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The properties of potential emerging persistent contaminants, perfluoroalkyl substances (PFAS), in an andosol rice paddy lysimeter were analyzed to determine their mobility and leaching behavior regarding carbon chain length and functional groups. For this purpose, simulated contaminated water (ΣPFAS = 1,185,719 ng/L) was used in the lysimeter. The results showed that PFAS distribution in the paddy soil lysimeter was influenced by the migration of these substances into irrigation water and their adsorption into the soil. PFHxS (C6) and PFOS (C8), which are the main components of the simulated contaminated water, were mostly captured in the soil layers of the low-humic andosol layer (0–35 cm). PFAS distribution may depend on soil properties, such as total carbon (TC) content. Compared with perfluoroalkane sulfonic acids (PFSAs), the distribution of perfluoroalkyl carboxylic acids (PFCAs) in soil showed significant variation. The remaining PFCAs were distributed across all layers of the lysimeter, except for the longer-chain PFCAs. Moreover, the PFSA distribution was directly correlated with the carbon chain number, whereby longer- and shorter-chain PFSAs accumulated in the top and bottom soil layers, respectively. This study provides detailed information on the distribution, leaching, uptake, and accumulation of individual PFAS in andosol paddy fields in Japan.

Information regarding the size-dependent distribution of per- and polyfluoroalkyl substances (PFAS) in atmospheric particulate matter (PM) is very limited. In this study, 248 size-specific PM samples were collected from 9 Asian cities using a portable 4-stage cascade impactor for the analysis of PFAS. Of the 34 investigated PFAS, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) were the major compounds. In particular, the emerging PFAS, hexafluoropropylene oxide dimer acid, was quantified in the PM for the first time, with concentrations ranging from

Novel per- and polyfluoroalkyl substances (PFASs) have become a key issue in global environmental studies. Although several novel PFASs have been discovered in atmospheric particulate matter through nontarget analysis, information on the environmental occurrence of novel PFASs in atmospheric gaseous phases and conventional sampling techniques is somewhat deficient. Therefore, this Article describes a new type of air sampler, the cryogenic air sampler (CAS), which was used to collect all atmospheric components simultaneously. Nontarget analysis then was performed through PFASs homologue analysis. A total of 117 PFAS homologues (38 classes) were discovered, 48 of which (13 classes) were identified with confidence Level 4 or above. Eleven chlorinated perfluoropolyether alcohols (3 classes) and four chlorinated perfluoropolyether carboxylic acids (2 classes) have been reported for the first time in this Article. This Article is also the first report of 12 hydrosubstituted perfluoroalkyl carboxylates (H-PFCAs) in the atmosphere. H-PFCAs and chlorinated perfluoropolyether carboxylic acids were mainly distributed in the particular phase. These results are evidence that novel chlorinated polyether PFASs should be the focus of future study.

Given that only a small number of per- and polyfluoroalkyl substances (PFAS) are routinely monitored, levels of PFAS in the atmosphere may be underestimated. A protocol including analyses of target PFAS (n = 50), water-soluble fluoride, and total fluorine has been proposed and applied to atmospheric samples. The whole method recovery (including extraction recovery and sampling efficiency) of 90-110% were obtained for the majority of compounds (48/50) with low deviations between replicates (20%). Fluorotelomer alcohols were the most prevalent PFAS in the indoor air, while the outdoor air was dominated by the ultrashort-chain ionic PFAS (e.g., trifluoroacetic acid and perfluoropropanoic acid). Concentrations of organofluorine (OF) compounds calculated from the fluorine mass balance ranged from 1.74 ng F/m

Per- and polyfluoroalkyl substances (PFASs) as emerging organic pollutants have received great attention, but the scavenging efficiency of particulate PFASs by wet deposition was rarely studied. For the first time, we reported the scavenging efficiency of PFASs on different particle sizes. In this study, both rainwater and particle samples were collected for a whole year from Xiamen, a subtropical city of China. Particulate PFASs ranged from 4.11 to 67.41 pg m

Perfluoroalkyl substances (PFASs) are a group of contaminants of concern in agricultural crops, but little is known of their accumulation or behavior in grains. We grew Japanese rice (Oryza sativa subsp. indica) in lysimeters irrigated with tap water or tap water plus simulated contaminated water for 2 years, then analyzed the roots, straw, unhulled rice, white rice, bran, soil, and water for PFASs residues. Total fluorine was measured by combustion ion chromatography. Estimated per-plant residue levels were 3.0 pg perfluorooctanesulfonic acid (PFOS) (bran: 0.5%, hull: 99.5%), 0.54 pg N-ethylperfluorooctanesulfonamide (N-EtFOSA) (white rice: 67%, hull: 33%), 1.2 pg perfluorobutanoic acid (PFBA) (white rice: 13%, bran: 7%, hull: 79%), 0.68 pg perfluoropentanoic acid (hull: 100%), 0.50 pg perfluorohexanoic acid (PFHxA) (white rice: 65%, bran: 16%, hull: 19%), 0.21 pg perfluoroheptanoic acid (hull: 100%), 0.25 pg perfluorooctanoic acid (PFOA) (hull: 100%), and 0.12 pg perfluorodecanoic acid (PFNA) (white rice: 81%, bran: 19%). Estimated daily PFASs intakes were1-3 ng perfluorooctanesulfonamide,1-7 ng N-EtFOSA, 1-2 ng PFBA,3-4 ng PFHxA, and 1-2 ng PFNA. Estimated PFOS, PFOA, and total PFASs in straw feed were 0.4, 0.1, and 2 kg yr

Twenty-five per- and polyfluoroalkyl substances (PFASs) were analyzed in water, sediment and biota from the Dongshan Bay (DSB) to study their seasonal variations, composition profiles, potential pollution sources, partitioning behavior and risk assessments. The total concentrations of PFASs (∑PFASs) in water ranged from 3.2 to 6.5 ng L−1 (mean 4.0 ng L−1) during the dry season, and 0.11–4.5 ng L−1 (mean 1.3 ng L−1) during the wet season. Perfluoro-butane sulfonic acid (PFBS), perfluoro-butanoic acid (PFBA) and perfluoro-octanoic acid (PFOA) were dominated and frequently detected in water. ∑PFASs in sediment were 0.15–0.37 ng g−1 dw (mean 0.24 ng g−1 dw) with the long-chain PFASs perfluoro-octane sulfonic acid (PFOS) dominating. High concentrations of PFASs in land-based drainage outlets (2.0–384.6 ng L−1 in water) and Zhangjiang estuary indicated that land-based discharges and the river discharge were the main sources. High concentration (366.1 ng L−1) and proportion (94%) of PFBA on one drainage outlet agreed with the trend that PFBA was as an alternative to long-chain PFASs. ∑PFASs in biota ranged from 0.11 to 0.40 ng g−1 ww, and only long-chain PFASs were detected. The partition coefficients (log Kd) of PFASs between water and sediment ranged from 1.13 to 2.90, increased with carbon chain length, implied long-chain PFASs are more likely to adsorb to sediment. Results of ecological and health risk assessments indicated that PFASs had no significant risk for the aquatic organisms and local residents.

