the Yangtze River Basin and Pearl River Basin. Fish was the most sensitive taxa to 17ß-estradiol (ßE2) and EE2, which was almost 100,000 times higher risk than algae and worms. Atrazine (ATZ) and galaxolide (HHCB), posed comparably higher risks to algae and worms. The results of this work provide a sound guidance for future monitoring and management of chemicals in China.

Drivers of change in China's energy-related CO2 emissions.

CO2 emissions are of global concern because of climate change. China has become the largest CO2 emitter in the world and presently accounts for 30% of global emissions. Here, we analyze the major drivers of energy-related CO2 emissions in China from 1978 when the reform and opening-up policy was launched. We find that 1) there has been a 6-fold increase in energy-related CO2 emissions, which was driven primarily (176%) by economic growth followed by population growth (16%), while the effects of energy intensity (-79%) and carbon intensity (-13%) slowed the growth of carbon emissions over most of this period; 2) energy-related CO2 emissions are positively related to per capita gross domestic product (GDP), population growth rate, carbon intensity, and energy intensity; and 3) a portfolio of command-and-control policies affecting the drivers has altered the total emission trend. However, given the major role of China in global climate change mitigation, significant future reductions in China's CO2 emissions will require transformation toward low-carbon energy systems.

Hydrogeochemistry and quality of surface water and groundwater in the drinking water source area of an urbanizing region.

The water quality in drinking water source area is essential for human health. Due to rapid urbanization and industrialization, the pollutants, especially trace elements, are continuously discharged into aquatic environment and pose a risk to human health. An extensive investigation was carried out in drinking water source area in highly urbanized Tianjin of China. Long-term monitoring data of the water body was collected on conventional physical and chemical parameters (pH, ions, TOC etc.) and metallic elements (Hg, As Cd, Pb, Co, U etc.) from 2005 to 2017. Our results showed that CaMg-Cl-SO4 and CaMg-HCO3 were the two prominent hydrochemical materials, implying that the pollution of aquatic system was mainly caused by anthropogenic activities and mineral dissolution within terms of drinking water guidelines (national and international standards), the concentrations of arsenic (As) and iron (Fe) were beyond the quality standards. Multivariate statistical approaches were applied to assess the origins of the elements. The results showed that human activities, as well as endogenous release, contributed significantly to appearance of trace elements. A transformation from low-trophic state to high-trophic state was in progress from 2005 to 2017 in Yuqiao reservoir, and most of the water was not heavily polluted by trace elements. The health risk assessment suggested that As had the potential to cause carcinogenic harm to the local residents, with daily dietary ingestion as the most predominant pathway.

Urban-rural gradients of polycyclic aromatic hydrocarbons in soils at a regional scale: Quantification and prediction.

The quantitative study of urban-rural gradients for persistent organic pollutants (POPs) is extremely important to understand the behavior of POPs as well as for ecological risk assessment and management. In this study, a practical urban-rural gradient model (URGM) was developed using atmospheric point source diffusion combined with a fugacity approach to test potential mathematical relationships among urban and rural soils. The mean value of polycyclic aromatic hydrocarbons (PAHs) for urban soils (0-2-km sites) was 570.80 ng/g, and was approximately 3.5 times higher than rural soils (30-50 km sites). Significant linear correlations were found between the amounts of PAHs in the surface soil and the city population and between the soil concentration and artificial surface area. Urban-rural PAH concentrations were simulated by the URGM and calibrated by city population and land-cover data, with average relative errors of 12.84%. The results showed that the URGM was suitable for simulating urban-rural PAH concentrations at a regional scale. The combustion of fossil fuels, biomass, and coal was the main source of soil PAHs in the study area, and the characteristic ratios of PAHs indicated a transition trend from pyrogenic to petrogenic sources along the urban-rural transects. This study thus provides a combined method for quantifying urban-rural gradients of PAHs and can thereby promote quantitative research on coupling among land cover, socio-economic data, and POP concentrations.

Prevalent fecal contamination in drinking water resources and potential health risks in Swat, Pakistan.

