Bisphenol A sorption on commercial polyvinyl chloride microplastics: Effects of UV-aging, biofilm colonization and additives on plastic behaviour in the environment.

Chemical additives are important components in commercial microplastics and their leaching behaviour has been widely studied. However, little is known about the potential effect of additives on the adsorption/desorption behaviour of pollutants on microplastics and their subsequent role as vectors for pollutant transport in the environment. In this study, two types of commercial polyvinyl chloride (PVC1 and PVC2) microplastics were aged by UV irradiation and biotic modification via biofilm colonization to investigate the adsorption and desorption behaviour of bisphenol A (BPA). Surface cracks and new functional groups (e.g., O-H) were found on PVC1 after UV irradiation, which increased available adsorption sites and enhanced H‒bonding interaction, resulting in an adsorption capacity increase from 1.28 µg/L to 1.85 µg/L. However, the adsorption and desorption capacity not showed significant changes for PVC2, which might be related to the few characteristic changes after UV aging with the protection of light stabilizers and antioxidants. The adsorption capacity ranged from 1.28 µg/L to 2.06 µg/L for PVC1 and PVC2 microplastics, and increased to 1.62 µg/L-2.95 µg/L after colonization by biofilms. The increased adsorption ability might be related to the N-H functional group, amide groups generated by microorganisms enhancing the affinity for BPA. The opposite effect was observed for desorption. Plasticizers can be metabolized during biofilm formation processes and might play an important role in microorganism colonization. In addition, antioxidants and UV stabilizers might also indirectly influence the colonization of microorganisms' on microplastics by controlling the degree to which PVC microplastics age under UV. The amount of biomass loading on the microplastics would further alter the adsorption/desorption behaviour of contaminants. This study provides important new insights into the evaluation of the fate of plastic particles in natural environments.

Roles of varying carbon chains and functional groups of legacy and emerging per-/polyfluoroalkyl substances in adsorption on metal-organic framework: Insights into mechanism and adsorption prediction.

Metal-organic frameworks (MOFs) are promising adsorbents for legacy per-/polyfluoroalkyl substances (PFASs), but they are being replaced by emerging PFASs. The effects of varying carbon chains and functional groups of emerging PFASs on their adsorption behavior on MOFs require attention. This study systematically revealed the structure-adsorption relationships and interaction mechanisms of legacy and emerging PFASs on a typical MOF MIL-101(Cr). It also presented an approach reflecting the average electronegativity of PFAS moieties for adsorption prediction. We demonstrated that short-chain or sulfonate PFASs showed higher adsorption capacities (µmol/g) on MIL-101(Cr) than their long-chain or carboxylate counterparts, respectively. Compared with linear PFASs, their branched isomers were found to exhibit a higher adsorption potential on MIL-101(Cr). In addition, the introduction of ether bond into PFAS molecule (e.g., hexafluoropropylene oxide dimeric acid, GenX) increased the adsorption capacity, while the replacement of CF2 moieties in PFAS molecule with CH2 moieties (e.g., 6:2 fluorotelomer sulfonate, 6:2 FTS) caused a decrease in adsorption. Divalent ions (such as Ca2+ and SO42-) and solution pH have a greater effect on the adsorption of PFASs containing ether bonds or more CF2 moieties. PFAS adsorption on MIL-101(Cr) was governed by electrostatic interaction, complexation, hydrogen bonding, π-CF interaction, and π-anion interaction as well as steric effects, which were associated with the molecular electronegativity and chain length of each PFAS. The average electronegativity of individual moieties (named Me) for each PFAS was estimated and found to show a significantly positive correlation with the corresponding adsorption capacity on MIL-101(Cr). The removal rates of major PFASs in contaminated groundwater by MIL-101(Cr) were also correlated with the corresponding Me values. These findings will assist with the adsorption prediction for a wide range of PFASs and contribute to tailoring efficient MOF materials.

Simulating behavior of perfluorooctane sulfonate (PFOS) in the mainstream of a river system with sluice regulations.