An inter-laboratory trial (ILT) has been performed to validate ISO 21675 method for the measurement of per-and polyfluoroalkyl substances (PFAS) in water samples using solid phase extraction method and high-performance liquid chromatography-tandem mass spectrometry. A total of twenty-seven laboratories from eleven countries (Belgium: 1, Canada: 2, China: 2, France: 1, Germany: 3, Italy: 2, Japan: 6, Netherlands: 2, South Korea: 1, Sweden: 4, and USA: 3) participated in the ILT. Results of the homogeneity of ILT water samples showed that the repeatability tended to increase from short-chain to long-chain of PFAS. Results of stability of PFAS in Milli-Q water stored at 5 ± 3 °C ranged from 75% to 121% including those ultra-short-chain compounds, except for N-MeFOSA (44%), N-EtFOSA (44%), and 8:2 FTOH (30%) at 168 days. As for stability of PFAS in environmental waters, they were in acceptable range (between 70 and 125%) for most of PFAS, except for 8:2 FTUCA in the river water, seawater, and wastewater, and 8:2 FTSA and 8:2 FTOH in wastewater. Based on the performance data (reproducibility (CVR)

A simultaneous sampling of atmospheric and seawater samples was performed in the Taiwan Western Strait, western Arctic Ocean, and the Antarctic Ocean. Analysis of both particle and gas phase PFAS in oceanic air was conducted using cascade impactor particle fractionator, cryogenic air sampler and activated charcoal fiber sorbent for the first time with application in the Taiwan Western Strait. Mean concentration of Σ12PFAS in surface seawater and atmospheric samples were 1178 pg/L and 24 pg/m3 in the Taiwan Western Strait, 430 pg/L and 6 pg/m3 in the western Arctic Ocean, and 456 pg/L and 3 pg/m3 in the Antarctic Ocean. In oceanic air from the Taiwan Western Strait, fluorotelomer alcohol (FTOH) and the ionic PFAS [perfluoroalkyl sulfonic acid (PFSA) and perfluoroalkyl carboxylic acid (PFCA)] were found in 76% and 7% respectively. Regional comparison of air/water exchange (KAW) and gas-particle (Kp) partition coefficients of PFAS in the oceanic environment indicated potential partitioning of ionic PFAS between surface seawater and oceanic air. These findings highlight the advancement in atmospheric PFAS measurements through combined novel technologies, namely size-fractionated particle sampling with cryogenic air trapping and/or activated charcoal sorption. Correlation between Kp and carbon chain length of PFAS was observed using both hyphenated techniques.

The occurrence of selected pharmaceuticals (trimethoprim, sulfamethoxazole, chloramphenicol, bezafibrate, ceftriaxone, and naproxen) in two west-flowing tropical rivers (Swarna and Nethravati) of southwestern India is reported for the first time. Water samples were collected during the monsoon and post-monsoon seasons from river water end members and further downstream up to their confluence with the adjacent Arabian Sea. Samples were analyzed using HPLC–MS/MS. Results revealed that there were no significant seasonal variations in concentrations of target analytes in both the rivers. Of the total number of samples analyzed (n = 24), trimethoprim was detected in 100% of the samples, whereas sulfamethoxazole (SMX), chloramphenicol (CAP), ceftriaxone (CTX), and naproxen (NPX) were detected in between 91 and 58% of the samples. Bezafibrate (BZF) was not detected in the samples. Nethravathi river showed higher concentrations of pharmaceuticals than the Swarna river which may be attributed to comparatively larger human population in the basin. Possible impacts of PPCPs on aquatic life offer further scope for study.

Per- and polyfluoroalkyl substances (PFAS) have received continuous attention; however, there is limited understanding of their sources in the atmosphere and related human exposure risks. This study measured PFAS in the atmospheric total suspended particles collected from Karachi, Pakistan, during the winter. Among the quantified PFAS, perfluorobutanoic acid (PFBA) showed the highest average concentration (3.11 ± 2.64 pg/m3), accounting for 32% of the total PFAS. Wind speed was positively correlated with perfluorohexanoic acid (PFHxA) and N-ethyl perfluorooctanesulfonamide (N-EtFOSA), while relative humidity was negatively correlated with perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Weighted potential source contribution function (WPSCF) and concentration weighted trajectory (WCWT) analyses suggested that northwestern Pakistan and western Afghanistan areas were highly associated with the long-range atmospheric transport of PFAS. We also calculated the daily intake of PFAS via inhalation, which were in the range of 0.07–3.98 and 0.01–0.33 pg/kg bw/d for children and adults, respectively. The calculated hazard quotient (HQ) of PFOS and PFOA was significantly lower than 1, indicating less or unlikely to cause non-carcinogenic effect via inhalation exposure. Overall, this study contributes to the understanding of geographic origins and human inhalation risks of airborne PFAS on a regional scale.