Fecal bacteria contaminate water resources and result in associated waterborne diseases. This study assessed drinking water quality and evaluated their potential health risks in Swat, Pakistan. Ground and surface drinking water were randomly collected from upstream to downstream in the River Swat watershed and analyzed for fecal contamination using fecal indicator bacteria (Escherichia coli) and physiochemical parameters (potential of hydrogen, turbidity, temperature, electrical conductivity, total dissolved solid, color, odor and taste). The physiochemical parameters were within their safe limits except in a few locations, whereas, the fecal contaminations in drinking water resources exceeded the drinking water quality standards of Pakistan Environmental Protection Agency (Pak-EPA), 2008 and World Health Organization (WHO), 2011. Multivariate and univariate analyses revealed that downstream urbanization trend, minimum distance between water sources and pit latrines/sewerage systems, raw sewage deep well injection and amplified urban, pastures and agricultural runoffs having human and animal excreta were the possible sources of contamination. The questionnaire survey revealed that majority of the local people using 10-20years old drinking water supply schemes at the rate of 73% well supply, 13% hand pump supply, 11% spring supply and 3% river/streams supply, which spreads high prevalence of water borne diseases including hepatitis, intestinal infections and diarrhea, dysentery, cholera, typhoid fever, jaundice and skin diseases in children followed by older and younger adults.

Multimedia fate and transport simulation of perfluorooctanoic acid/ perfluorooctanoate in an urbanizing area.

Strong global demand leads to significant production of fluoropolymers (FP) in China which potentially release large quantities of perfluorooctanoic acid/perfluorooctanoate (collectively called PFOA/PFO) to the environment. Modelling the fate and transport of PFOA/PFO provides an important input for human health risk assessment. Considering the effects of urbanization and existing forms of PFOA/PFO, this study used the modified multispecies Berkeley-Trent-Urban-Rural model to simulate the transfer behavior of PFOA/PFO in the Bohai Rim, China. Spatial distributions of PFOA/PFO emissions during the year 2012 for the study area were illustrated. About two thirds of the total amount of PFOA/PFO was estimated to be released into fresh water, and the total releases to rural areas were 160-fold higher than those to urban areas due to the location of fluorochemical industrial parks. The simulations predicted that hydrosphere was the fate of PFOA/PFO, followed by soil and vegetation, which was consistent with field data. The highest PFOA/PFO concentration was modeled in the Xiaoqing River basin with a value of 32.57 µg/L. The PFOA/PFO concentrations in urban soils were generally higher than those in rural soils except for grids 1, 3 and 46. In addition, it was estimated that the total flux of PFOA/PFO entering into the Bohai Sea was 24.57 ton/year, 100-fold higher than that of perfluorooctane sulfonates (PFOS).

Distribution, source, and risk of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in urban and rural soils around the Yellow and Bohai Seas, China.

Between 1945 and 1983, China was the world's largest producer of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), and the second largest producer of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs). The provinces of Liaoning, Hebei, Tianjin, Shandong, and Jiangsu around the Yellow and Bohai Seas have a long history of production and usage of OCPs and PCBs. To investigate their residual concentration, distribution, risk level, and temporal degradation, 7 OCPs and 7 indicator PCBs were determined in surface soils collected around the Yellow and Bohai Seas. Residues of the 7 OCPs and 7 PCBs were in the range of 5.89-179.96 ng g-1 dry weight (dw) and non-detectable (ND)-385.67 ng g-1 dw, respectively. Tianjin and Hebei provinces recorded the highest concentrations of OCPs and PCBs, respectively. Moreover, OCPs residues had a significant relationship with agriculture and orchard land-use types, whereas PCBs residues occurred more in wasteland. Lifetime carcinogenic and non-carcinogenic risks of OCPs and PCBs through ingestion, inhalation, and dermal contact indicated that OCPs and PCBs residues in surface soils are at a low risk level.

An overview of hexabromocyclododecane (HBCDs) in environmental media with focus on their potential risk and management in China.