Perfluorooctane sulfonate (PFOS) is a persistent, anionic and ubiquitous contaminant that undergoes long-range transport within the environment. Its behavior has attracted wide-range academic and regulatory attention. In this article, a mass balance model was employed to simulate PFOS concentrations in the mainstream of Haihe River water system, encompassing sluices and artificial rivers. The dynamic simulation of PFOS concentrations in both sediment and freshwater took into account fluctuations in PFOS emissions, water levels and water discharge. Furthermore, the study delved into exploring the impacts of sluices and artificial rivers on the behavior of PFOS. The simulated concentrations of PFOS in steady state agreed with the measured concentrations in surveys carried out in Nov. 2019, July 2020, Oct. 2020, and June 2021. Every year, approximately 24 kg PFOS was discharged into the Bohai Sea with Chaobai New River being the largest contributor for 44 %. Moreover, the transport of PFOS in the original rivers is likely to be restricted by sluices and replaced by artificial rivers. Monte Carlo analysis showed that model predictions of PFOS concentrations in sediment were subject to greater uncertainty than those in freshwater as the former is impacted by more parameters, such as density of sediment. This study provides a scientific basis for the local government to manage and control PFOS.

Tissue-specific distribution and bioaccumulation of perfluoroalkyl acids, isomers, alternatives, and precursors in citrus trees of contaminated fields: Implication for risk assessment.

The ingestion of fruits containing perfluoroalkyl acids (PFAAs) presents potential hazards to human health. This study aimed to fill knowledge gaps concerning the tissue-specific distribution patterns and bioaccumulation behavior of PFAAs and their isomers, alternatives, and precursors (collectively as per-/polyfluoroalkyl substances, PFASs) within citrus trees growing in contaminated fields. It also assessed the potential contribution of precursor degradation to human exposure risk of PFASs. High concentrations of total target PFASs (∑PFASstarget, 92.45-7496.16 ng/g dw) and precursors measured through the total oxidizable precursor (TOP) assay (130.80-13979.21 ng/g dw) were found in citrus tree tissues, and short-chain PFASs constituted the primary components. The total PFASs concentrations followed the order of leaves > fruits > branches, bark > wood, and peel > pulp > seeds. The average contamination burden of peel (∑PFASstarget: 57.75%; precursors: 71.15%) was highest among fruit tissues. Bioaccumulation factors (BAFs) and translocation potentials of short-chain, branched, or carboxylate-based PFASs exceeded those of their relatively hydrophobic counterparts, while ether-based PFASs showed lower BAFs than similar PFAAs in above-ground tissues of citrus trees. In the risk assessment of residents consuming contaminated citruses, precursor degradation contributed approximately 36.07% to total PFASs exposure, and therefore should not be ignored.

Transport and transformation of perfluoroalkyl acids, isomer profiles, novel alternatives and unknown precursors from factories to dinner plates in China: New insights into crop bioaccumulation prediction and risk assessment.

Perfluoroalkyl acids (PFAAs) are contaminants of global concern, and the inadvertent consumption of PFAA-contaminated crops may pose a threat to public health. Therefore, systematically studying their source tracing, bioaccumulation prediction and risk assessments in crops is an urgent priority. This study investigated the source apportionment and transport of PFAAs and novel fluorinated alternatives (collectively as per- and polyfluoroalkyl substances, PFASs) from factories to agricultural fields in a fluorochemical industrial region of China. Furthermore, bioaccumulation specificities and prediction of these chemicals in different vegetables were explored, followed by a comprehensive risk assessment from agricultural fields to dinner plates which considered precursor degradation. A positive matrix factorization model revealed that approximately 70 % of PFASs in agricultural soils were derived from fluorochemical manufacturing and metal processing. Alarming levels of ∑PFASs ranged 8.28-84.3 ng/g in soils and 163-7176 ng/g in vegetables. PFAS with short carbon chain or carboxylic acid group as well as branched isomers exhibited higher environmental transport potentials and bioaccumulation factors (BAFs) across a range of vegetables. The BAFs of different isomers of perfluorooctanoic acid (PFOA) decreased as the perfluoromethyl group moved further from the acid functional group. Hexafluoropropylene oxide dimer acid (GenX) showed relatively low BAFs, probably related to its ether bond with a high affinity to soil. Vegetables with fewer Casparian strips (e.g., carrot and radish), or more protein, possessed larger BAFs of PFASs. A bioaccumulation equation integrating critical parameters of PFASs, vegetables and soils, was built and corroborated with a good contamination prediction. After a total oxidizable precursors (TOP) assay, incremental perfluoroalkyl carboxylic acids (PFCAs) were massively found (325-5940 ng/g) in edible vegetable parts. Besides, precursor degradation and volatilization loss of PFASs was firstly confirmed during vegetable cooking. A risk assessment based on the TOP assay was developed to assist the protection of vegetable consumers.