We investigated mass loading and the spatial distribution of volatile methylsiloxanes (VMSs) including four cyclic VMSs (D3–D6; cVMSs, the number refers to the number of Si O bonds) and three linear VMSs (L3–L5; lVMSs) in Tokyo Bay, Japan, which is one of the most industrialized, urbanized, and populated areas in the world. Based on the VMS concentrations determined in eight main inflow rivers to the bay, the mass loading of VMSs via inflow rivers and sewage treatment plants located in Tokyo Bay was estimated at 2700 kg/y for total VMSs. Elevated mass loadings of VMSs were found in three of the rivers, inflowing to the inner west of Tokyo Bay. The distribution and deposition characteristics of VMSs were observed depending on the estuarine condition. Estuarine sediments were found to be efficient and effective traps for VMSs and the salting-out effect is one possible mechanism to explain this phenomenon. The overall profiles of D4, D5, and D6 in surface water and sediment were observed across Tokyo Bay; elevated concentrations were identified in the inner west bay with dispersed low concentrations in the outer bay, except for one hotspot of D4 in the sediment, indicating a major emission route of VMSs via inflow rivers. Additionally, the historical pollution profiles of VMSs in Tokyo Bay were reconstructed based on the VMS concentrations determined in a dated sediment core. VMSs were identified throughout the upper 40 cm of the sediment core (representing the mid 1980s); the profiles correspond with the historical use of VMSs in wash-off personal care-products. The noted decreasing trend of D4 might be a reflection of the early 2000s replacement of D4 with D5 in such products. The elevated VMS concentrations in the estuarine sediment raise concerns about the impact on the aquatic environment.

In this work, the distribution of quaternary ammonium compounds (QACs) in two dated sediment cores, collected from the Pearl River Estuary (PRE) and Tokyo Bay (TB), were investigated to understand the historical input of QACs and their diagenetic behavior in urban estuarine environments. The vertical variation profiles of QAC concentrations showed that benzylalkyldimethyl ammonium compounds (BACs) and dialkyldimethyl ammonium compounds (DADMACs) were widely used during 1970s and 1980s both in China and Japan. The declining environmental concentrations of QACs suggested a compositional change of commodities and the effectiveness of emission control strategies. For the individual QAC homologues, BAC homologues decreased significantly over time, while DADMAC compositions remained relatively stable. The differences in concentration and composition profiles of BACs and DADMACs in the sediment cores provided useful information on the patterns of use of QACs in China and Japan, as well as their diagenetic behaviors in the sediments.

A new method is preliminarily validated for the simultaneous analysis of ionic and neutral per- and polyfluoroalkyl substances (PFASs) in both particulate and gaseous phases in air using a nanosampler-20 air sampler (NS20) composed of quartz fiber filters (QFFs), polyurethane foam (PUF) and artificial activated charcoal (GAIAC™). Perfluoroalkane sulfonamido ethanols (FOSEs) mainly remained in PUF, whereas the other neutral analytes were mainly found in GAIAC. Satisfactory recoveries were obtained for FOSEs, fluorotelomer alcohols (FTOHs), fluorotelomer iodides (FTIs), ranging fron 70%–120%, moderate recoveries were achieved for perfluorinated iodine alkanes (FIAs) and diiodofluoroalkanes (FDIAs), ranging from 50%–70%, while poor recoveries were found for perfluoroalkane sulfonamides (FOSAs). Breakthrough experiments revealed that almost all the target analytes were well trapped in GAIAC™, including the very volatile 4:2 FTOH. Applying to real sampling, our results showed that 6:2 and 8:2 FTOH were the most abundant species, with levels detected at 190 pg/m3 and 160 pg/m3. To the best of our knowledge, FDIAs were detected in ambient air for the first time at an average level of 8.3 pg/m3. Overall, the profiles observed from the real air samples reflected current industrial transition from longer chain to shorter chain in PFAS production. Our results revealed that the current method is promising for a more comprehensive understanding on the fates of PFASs in air.

To examine the impacts of urbanization and industrialization on the coastal environment, and assess the effectiveness of control measures on the contamination by chlorinated paraffins (CPs) in East Asia, surface and core sediments were sampled from the urbanized coastal zones in China and Japan (i.e., Pearl River Delta (PRD), Hong Kong waters and Tokyo Bay) and analyzed for short-chain (SCCPs) and medium-chain CPs (MCCPs). Much higher concentrations of CPs were found in the industrialized PRD than in adjacent Hong Kong waters. Significant correlation between CP concentration and population density in the coastal district of Hong Kong was observed (r2 = 0.72 for SCCPs and 0.55 for MCCPs, p < 0.05), highlighting the effect of urbanization. By contrast, a relatively lower pollution level of CPs was detected in Tokyo Bay. More long-chain groups within SCCPs in the PRD than in Hong Kong waters and Tokyo Bay implied the effect of industrialization. Comparison of temporal trends between Hong Kong outer harbor with Tokyo Bay shows the striking difference in historical deposition of CPs under different regulatory situations in China and Japan. For the first time, the declining CP concentrations in Tokyo Bay, Japan, attest to the effectiveness of emissions controls.

This reconnaissance study was undertaken in 2012 to examine the occurrence of common perfluoroalkyl substances (PFAS), including perfluoroalkyl sulphonic acids and perfluoroalkyl carboxylic acids in rivers and estuaries in Port Philip Bay, Victoria, Australia. In total, 19 PFAS were screened in grab samples of water using a combination of solid phase extraction and liquid chromatography - mass spectrometry measurement techniques. Eighteen of the PFAS screened were observed in samples. The highest level of PFOS observed at a freshwater site was 0.045 μg/L; this concentration is approximately half the draft Australian 95% species protection level for total PFOS. The highest level of PFOA in the study (0.014 μg/L) was some four orders of magnitude lower than the draft Australian trigger value for PFOA (220 μg/L). However, none of the PFAS observed at the freshwater sites had research quotient (RQ) or toxicity unit (TU) values above 1 or -3, respectively. The highest concentration of PFOS observed at an estuarine site was 0.075 μg/L; the highest level of PFOA, 0.09 μg/L). There are no Australian marine water quality trigger values for PFAS, so potential risk was assessed using the European environment quality standards (EQS) adopted in EU Directive 2013/39/EU, RQ and TU methods. In that context, none of the PFAS observed at estuary sites had concentrations higher than the EU standards, or RQ above 1 or Log10TU above -3. Together these assessments suggest none of the PFAS screened would have posed an acute risk to organisms in the fresh or estuary waters studied at the time of sampling on an individual or collective basis. However, the detection of these PFAS in Victorian estuaries highlights that the issue is not just an issue for more densely populated countries in the northern hemisphere, but also potentially of concern in Australia. And, in that context, more sampling campaigns in Port Philip Bay are of paramount importance to assess the potential risk pose by these compounds to aquatic ecosystems.