Hexabromocyclododecanes (HBCDs) are the subject of recent interest and potential risk assessment particularly in China due to its ubiquitous existence in a variety of environmental media. This paper reviews the recent studies conducted on HBCDs in different environmental media (air, soil, water, river sediment, sewage sludge, biota and daily food) in China. At the same time, human health risks via food and occupational exposure of HBCDs in production plants, expanded polystyrene (EPS) and extruded polystyrene (XPS) plants were assessed. The review reveals that HBCDs levels of air, soil, sediment, sewage sludge, biota and food presented a geographical variation in the eastern coastal regions of China. There were many factors resulting in the variation, such as sampling sites, climate and analytical method. In terms of diastereoisomer, α-HBCD and γ-HBCD were the predominant diastereoisomers in air, soil, sediment, and sewage sludge. In the water, α-HBCD and γ-HBCD shared the major proportion to the total HBCDs. However, only α-HBCD was the predominant diastereoisomer in biota. With regard to human exposure pathway to HBCDs, food was the major route for human exposure to HBCDs, especially meat. In addition, soil and road dust were also important exposure pathways. Furthermore, workers and residents, especially infants in and around waste dumping sites and industrial areas are exposed to the highest HBCDs levels among all the populations studied thus far. HBCDs posed a potential threat to the environment and human health. Therefore, risk assessment and management have an important role to play in preventing and mitigating HBCDs risks.

Pollution pathways and release estimation of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in central and eastern China.

China has gradually become the most important manufacturing and consumption centre for perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the world, and inadvertently become the world's major contamination hotspots. However, a systematic analysis of pollution pathways for PFOS/PFOA into the different environmental compartments and their quantification in China has yet to be carried out. This study focused on PFOS and PFOA release into the environment in the central and eastern region of China, which accounts for the vast majority of national emission. About 80-90% of PFOS/PFOA contamination in the Chinese environment was estimated to come directly from manufacturing and industrial sites mostly via wastewater discharge from these facilities. The other major contamination sources for PFOS were identified as being linked to aqueous fire-fighting foams (AFFFs), and pesticides including sulfluramid. For PFOA, following some way behind industrial wastewater, were industrial exhaust gas, domestic wastewater and landfill leachate as contamination sources. For surface water contamination, the major pollution contributors after industrial wastewater were AFFF spill runoff for PFOS, and domestic wastewater and precipitation-runoff for PFOA. The majority of PFOS that contaminated soil was considered to be linked with infiltration of AFFF and pesticides, while most PFOA in soil was attributed to atmospheric deposition and landfill leachate. Where groundwater had become contaminated, surface water seepage was estimated to contribute about 50% of PFOS and 40% of PFOA while the remainder was mostly derived from soil leaching. A review of the available monitoring data for PFOS/PFOA in the literature supported the view that industrial wastewater, landfill leachate and AFFF application were the dominant sources. Higher concentrations of PFOA than PFOS found in precipitation also corroborated the prediction of more PFOA release into air. To reduce PFOS/PFOA contamination of the Chinese environment the focus for control should be on industrial wastewater emissions.

Effects of Perfluorooctane sulfonate on immobilization, heartbeat, reproductive and biochemical performance of Daphnia magna.

In recent years, Perfluorooctane sulfonate (PFOS) was widely detected in Yellow-Bohai Sea and other areas, causing a series of adverse effects in aquatic organisms. However, present studies of its chronic and acute toxicity on aquatic organisms were far more inadequate. Therefore, in the present study, Daphnia magna was used to investigate PFOS toxicity on their immobilization, heartbeat, reproductive and biochemical performance in acute, subchronic and chronic exposure. The results showed that the 48h-EC50 value for immobilization was 79.35 mg L-1 and the toxicity was classified as intermediate. Heartbeat was significantly stimulated and reproductive parameters were significantly suppressed by PFOS, which can be used to reflect the toxicological effects on individuals. On the other hand, intrinsic rate of natural increase was more sensitive than reproductive parameters, which indicated negative responses on population dynamics of Daphnia magna. In addition, there were different degrees of inhibition on GST, CAT and ChE activity, which indicated three types of enzyme could become biomarkers to chronic PFOS exposure. Most of selected and evaluated endpoints have significant sensitivity to PFOS at the concentration of 8 mg L-1 during subchronic and chronic exposure.