Sorption and desorption of bisphenols on commercial plastics and the effect of UV aging.

Plastics gradually degrade in the natural environment from the effect of irradiation, which can change the surface properties of plastics and affect the migration behaviour of pollutants. Up to now, studies on the sorption/desorption behaviour of organic pollutants on aged plastics are still limited. In this study, several types of commercial plastics (polyurethane (PU), polyamide (PA), polyvinyl chloride (PVC), expanded polystyrene (EPS)) were selected to investigate the sorption and release behaviour for four kinds of bisphenols (bisphenol-F, A, B, AP). The results from Raman spectroscopy and scanning electron microscopy (SEM) analysis showed evidence of oxidization and surface cracks of plastics after irradiation. The sorption behaviour for both fresh and aged plastics were dominated by hydrophobicity. In addition, the electrostatic force, H-bonding interaction, and π-π interaction were also the important factors impacting the sorption process. The desorption kinetics behaviour indicates that desorption becomes faster after aging. Hydrophobicity is also an important factor that affects desorption behaviour. This study showed that sorption capacity for most fresh and aged plastics was enhanced by the impact of salinity and dissolved organic matter (DOM). Increased temperature could increase the desorption of bisphenols on both fresh and aged plastics, which illustrated that warm environments would promote more pollutants be released from plastics to water bodies.

Impact of short-term control measures on air quality: A case study during the 7th Military World Games in central China.

The 7th Military World Games held in Wuhan (WH) in Oct 2019 provided an opportunity to clarify the impact of short-term control measures on air quality. Fine particulate matters (PM2.5) were collected in WH, Huangshi (HS), and Huanggang (HG) during the control (Oct 13-28, 2019) and non-control periods (Oct 29- Nov 5, 2019). The results showed that air quality was good during the control period, with the concentrations of PM2.5 and gaseous pollutants being below the Grade Ⅱ of China Ambient Air Quality Standard. Concentrations of PM2.5 and its major chemical components in the control period were significantly lower than those in the non-control period, with reductions ranging from 17% (trace elements) to 46% (elemental carbon). However, higher contributions of secondary components such as SO42-, NO3-, NH4+ and secondary organic carbon (SOC) to PM2.5 were observed during the control period, suggesting the important role of secondary transformation. Potential source contribution function (PSCF) of PM2.5 showed that the main source regions were potentially located in surrounding cities Hubei Province, but regional transport can't be ignored. Six sources were identified by positive matrix factorization (PMF) for both control and non-control period. The contributions of combustion emissions and vehicle emissions were amplified in the control period, while the contribution of construction dust increased significantly when the control measures ended. Emission reductions contributed more to PM2.5 concentration decrease in WH (55%) than that in HS (51%) and HG (49%), which was consistent with the stricter control measures implemented in WH. These results indicated that short-term controls were effective at lowering PM2.5 concentration. However, the elevated contributions of secondary aerosols and the influence of regional transport on the study areas also need to be paid attention for air quality improvement in the future.

A year-long passive sampling of phenolic endocrine disrupting chemicals in the East River, South China.