Perfluoroalkyl substances (PFASs) have become an important class of global environmental contaminants, yet their vertical profile in the marine water column is still less understood, especially for the semi-closed seas. In this study, the contamination level and spatial distribution of 8 PFASs were investigated in both surface and vertical water samples from two semi-closed seas, the Japan Sea and the Mediterranean Sea. Similar levels and compositions of PFASs were found between these two seas. The vertical profile of PFASs in the Mediterranean Sea was variable while that was relatively steady in the Japan Sea, probably due to their different pollution sources. The accumulation rate of PFASs from the East China Sea to the Japan Sea was calculated, for which perfluorooctanesulfonic acid and perfluorooctanoic acid were found to have high accumulation potency in both surface and deep water; most of the investigated PFASs were accumulated in the deep water due to the long residence time while they were more likely to escape to the Pacific Ocean in the surface water. This work aimed (i) to study the distribution of PFASs in both surface and vertical water samples in two semi-closed seas, namely the Japan Sea and for the first time the Mediterranean Sea, (ii) to assess the temporal trend in the Japan Sea, and (iii) to firstly investigate the potential transport of PFASs from the East China Sea and Taiwan Strait in order to estimate the inventory of PFASs in whole water mass in the Japan Sea.

In recent years, environmental issues emerging from per- and polyfluoroalkyl substances (PFAS) have raised high concern worldwide. Levels of human exposure to PFAS remain unknown in India. Biomonitoring data obtained from hair analysis have been evidenced to provide insight into retrospective human exposure to PFAS. In this study, 25 PFAS, including perfluoroalkyl acids and their precursors, were measured in 39 human hair samples collected from 14 cities in India. The inuflence of gender on the PFAS levels was also examined. To our knowledge, this is the first attempt to provide preliminary indicative data (due to the limited sample size and variability in hair-length sampling) on the levels of PFAS in Indian hair. The concentrations of total PFAS in hair varied from below matrix-specific limit of quantification (

The international regulation of persistent organic pollutants (POPs) according to the Stockholm convention started in May 2001, and is intended to regulate the production and use of hazardous chemicals on a global scale. PFOS is one of the newly listed emerging POPs and only one of a diverse huge group of perfluoroalkyl substances (PFASs), which are known as a “super set” of chemical tracers that include more than ninety related chemicals. The comprehensive monitoring of PFASs is necessary to develop a reliable understanding of environmental kinetics related to these pollutants. However, the extent of atmospheric pollution by PFASs is still unclear because their distribution and sources are not fully understood. Hence, a reliable analytical method for precisely measuring the levels of PFASs in particulate matter is needed. In this study, in order to investigate the levels of PFASs in atmospheric particles including PM2.5, the use of new sampling equipment was evaluated by obtaining multiple samples of air from a stable meeting room environment. Meanwhile, by simultaneously obtaining samples from a roadside environment, the characteristics of PFASs from two different types of air samples were compared.

Seasonal and local characteristics of perfluorinated alkylated substances (PFASs) were examined using size-segregated particles including an ultrafine range. The examination included sampling and analysis of ambient particles collected at four sites located in different environments in three different countries, Japan (Kanazawa and Okinawa), Hong Kong and India. To minimize the evaporation artefacts derived from PFASs during the sampling, an air sampler that permitted particles smaller than 0.1 μm (PM0.1) to be separated at a moderate pressure drop (

Bisphenol A (BPA) has been frequently found in surface waters worldwide, and its estrogenic effects in humans are well documented. Nevertheless, less is known about other bisphenol analogues (BPs), such as bisphenol S (BPS) and bisphenol F (BPF) which are alternative to BPA. There have been few environmental investigations on BPs in developing countries, especially India. In the present study, eight BPs were analyzed, among which BPA, BPS, and BPF were found prevalent in surface water and wastewater from drains collected from 12 states and Delhi-National Capital Territory in India. The detection frequencies of BPA, BPS, and BPF were 67.6%, 41.9%, and 29.7%, respectively in all samples (n = 74). BPA was the predominant species among the three analogues. The highest BPA concentration was observed in the Yamuna River (14,800 ng/L), followed by the Cooum River (1,420 ng/L). The highest concentrations of BPS and BPF were 438 ng/L and 333 ng/L, respectively, both found in wastewater samples. The occurrence of BPS and BPF in nationwide surface water and wastewater samples from India for the first time suggests that new BPs as BPA replacements are being used and released in India. Ecological risk assessment of BPA, BPS and BPF exposure was performed using hazard quotient (HQ) for three aquatic taxonomic groups: algae, crustaceans, and fish, with the last group exhibiting the highest HQs (0.89–148) for BPA exposure. The human exposure risk of BPA through drinking river water was observed negligible in the present study. Our findings indicate the urgent need for, (1) regulations on the use and release of BPs in India, (2) effective processes to remove BPs in wastewater treatment plants, (3) more investigations on the distribution and toxicity of BPs in India, in particular BPA, BPS and BPF, as these analogues were detected at substantial concentration in Indian waters.

Solutions of technical polychlorinated naphthalene (PCN) Halowax formulations (Halowax 1014 and Halowax 1051) diluted with Milli-Q water and sealed in the Pyrex glass tubes and quartz tubes were subjected to artificial solar and natural solar irradiation under different time intervals and field conditions. In particular, the results of several field irradiation experiments have shown increased PCN photodegradation as altitude increases above sea level. Irradiation in artificial solar conditions caused a substantial change in the PCN congener profiles of Halowax 1014 and Halowax 1051 test solutions. Interestingly, in long-term experiments, the relative abundance of congeners that contribute to dioxin-like activity, i.e. the compounds such as 1,2,3,5,7- and 1,2,4,6,7-PentaCN (PeCNs #52/60), 1,2,3,4,6,7- and 1,2,3,5,6,7-HexaCN (HxCNs #66/67), and 1,2,3,4,5,6,7-HeptaCN (HpCN #73), temporally increased substantially. In the field photodegradation experiments, the PCNs #52/60 and #66/67 were formed, while a relative persistence of PCN #73 was evident. Highest chlorinated octachloronaphthalene (OcCN #75), exposed to strong UV radiation at high altitude, was much less stable than lower molecular mass PCNs. Photodegradation of the technical PCN formulations produced also an unidentified aromatic compound. We conclude, that photodegradation of PCNs, which are considered as a widespread anthropogenic pollutants, is not restricted to any specific environmental condition. It can also be observed at low altitudes.

The concentrations and spatial distribution of 14 organophosphorus flame retardants (OPFRs) and plasticizers were studied in aquatic environments of China, namely, the Pearl River Delta (PRD), South China Sea (SCS) and Yellow River Estuary (YRE), as well as Tokyo Bay (TB) in Japan. These locations were characterized by different levels of socioeconomic development and human activities. The spatial pattern of OPFRs revealed their ubiquity along the coasts of China and Japan; the concentrations ranged from 15 to 1790, 1 to 147, 253 to 1720, and 107 to 284 ng L−1 in the PRD, SCS, YRE and TB, respectively. The most frequently detected OPFR was triethyl phosphate (TEP), followed by triphenylphosphine oxide (TPPO) and tris(2-chloroethyl) phosphate (TCEP). A positive relationship (R2 = 0.668, p = 0.004) was observed between OPFR contamination and socioeconomic activity, measured by gross domestic product (GDP) per capita, for the studied cities in China and Japan. The results suggest that an increase in manufacturing and construction activities in the studied areas may aggravate coastal contamination with OPFRs. The potential threat to aquatic organisms from exposure to TCEP, a suspected carcinogen, was revealed by the hazard quotient (HQ) and probabilistic assessments. Further investigation of OPFR exposure in the aquatic environment of China is urgently required.

The occurrence and removal of seven selected pharmaceutical compounds (PCs) in sewage treatment plants (STPs) in South India were investigated. The PCs selected for this study were sulfamethoxazole (SMX), trimethoprim (TMP), chloramphenicol (CAP), erythromycin (ERY), naproxen (NPX), bezafibrate (BZF), and ampicillin (AMP). Wastewater samples were collected from inlet and outlet of the STPs during pre-monsoon, monsoon, and post-monsoon seasons to investigate the seasonal influences in occurrence and removal rates. The analytical method was based on simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic-balanced (HLB) sorbent followed by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The STP that catered exclusively to domestic wastewater had lesser concentrations of PCs compared to the STPs serving the combined hospital and domestic effluents. SMX was the dominant compound in all effluents with the highest concentration at 3.2 μg/L in the outlet of an STP. TMP and ERY were the other PCs present at higher concentrations in STP outlets (1 μg/L and 0-0.13 μg/L, respectively). Removal rates varied from 100 % for BZF to 60-100 % for SMX, CTX, and AMP.

Despite the high consumption of pharmaceuticals, mass loading and removal of these compounds in sewage treatment plants (STPs) in India have not been investigated. In this study, 43 pharmaceuticals and personal care products as well as 13 of their metabolites were analyzed in five domestic STPs (wastewater influent, effluent, and sludge) and in raw domestic sewage collected in open sewerage channels in residential areas in India. The mean concentrations of amphetamine in two of the five STPs (mean: 4300 ng/L and 4720 ng/L) were the highest ever reported for wastewater influents, globally. Among artificial sweeteners, saccharin was the most abundant compound in influents (mean: 303,000 ng/L, df: 100%), followed by cyclamate [3460 ng/L, detection frequency (df): 75%] and sucralose (1460 ng/L, df: 100%). Elevated mean concentrations of an antimicrobial (triclocarban = 6180 ng/L), analgesic (ibuprofen = 2320 ng/L), antihypertensive (atenolol = 3180 ng/L), illicit drug (amphetamine = 984 ng/L), and saccharin (419,000 ng/L) were found in the Cooum River in Chennai. The median removal efficiencies of pharmaceuticals and personal care products (PPCPs) ranged from 5% (norcocaine) to 100% (triclosan) for the five STPs. On the basis of the concentrations measured in influents, the mass loadings of PPCPs were estimated to range from 0.1 (norquetiapine) to 77,800 (saccharin) mg/d/1000 people. An estimated 2.55 kg of triclocarban, 3.24 kg of carbamazepine, 6.93 kg of amphetamine, and 252 kg of saccharin were discharged from a typical STP with an average flow rate of 20.7 million liters per day (serving a population of 325,000) in India.

Concentrations of eight bisphenol analogues (Bps) including BPA, BPS, and BPF were determined in surface waters collected from select rivers in Japan, Korea, China, and India. BPA was found at a concentration in the range of several tens to several hundreds of nanograms per liter in most of the rivers surveyed and some of the highest concentrations (54-1950 ng/L) were found in rivers in Chennai, India. Concentrations of BPF were one to two orders of magnitude higher than those of BPA in river and sea waters collected from Japan, Korea and China, which suggested that BPF is a major contaminant in surface waters in several Southeast Asian countries. BPF concentrations as high as 2850 ng/L were found in the Tamagawa River in Japan. The flux of BPs through riverine discharges into Tokyo Bay was calculated to be approximately 5.5 t per year. Based on the flux estimates and the mass of BPF found in water column and sediment in Tokyo Bay, it was found that BPF degrades faster than BPA in the environment. Elevated concentrations of BPF found in surface waters suggest the need for further studies to determine the fate and toxicity of this compound. (C) 2015 Elsevier Inc. All rights reserved.

Water samples collected along the Japanese coast and in the open Pacific Ocean in 2010, 2011, and 2012 were analyzed for perfluoroalkyl substances (PFASs) to evaluate the effect of Great East Japan Earthquake (EQ 3.11), which occurred on March 11, 2011, on the dispersion of chemical pollutants. Ultratrace analysis of PFASs in water, a super computer simulation, and an inventory analysis from industrial records revealed the sources and dynamics of PFASs during the EQ 3.11 disaster. In this respect, EQ 3.11 destroyed solid infrastructure on land, and within minutes, PFASs stocked therein were released into the open environment. The historically significant tsunami backwash swept them away from their origin to the coastal water within several hours. It was estimated that from 0.8 to 1.0 tons of perfluorooctanesulfonate (PFOS) and 4.8 to 5.1 tons of PFOA were discharged into the coastal waters after EQ 3.11 and the tsunami that followed. The reconstruction of EQ 3.11 also traced the influence of this pollution in open ocean water until March 2012, and a statistical and finger printing analysis revealed that there were different distribution mechanisms in coastal regions than in the open ocean for PFOS, other shorter chain perfluorinated sulfonic acids and perfluorinated carboxylic acids.