The occurrence of endocrine disrupting chemicals (EDCs) in the aquatic environment is a global concern. In this study, we employed two different passive samplers Diffusive Gradients in Thin-films (DGT) and Chemcatcher for in situ measurement of 8 phenolic EDCs in the East River of the Pearl River system over one-year. These data were assessed alongside results from traditional grab sampling. Six chemicals (4tOP, 4NP, BPA, E1, EE2 and DES) were regularly detected in the water samples, of which the three phenols (i.e. 4tOP, 4NP and BPA) were in all samples and at high concentrations (0.4-1040 ng/L for 4tOP, 2.6-58500 ng/L for NP and 11.4-123300 ng/L for BPA). Fewer target chemicals were detected in both passive samplers, with only 4tOP, 4NP and BPA found in most samplers; E1 and DES were occasionally measurable above detection limits. The higher (by about a factor of 2-3) measurements provided by DGT compared to Chemcatcher could be attributed to the effect of the diffusive boundary layer on Chemcatcher uptake or the strong adsorption of target chemicals on the Chemcatcher PES filter. The temporal trends of EDC monthly loadings indicated that they were from different sources and that WWTPs were not effective in EDC removal and/or there was still some untreated wastewater discharged into the rivers.

Exposure of polychlorinated naphthalenes (PCNs) to Pakistani populations via non-dietary sources from neglected e-waste hubs: A problem of high health concern.

To date limited information's are available concerning unintentional productions, screening, profiling, and health risks of polychlorinated naphthalenes (PCNs) in ambient environment and occupational environment. Literature reveals that dust is a neglected environmental matrix never measured for PCNs. To our knowledge, this is the first study to investigate the concentrations and health risks of PCNs in indoor dust, air, and blood of major e-waste recycling hubs in Pakistan. Indoor air (n = 125), dust (n = 250), and serum (n = 250) samples were collected from five major e-waste hubs and their vicinity to measure 39 PCN congeners using GC-ECNI-MS. ∑39PCN concentrations in indoor air, dust, and serum (worker > resident > children) samples ranged from 7.0 to 9583 pg/m3, from 0.25 to 697 ng/g, and from 0.15 to 401 pg/g lipid weight, respectively. Predominant PCN congeners in indoor air and dust were tri- and tetra-CNs, while tetra- and penta-CNs were dominant in human serum samples. The higher PCNs contribution was recorded at the recycling units, while the lower was observed at the shops of the major e-waste hubs. Higher contribution of combustion origin CNs in air, dust and human samples showed combustion sources at the major e-waste hubs, while Halowax and Aroclor based technical mixture showed minor contribution in these samples. Mean toxic equivalent (TEQ) concentrations of PCNs were 2.79E+00 pg-TEQ/m3, 1.60E-02 ng-TEQ/g, 8.11E-01 pg-TEQ/g, 7.14E-01 pg-TEQ/g, and 6.37E-01 pg-TEQ/g for indoor air, dust, and serum samples from workers, residents, and children, respectively. In our study, CNs- 66/67 and -73 in indoor air, dust, and human serum were the great contributors to total TEQ concentrations of PCNs. This first base line data directs government and agencies to implement rules, regulation to avoid negative health outcomes and suggests further awareness in regard of provision of proper knowledge to the target population.

Evidence for Major Contributions of Unintentionally Produced PCBs in the Air of China: Implications for the National Source Inventory.

Polychlorinated biphenyls (PCBs) were not widely manufactured or used in China before they became the subject of international bans on production. Recent work has shown that they have reached China associated with imported wastes and that there are considerable unintentional sources of PCBs that have only recently been identified. As such, it was hypothesized that the source inventory and profile of PCBs may be different or unique in China, compared to countries where they were widely used and which have been widely studied. For the first time in this study, we undertook a complete analysis of 209 PCB congeners and assessed the contribution of unintentionally produced PCBs (UP-PCBs) in the atmosphere of China, using polyurethane foam passive air samplers (PUF-PAS) deployed across a wide range of Chinese locations. ∑209 PCBs ranged from 9 to 6856 pg/m3 (median: 95 pg/m3) during three deployments in 2016-2017. PCB 11 was one of the most detected congeners, contributing 33 ± 19% to ∑209 PCBs. The main sources to airborne PCBs in China were estimated and ranked as pigment/painting (34%), metallurgical industry/combustion (31%), e-waste (23%), and petrochemical/plastic industry (6%). For typical Aroclor-PCBs, e-waste sources were dominated (>50%). Results from our study indicate that UP-PCBs have become the controlling source in the atmosphere of China, and an effective control strategy is urgently needed to mitigate emissions from multiple industrial sources.

Multiple crop bioaccumulation and human exposure of perfluoroalkyl substances around a mega fluorochemical industrial park, China: Implication for planting optimization and food safety.

Perfluoroalkyl substances (PFASs) have become a recognized concern due to their mobility, persistence, ubiquity and health hazards in the environment. In this study, ten types of vegetables and three types of grain crops were collected in two open-air fields with different distances (0.3 km, 10 km) from a mega fluorochemical industrial park (FIP), China. Bioaccumulation characteristics of PFASs in light of crop types and organs were explored, followed by analyzing human exposure and risks to local residents with different age groups and dietary habits. Elevated levels of ∑PFASs were found nearby the FIP ranging from 79.9 ng/g to 200 ng/g in soils and from 58.8 ng/g to 8085 ng/g in crops. Perfluorooctanoic acid (PFOA) was the predominant PFAS component in soil; while shorter-chain perfluoroalkyl carboxylic acids (PFCAs), especially perfluorobutanoic acid (PFBA), were the major PFAS contaminants in multiple crops, resulting from their bioaccumulation preference. Depending on the crop types, the bioaccumulation factors (BAFs) of ∑PFASs for edible parts varied from 0.36 to 48.0, and the highest values were found in shoot vegetables compared with those in fruit vegetables, flower vegetables, root vegetables and grain crops. For typical grains, the BAFs of ∑PFASs decreased in the order of soybean (Glycine max (Linn.) Merr.), wheat (Triticum aestivum L.) and corn (Zea mays L.), possibly related to their protein and lipid content. Among specific organs in the whole plants, leaves exhibited the highest BAFs of ∑PFASs compared with corresponding roots, stems, husks or grains. With increasing carbon chain lengths of individual PFCAs (C4-C8), the logarithm of their BAFs for edible parts of various crops showed a linear decrease (0.1-1.16 log decrease per CF2 unit), and the largest decrease was observed in grains. Human exposure to PFOA via the consumption of contaminated crops represents a health risk for local residents, especially for low-age consumers or urban consumers with higher vegetable diet. Implications for planting optimization and food safety were provided aiming to reduce health hazards of PFASs.

The occurrence of home and personal care products in the Haihe River catchment and estimation of human exposure.

A sub-catchment of the Haihe River basin goes through the Beijing-Tianjin region with a population of 26 million, therefore, the use and release of home and personal care product ingredients (HPCPs) to the river catchment could be potentially substantial. Many HPCPs have been shown to be toxic to human and animals. So, it is essential to know the exposure level of HPCPs in the river basin. The average concentrations of five preservatives, three disinfectants and an antioxidant were found to be 398, 352 and 77.7 ng L-1, respectively, in the dry season. The chemical concentrations in the effluents of wastewater treatment plants (WWTPs) and untreated wastewater discharge were respectively ca. 1.3-2.2 and 1.6-7.5 times higher than those in river water. The mass flux of ∑HPCPs has been estimated to be 8.7 g/h at the outfall of the Shahe Reservoir and 181 g/h and 214 g/h at the estuary of the Haihe River and Yongdingxin River to Bohai Bay, respectively. The attenuation of ∑HPCPs was over 79% along the Wenyu River. By using the backward method, the estimated average loadings to WWTPs ranged from 0.51 to 2.0 mg/day/cap for the various individual compounds. They were 1-3 orders of magnitude higher than the estimation from the forward calculation for parabens. This indicates the possible underestimation of chemical usage and human exposure levels by the current published studies or the probably additional industrial release to the target catchment. Such a study provides useful information for the development of chemical management approaches and indicates that further research is needed to improve the estimation of HPCPs usage and emissions to aquatic environment.

Modeling the Time-Variant Dietary Exposure of PCBs in China over the Period 1930 to 2100.