The sewage treatment plant (STP) is one of the most important interfaces between the human population and the aquatic environment, leading to contamination of the latter by antimicrobial-resistant bacteria. To identify factors affecting the prevalence of antimicrobial-resistant bacteria, water samples were collected from three different STPs in South India. STP1 exclusively treats sewage generated by a domestic population. STP2 predominantly treats sewage generated by a domestic population with a mix of hospital effluent. STP3 treats effluents generated exclusively by a hospital. The water samples were collected between three intermediate treatment steps including equalization, aeration, and clarification, in addition to the outlet to assess the removal rates of bacteria as the effluent passed through the treatment plant. The samples were collected in three different seasons to study the effect of seasonal variation. Escherichia coli isolated from the water samples were tested for susceptibility to 12 antimicrobials. The results of logistic regression analysis suggest that the hospital wastewater inflow significantly increased the prevalence of antimicrobial-resistant E. coli, whereas the treatment processes and sampling seasons did not affect the prevalence of these isolates. A bias in the genotype distribution of E. coli was observed among the isolates obtained from STP3. In conclusion, hospital wastewaters should be carefully treated to prevent the contamination of Indian environment with antimicrobial-resistant bacteria.

In this study, we evaluated the efficacy of a novel minipig strain, the Microminipig (MMPig), as an animal model for studying the pharmacokinetics of a mixture of 10 perfluoroalkyl acids (PFAAs). After a single oral dose was given, we found that the blood depuration of PFAAs (blood t1/2), which we calculated using first-order elimination curves, ranged from 1.6 to 86.6 days. Among the five body compartments analyzed, the liver was the greatest site of accumulation of perfluorooctanesulfonate and longer chain perfluorinated carboxylates such as perfluorodecanoic acid, perfluoroundecanoic acid and perfluorododecanoic acid. We observed an increasing accumulation trend of perfluorinated carboxylates in the organs associated with the fluorinated carbon chain length. The perfluorononanoic acid burden was the highest among the treated compounds 21 days after a single exposure, as 29% of the given perfluorononanoic acid dose was accumulated in the tissues. The persistence of PFAAs in edible pig tissues even after 21 days post-exposure raises concerns about the safety of swine products. This was the first study to use MMPigs to elucidate the pharmacokinetics of a group of environmental pollutants. We found that MMPigs could be excellent experimental animals for toxicological studies due to their easy handling, cost efficacy for target compounds and ease of waste treatment. Copyright © 2015 John Wiley & Sons, Ltd.

Concentrations of 23 per- and polyfluoroalkyl substances (PFASs), including new classes of PFASs, in seawater samples were investigated for their occurrence and the interaction of the ocean currents with the distribution of PFASs in the South China Sea. This study revealed that socio-economic development was associated with the PFAS contamination in coastal regions of South China. Significant correlations between concentration of total PFASs with gross domestic product (GDP) per capita and population density were found in the areas, suggesting that the influence of intense human activities in these areas may have resulted in higher PFAS contamination to the adjacent environment. Di-substituted polyfluoroalkyl phosphate (diPAP), one of the potential replacements for PFASs, was only detected in the heavily developed region, namely Pearl River Delta (PRD). Total PFAS concentrations, ranging from 195 to 4925 pg/L, were detected at 51 sampling stations of the South China Sea. The results also confirmed that PFAS contamination in the South China Sea is strongly affected by the ocean currents. In comparison to perfluoroactane sulfonate (PFOS) concentrations measured nine years ago at the same locations, the concentrations in this study were found to be two times higher. This indicated that the use and production of perfluoroalkyl sulfonates (PFSAs) has been continuing in the region.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) receive increasing attention as hazardous pollutants in terms of the high environmental persistence and toxicities. Ambient concentrations of 24 ClPAHs and 24 PAHs were investigated at 14 sites in the Tokyo Bay area of Japan. Twelve of 18 ClPAH species were detected in air samples, in spite of small sampling volumes. Mean concentrations of total PAHs in gas and particle phases were 5400 and 1400 pg/m3, and mean concentrations of total ClPAHs in gas and particle phases were 40 and 14 pg/m3, respectively. The spatial distributions of both total ClPAH and PAH concentrations indicated heavy pollution at sites in industrial activity areas. Principal component analysis suggested that the dominant sources of gaseous and particulate ClPAHs differed substantially from each other. In particular, gaseous ClPAHs could be produced by specific sources different from those of particulate ClPAHs. However, the dominant sources of particulate ClPAHs could be the same as those of particulate PAHs, including industrial activities such as steel and gas-production plants and natural gas-fired power plants. The influences of spatial relationships among sampling sites were represented using a network analysis. The constructed network showed that ambient ClPAHs and PAHs were dominated by local rather than regional pollution, because there were weaker relationships among nearby sites. Finally, exposure risks for ClPAHs were dominated by 7-chlorobenz[a]anthracene, followed by 9-chlorophenanthrene and 6-chlorobenzo[a]pyrene, and total risk was ∼1/200 that of PAHs.

Perfluoroalkyl substances (PFASs) were investigated in three types of vegetables (fruit, leafy, and root vegetables) that were cultivated and harvested from 2014 to 2017. The cultivated soil was mainly affected by perfluoroalkyl carboxylic acid (PFCAs; 91.8% detection rate) rather than perfluoroalkyl sulfonic acids (PFSAs; 8.2%). The cultivated soil (i.e., a volcanic cohesive soil) had a high total organic carbon (TOC = 3.4%) and therefore showed strong adsorption of long-chain PFASs. Short-chain PFCAs (i.e., under C9) were mainly detected in vegetables; specifically, PFBA showed high concentration in tomato shoots. Principal component analysis (PCA) plots clearly showed that PFASs in vegetables were different from those of cultivated soil, air, and rainwater. Interestingly, the whole potato (i.e., including peel) was in the same group as soil, indicating that the whole potato can easily be affected by the cultivated soil. Energy Dispersive X-ray Spectrometry-Scanning Electron Microscope (EDS-SEM) results showed that presence of unremovable micron-sized cultivated soil particles on the potato surface. Comparing the regional differences between the cultivated area of Tsukuba city (East Japan) and Osaka city (West Japan), PFASs patterns were similar in cucumber but differed in green perilla and potato.