This study aimed for the first time to reconstruct historical exposure profiles for PCBs to the Chinese population, by examining the combined effect of changing temporal emissions and dietary transition. A long-term (1930-2100) dynamic simulation of human exposure using realistic emission scenarios, including primary emissions, unintentional emissions, and emissions from e-waste, combined with dietary transition trends was conducted by a multimedia fate model (BETR-Global) linked to a bioaccumulation model (ACC-HUMAN). The model predicted an approximate 30-year delay of peak body burden for PCB-153 in a 30-year-old Chinese female, compared to their European counterpart. This was mainly attributed to a combination of change in diet and divergent emission patterns in China. A fish-based diet was predicted to result in up to 8 times higher body burden than a vegetable-based diet (2010-2100). During the production period, a worst-case scenario assuming only consumption of imported food from a region with more extensive production and usage of PCBs would result in up to 4 times higher body burden compared to consumption of only locally produced food. However, such differences gradually diminished after cessation of production. Therefore, emission reductions in China alone may not be sufficient to protect human health from PCB-like chemicals, particularly during the period of mass production. The results from this study illustrate that human exposure is also likely to be dictated by inflows of PCBs via the environment, waste, and food.

Diffusive gradients in thin-films (DGT) for in situ sampling of selected endocrine disrupting chemicals (EDCs) in waters.

A passive water sampler based on the diffusive gradients in thin-films (DGT) technique was developed and tested for 3 groups of endocrine disrupting chemicals (EDCs, including oestrogens, alkyl-phenols and bisphenols). Three different resins (hydrophilic-lipophilic-balanced (HLB), XAD18 and Strata-XL-A (SXLA)) were investigated for their suitability as the binding phase for DGT devices. Laboratory tests across a range of pH (3.5-9.5), ionic strength (0.001-0.5 M) and dissolved organic matter concentration (0-20 mg L-1) showed HLB and XAD18-DGT devices were more stable compared to SXLA-DGT. HLB-DGT and XAD18-DGT accumulated test chemicals with time consistent with theoretical predictions, while SXLA-DGT accumulated reduced amounts of chemical. DGT performance was also compared in field deployments up to 28 days, alongside conventional active sampling at a wastewater treatment plant. Uptake was linear to the samplers over 18 days, and then began to plateau/decline, indicating the maximum deployment time in those conditions. Concentrations provided by the DGT samplers compared well with those provided by auto-samplers. DGT integrated concentrations over the deployment period in a way that grab-sampling cannot. The advantages of the DGT sampler over active sampling include: low cost, ease of simultaneous multi-site deployment, in situ analyte pre-concentration and reduction of matrix interferences compared with conventional methods. Compared to other passive sampler designs, DGT uptake is independent of flow rate and therefore allows direct derivation of field concentrations from measured compound diffusion coefficients. This passive DGT sampler therefore constitutes a viable and attractive alternative to conventional grab and active water sampling for routine monitoring of selected EDCs.

Drivers of contaminant levels in surface water of China during 2000-2030: Relative importance for illustrative home and personal care product chemicals.

Water pollution are among the most critical problems in China and emerging contaminants in surface water have attracted rising attentions in recent years. There is great interest in China's future environmental quality as the national government has committed to a major action plan to improve surface water quality. This study presents methodologies to rank the importance of socioeconomic and environmental drivers to the chemical concentration in surface water during 2000-2030. A case study is conducted on triclosan, a home and personal care product (HPCP) ingredient. Different economic and discharge flow scenarios are considered. Urbanization and wastewater treatment connection rates in rural and urban areas are collected or projected for 2000-2030 for counties across China. The estimated usage increases from ca. 86 to 340 t. However, emissions decreases from 76 to 52 t during 2000-2030 under a modelled Organisation for Economic Co-operation (OECD) economic scenario because of the urbanization, migration and development of wastewater treatment plants/facilities (WWTPs). The estimated national median concentration of triclosan ranges 1.5-8.2 ng/L during 2000-2030 for different scenarios. It peaks in 2009 under the OECD and three of the Intergovernmental Panel on Climate Change (IPCC), A2, B1 and B2 economic scenarios, but in 2025 under A1 economic scenario. Population distribution and surface water discharge flow rates are ranked as the top two drivers to triclosan levels in surface water over the 30 years. The development of urban WWTPs was the most important driver during 2000-2010 and the development of rural works is projected to be the most important in 2011-2030. Projections suggest discharges of ingredients in HPCPs - controlled by economic growth - should be balanced by the major expenditure programme on wastewater treatment in China.

Potential effects of changes in climate and emissions on distribution and fate of perfluorooctane sulfonate in the Bohai Rim, China.

Climate change and emissions rates of contaminants are expected to affect distribution and fate of Persistent Organic Pollutants (POPs) in the environment, however, studies on these combined factors are rare. In this study, Perfluorooctane Sulfonate (PFOS) is used as an example to assess how those two factors synthetically affect fate and disposition of POPs in the Bohai Rim of China by using the Berkeley-Trent-Urban-Rural (BETR-Urban-Rural) model. We set up three climate change scenarios and four emission scenarios to conduct the simulations. The results show that climate change could have significant effects on the transport and fate of PFOS mainly including advection, inter-compartmental transfer under the "worst case" emission scenario. For most grids, a remarkable decrease in concentrations of PFOS are predicted for fresh water and urban soil in the future, with precipitation and temperature being predominant factors, whilst for coastal water and rural soil, an increasing trend is predicted. Additionally, predicted sum of sources to the Bohai Sea increases greater than removals from the Bohai Sea in the future, adding evidence that concentrations of PFOS in coastal water will increase more in the future. Under scenarios of reduced emissions and climate change, concentrations of PFOS in each compartment decreased more rapidly over time. We suggest that assessment of future climate change impacts on fate of PFOS could take emission reductions into consideration.

Can poly-parameter linear-free energy relationships (pp-LFERs) improve modelling bioaccumulation in fish?

A wide range of studies have characterized different types of biosorbent, with regard to their interactions with chemicals. This has resulted in the development of poly-parameter linear free energy relationships (pp-LFERs) for the estimation of partitioning of neutral organic compounds to biological phases (e.g., storage lipids, phospholipids and serum albumins). The aims of this study were to explore and evaluate the influence of implementing pp-LFERs both into a one-compartment fish model and a multi-compartment physiologically based toxicokinetic (PBTK) fish model and the associated implications for chemical risk assessment. For this purpose, fish was used as reference biota, due to their important role in aquatic food chains and dietary exposure to humans. The bioconcentration factor (BCF) was utilized as the evaluation metric. Overall, our results indicated that models incorporating pp-LFERs (R2 = 0.75) slightly outperformed the single parameter (sp) LFERs approach in the one-compartmental fish model (R2 = 0.72). A pronounced enhancement was achieved for compounds with log KOW between 4 and 5 with increased R2 from 0.52 to 0.71. The minimal improvement was caused by the overestimation of lipid contribution and underestimation of protein contribution by the sp-approach, which cancelled each other out. Meanwhile, a greater improvement was observed for multi-compartmental PBTK models with consideration of metabolism, making all predictions fall within a factor of 10 compared with measured data. For screening purposes, the KOW-based (sp-LFERs) approach should be sufficient to quantify the main partitioning characteristics. Further developments are required for the consideration of ionization and more accurate quantification of biotransformation in biota.

Pesticides contaminated dust exposure, risk diagnosis and exposure markers in occupational and residential settings of Lahore, Pakistan.

There are few studies documenting the dust loaded with pesticides as a potential non-dietary exposure source for occupational worker and populations living near agricultural farms and pesticides formulation plants. In present study we have evaluated the pesticide concentration in dust from potential sites and relevant health risk from dust ingestion. Furthermore, the effect of currently used pesticides was investigated on blood and urine parameters of subjects: farmer, factory worker, urban resident and rural resident and controlled subjects with presumably different levels of exposure. The urinary metabolites (TCPY and IMPY) were quantified as biomarkers of exposure to chlorpyrifos and diazinon in relation with biomarkers of effect including BuChE, LH, FSH, testosterone and oxidative stress. Results showed that chlorpyrifos and diazinon were present in higher concentration in dust and posed a high health risk to exposed subjects. The mean SOD value was high among the farmer (3048U/g Hb) followed by factory worker (1677.6U/g Hb). The urinary biomarkers - TCPY and IMPY- were found higher in exposed subjects as compared to control. Furthermore, testosterone was found in higher concentration in factory worker than control (12.63ng/ml vs 4.61ng/ml respectively). A decreased BuChE activity was noticed in occupational group and significant differences were observed in control verses exposed subjects. The PCA analysis evidenced the impact of pesticides on exposure biomarkers and male reproductive hormones. The study suggests that dust contaminated with pesticides engenders significant health risk particularly related to the nervous and endocrine system, not only for occupational workers exposed to direct ingestion but also for nearby residential community. Succinctly putting: Pesticides loaded dust in the city of Lahore, being a high priority concern for the government of Pakistan, demands to be addressed.