Organic UV filters are common ingredients of personal care products (PCPs), but little is known about their distribution in and potential impacts to the marine environment. This study reports the occurrence and risk assessment of twelve widely used organic UV filters in surface water collected in eight cities in four countries (China, the United States, Japan, and Thailand) and the North American Arctic. The number of compounds detected, Hong Kong (12), Tokyo (9), Bangkok (9), New York (8), Los Angeles (8), Arctic (6), Shantou (5) and Chaozhou (5), generally increased with population density. Median concentrations of all detectable UV filters were

The Great East Japan Earthquake on 11 March 2011, followed by the tsunami and fire, resulted in serious environmental problems in and around Japan. A huge amount of material was discharged into the ocean after the tremendous flood damage of the tsunami. A monitoring survey of the perfluoroalkyl substances (PFAs) found evi- dence showing an abrupt increase in the PFA concentration in the ocean east of Japan in 2011 after the earthquake. To confirm the anomalous input of two typical PFAs, perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS), from the Japanese coast into the ocean, associated with the earthquake, we conducted a series of chemical tracer simulations using an eddy-resolving ocean reanalysis product: JCOPE2. The simulation model involves pro- cesses representing the emission of PFAs from the land triggered by the tsunami flood, advection of the polluted waters, and decay of the concentration by the background oceanic turbulence. Comparison of the PFOA simulation results with the observation confirms a spike-like input of PFOA into the Western North Pacific after the earthquake. Advection and diffusion by the Kuroshio Extension and the mesoscale eddies play a key role in the dilution of the concentration. Optimization of unknown simulation parameters leads to an estimation of the total amount of the anomalous PFOA emission. In contrast, the PFOS simu- lations are not able to explain the observed distribution, suggesting possible differences in the oceanic transport processes between PFOS and PFOA.

Thiamazole, an anti-hyperthyroidism agent, was administered orally to pregnant cynomolgus monkeys at doses of 2.0 and 3.5 mg/kg per day from GD 120 to GD 150 to investigate effects on behavioral development of their infants. Swelling of the throat region due to enlargement of the thyroid glands was observed at birth in thiamazole-treated infants, and it returned to normal around postnatal day (PND) 30. At necropsy of infants at 12 months of age, thyroidal weight in the thiamazole groups was increased. This finding suggested the likelihood that administration of thiamazole to maternal animals during the late gestational period induced thyroid goiter in fetal/infant monkeys through placental transfer of thiamazole. No clear changes were noted in thyroid histopathology or serum thyroid hormone levels in maternal animals or infants, but goiter formation might have been indicative of exposure to high thyroid stimulating hormone (TSH) and low T3 or T4 in utero from maternal treatment with thiamazole. Age-related changes were observed in the control in behavioral development tests, while infants at 3.5 mg/kg showed no age-related decrease in contact behavior and no increase in exploratory activity on PND 90 or PND 170. In addition, the number of eye contacts between PND 210 and PND 240 was less frequent. This indicated that maternal exposure to thiamazole induced mental retardation-like behaviors in infants. Thiamazole may directly inhibit thyroid hormone synthesis in the fetus by placental transfer. From these results, it was speculated that oral administration of thiamazole to maternal animals during the late gestational period induced retardation of behavioral development in their infants.

The present cross-sectional study investigated 12 perfluoroalkyl substances (PFASs) in serum (n=79) and liver (n=66) samples from patients who had undergone liver transplantation for a range of conditions, such as hepatocellular carcinoma (HCC), cirrhosis due to chronic hepatitis C viral infection (HCV), both HCC and HCV, amyloidosis or acute liver failure. PFAS data from patients were compared to those in control serum (n=25) samples from liver donors with no known liver disease and to those in control liver (n=9) tissues collected during liver resection surgery. All samples showed detectable PFOS (serum: 0.621–126 ng/mL; liver: 0.375–42.5 ng/g wet wt) and PFOA (serum: 0.437–45.5 ng/mL; liver: 0.101–2.25 ng/g wet wt) concentrations. In general, in paired serum and liver samples, serum had higher PFOS, PFHxS, PFDA, PFNA, and PFOA concentrations than those in explanted livers from patients. These findings also suggest that pathological changes in diseased livers alter the distribution of PFASs between liver and serum. The results from control serum (2007–2008) suggested that PFOS, PFHxS, PFOA, and PFNA concentrations were lower than those previously reported from Australia for 2002–2003, and 2006–2007. The present study demonstrates, for the first time, the detection and comparison of a range of PFASs in the liver of patients with liver cancer and/or liver cirrhosis.

Parabens (alkyl esters of p-hydroxybenzoic acid) are widely used in cosmetics, pharmaceuticals, and foodstuffs as broad-spectrum antimicrobial preservatives. Laboratory animal studies have shown that parabens possess weak estrogenic activity. Widespread exposure of humans to parabens has raised significant public health concerns. Despite such concern, little is known about the occurrence of parabens in the environment. In this study, six paraben analogues, methyl- (MeP), ethyl- (EtP), propyl- (PrP), butyl- (BuP), benzyl-(BzP), and heptyl parabens (HepP), were determined in surface sediment and sediment core samples collected from several locations in the United States (U.S.), Japan, and Korea by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Concentrations of parabens also were determined in sewage sludge collected from several wastewater treatment plants (WWTPs) in Korea. MeP was found in all samples, including surface sediment, sediment core, and sludge samples, at concentrations ranging from 0.312 to 540 ng/g dry weight (dw). PrP was detected in the majority of samples (79%), and the concentrations were, in general, 1-2 orders of magnitude lower than MeP concentrations. Significant positive correlations were found among the concentrations of paraben analogues in sediment and sludge, which suggested the existence of similar sources of origin for these compounds. The sum concentrations of six parabens (∑PBs) in sludge (geometric mean: 66.3, median: 89.5 ng/g dw) were remarkably higher than those in sediment (5.48, 5.24 ng/g dw). Vertical profiles of parabens in sediment cores from the U.S. showed a gradual increase in concentrations in the past decade, although such a trend was not clear in sediment core from Tokyo Bay, Japan.