DGT Passive Sampling for Quantitative in Situ Measurements of Compounds from Household and Personal Care Products in Waters.

Widespread use of organic chemicals in household and personal care products (HPCPs) and their discharge into aquatic systems means reliable, robust techniques to monitor environmental concentrations are needed. The passive sampling approach of diffusive gradients in thin-films (DGT) is developed here and demonstrated to provide in situ quantitative and time-weighted average (TWA) measurement of these chemicals in waters. The novel technique is developed for HPCPs, including preservatives, antioxidants and disinfectants, by evaluating the performance of different binding agents. Ultrasonic extraction of binding gels in acetonitrile gave good and consistent recoveries for all test chemicals. Uptake by DGT with HLB (hydrophilic-lipophilic-balanced) as the binding agent was relatively independent of pH (3.5-9.5), ionic strength (0.001-0.1 M) and dissolved organic matter (0-20 mg L-1), making it suitable for applications across a wide range of environments. Deployment time and diffusion layer thickness dependence experiments confirmed DGT accumulated chemicals masses are consistent with theoretical predictions. The technique was further tested and applied in the influent and effluent of a wastewater treatment plant. Results were compared with conventional grab-sampling and 24-h-composited samples from autosamplers. DGT provided TWA concentrations over up to 18 days deployment, with minimal effects from biofouling or the diffusive boundary layer. The field application demonstrated advantages of the DGT technique: it gives in situ analyte preconcentration in a simple matrix, with more quantitative measurement of the HPCP analytes.

Crop bioaccumulation and human exposure of perfluoroalkyl acids through multi-media transport from a mega fluorochemical industrial park, China.

Significant quantities of perfluoroalkyl acids (PFAAs) are released to the environment from fluorochemical manufacturing processes through wastewater discharge and air emission in China, which may lead to human exposure and health risks through crop bioaccumulation from PFAAs-contaminated soil and irrigation water. This paper systematically studied the distribution and transport of PFAAs in agricultural soil, irrigation water and precipitation, followed by crop bioaccumulation and finally human exposure of PFAAs within a 10km radius around a mega-fluorochemical industrial park (FIP). Hotspots of contamination by PFAAs were found near the FIP and downstream of the effluent discharge point with the maximum concentrations of 641ng/g in agricultural soil, 480ng/g in wheat grain, 58.8ng/g in maize grain and 4,862ng/L in precipitation. As the distance increased from the FIP, PFAAs concentrations in all media showed a sharp initial decrease followed by a moderate decline. Elevated PFAA concentrations in soil and grains were still present within a radius of 10 km of the FIP. The soil contamination was associated with the presence of PFAAs in irrigation water and precipitation, and perfluorooctanoic acid (PFOA) was the dominant PFAA component in soil. However, due to bioaccumulation preference, short-chain perfluoroalkyl carboxylic acids (PFCAs), especially perfluorobutanoic acid (PFBA), became the major PFAA contaminants in grains of wheat and maize. The bioaccumulation factors (BAFs) for both grains showed a decrease with increasing chain length of PFAAs (approximately 0.5 log decrease per CF2 group). Compared to maize grain, wheat grain showed higher BAFs, possibly related to its higher protein content. The PFCA (C4-C8) concentrations (on a log10 basis) in agricultural soil and grain were found to show a linear positive correlation. Local human exposure of PFOA via the consumption of contaminated grains represents a health risk for local residents, especially for toddlers and children.