Fourteen perfluoroalkyl substances (PFASs) including short-chain perfluorocarboxylates (PFCAs, C4–C6) and perfluoroalkane sulfonates (PFSAs, C4 and C6) were measured in surface sediment samples from 26 stations collected in 2008 and sediment core samples from three stations (Niagara, Mississauga, and Rochester basins) collected in 2006 in Lake Ontario. Perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA) were detected in all 26 surface sediment samples, whereas perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonamide (FOSA), perfluorododecanoate (PFDoDA) and perfluorobutanoate (PFBA) were detected in over 70% of the surface sediment samples. PFOS was detected in all of the sediment core samples (range: 0.492–30.1 ng g−1 d.w.) over the period 1952–2005. The C8 to C11 PFCAs, FOSA, and PFBA increased in early 1970s. An overall increasing trend in sediment PFAS concentrations/fluxes from older to more recently deposited sediments was evident in the three sediment cores. The known PFCAs and PFSAs accounted for 2–44% of the anionic fraction of the extractable organic fluorine in surface sediment, suggesting that a large proportion of fluorine in this fraction remained unknown. Sediment core samples collected from Niagara basin showed an increase in unidentified organic fluorine in recent years (1995–2006). These results suggest that the use and manufacture of fluorinated organic compounds other than known PFCAs and PFSAs has diversified and increased. Keywords: Sediment, Core, Flux, PFAS, PFOS, Unidentified fluorine

Two capillary columns of different polarity were applied in a two-dimensional gas chromatography system coupled to a quadrupole mass spectrometric detection (GC x GC/qMS) in order to separate and identify all of the possible 22 isomers of tetra-, 14 of penta- and 10 of hexachloronaphthalene that may occur in selected industrial chemicals. The two-dimensional GC x GC separation was achieved using Rt- β DEXcst and DB-WAX phases, and data imaging was done by 2D and 3D mapping. This combination allows for the analysis of all tetra- to hexachloronaphthalene congeners in a single instrumental run without any pre-separation or fractionation of the analytes. The novel methodology described here can assist in the accurate determination and expression of dioxin-like toxicity of tetrachloronaphthalenes to octachloronaphthalene that are usually present as mixtures at least in abiotic materials such as technical chloronaphthalene formulations (e.g. Halowax mixtures), and wastes containing Halowaxes and other CN formulations.

The ISO 25101 (International Organization for Standardization, Geneva) describes a new international standard method for the determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) in unfiltered samples of drinking and surface waters. The method is based on the extraction of target analytes by solid phase extraction, solvent elution, and determination by high performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). For the determination of the performance of this method, more than 20 laboratories from 9 different countries participated in an inter-laboratory trial in 2006. In addition, inter-laboratory trials were conducted in 2008 and 2009 for the analysis of perfluoroalkylsubstances (PFASs), including PFOS and PFOA, in water samples by following the protocols of Japanese Industrial Standard (JIS). Overall, the repeatability coefficients of variation (i.e., within-laboratory precision) for PFOS and PFOA in all water samples were between 3 and 11%, showing a adequate precision of the ISO and JIS methods. The reproducibility coefficients of variation (i.e., between-laboratory precision) were found to vary within a range of 7–31% for surface water and 20–40% for wastewater. The recoveries of PFOS and PFOA, as a measure of accuracy, varied from 84 to 100% for surface water and from 84 to 100% for wastewater among the samples with acceptable criteria for internal standards recovery. The determined concentrations of PFASs in samples compared well with the “true” values. The results of the inter-laboratory trial confirmed that the analytical methods are robust and reliable and can be used as a standard method for the analysis of target compounds in water samples.

Perfluoroalkyl substances (PFAS) have been globally detected in various environmental matrices, yet their fate and transport to the Arctic is still unclear, especially for the European Arctic. In this study, concentrations of 17 PFAS were quantified in two ice cores (n=26), surface snow (n=9) and surface water samples (n=14) collected along a spatial gradient in Svalbard, Norway. Concentrations of selected ions (Na(+), SO4(2-), etc.) were also determined for tracing the origins and sources of PFAS. Perfluorobutanoate (PFBA), perfluorooctanoate (PFOA) and perfluorononanoate (PFNA) were the dominant compounds found in ice core samples. Taking PFOA, PFNA and perfluorooctane-sulfonate (PFOS) as examples, higher concentrations were detected in the middle layers of the ice cores representing the period of 1997-2000. Lower concentrations of C8-C12 perfluorocarboxylates (PFCAs) were detected in comparison with concentrations measured previously in an ice core from the Canadian Arctic, indicating that contamination levels in the European Arctic are lower. Average PFAS concentrations were found to be lower in surface snow and melted glacier water samples, while increased concentrations were observed in river water downstream near the coastal area. Perfluorohexanesulfonate (PFHxS) was detected in the downstream locations, but not in the glacier, suggesting existence of local sources of this compound. Long-range atmospheric transport of PFAS was the major deposition pathway for the glaciers, while local sources (e.g., skiing activities) were identified in the downstream locations.

A field study on the photolysis of perfluoroalkyl substances (PFASs) was conducted at high altitudes in Mt. Mauna Kea (Hawaii, USA; 4200 m) and Mt. Tateyama (Toyama, Japan; 2500 m). Results of photolysis of PFASs in the field were further confirmed in laboratory studies. Perfluorooctanesulfonate (PFOS), which is perceived as a non-degradable chemical in the environment, can undergo photolysis. Long chain PFASs can be successively dealkylated to short chain compounds such as perfluorobutyric acid (PFBA) and perfluorobutane sulfonate (PFBS), but the short chain compounds were relatively more resistant to photodegradation. These results suggest that environmental levels of short chain PFASs would increase both due to their formation from photolysis of long chain PFASs and from direct releases. Earlier studies on photolysis of PFASs were focused on the formation of perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs) from precursor compounds (such as fluorotelomer alcohols) under laboratory conditions. Our study suggests that PFSAs and PFCAs themselves can undergo photodegradation in the environment.