The ubiquitous distribution of microplastics (MP) is a serious environmental issue in Asian countries. In this study, 54 open-dumping site soils collected from Cambodia, India, Indonesia, Laos, the ...Philippines, and Vietnam were analyzed for MP. Soil samples were also divided into light (floating) and heavy (sedimentation) fractions by density separation and analyzed for plastic additives. The highest abundance of MP was found in a soil from Cambodia at 218,182 pieces/kg. The median of MP in soils ranged from 1411 pieces/kg in India to 24,000 pieces/kg in the Philippines, suggesting that dumping sites are a major source of MP into the environment. Polyethylene, polypropylene, and polyethylene terephthalate were dominant polymers in soil samples analyzed. This indicates that daily-used plastic products are main sources of MP in dumping site soils in Asian countries. The high concentrations and burdens of phthalates and an antioxidant were detected in floating fraction accounting for 40 to 60% of the total additives in soils. Previous studies on soil pollution have assumed that the organic hydrophobic chemicals analyzed are adsorbed on the surface of soil particles. However, this result indicates that approximately half of the additives in dumping site soils were derived from MP, not soil particle. Monitoring study on soil pollution should be considered the occurrence of MP in the matrices.
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•Microplastics (MP) was analyzed in 54 dumping site soils from 6 Asian countries.•The highest abundance of MP was identified in Cambodian samples at 218,182 pieces/kg.•PE and PP were dominant polymers, suggesting daily-used plastics are main sources of MP.•Soil samples were divided into floating and sedimentation fractions for additive analysis.•The half amount of plastic additives in dumping site soils are derived from MP.
A fish plasma model (FPM) has been proposed as a screening technique to prioritize potential hazardous pharmaceuticals to wild fish. However, this approach does not account for inter- or intraspecies ...variability of pharmacokinetic and pharmacodynamic parameters. The present study elucidated the uptake potency (from ambient water), tissue distribution, and biological risk of 20 pharmaceutical and personal care product (PPCP) residues in wild cyprinoid fish inhabiting treated-wastewater-impacted streams. In order to clarify the uncertainty of the FPM for PPCPs, we compared the plasma bioaccumulation factor in the field (BAFplasma = measured fish plasma/ambient water concentration ratio) with the predicted plasma bioconcentration factor (BCFplasma = fish plasma predicted by use of theoretical partition coefficients/ambient water concentration ratio) in the actual environment. As a result, the measured maximum BAFplasma of inflammatory agents was up to 17 times higher than theoretical BCFplasma values, leading to possible underestimation of toxicological risk on wild fish. When the tissue–blood partition coefficients (tissue/blood concentration ratios) of PPCPs were estimated, higher transportability into tissues, especially the brain, was found for psychotropic agents, but brain/plasma ratios widely varied among individual fish (up to 28-fold). In the present study, we provide a valuable data set on the intraspecies variability of PPCP pharmacokinetics, and our results emphasize the importance of determining PPCP concentrations in possible target organs as well as in the blood to assess the risk of PPCPs on wild fish.
The present study determined contamination levels of POPs, such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), ...polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs), in oysters (Saccostrea mordax) collected throughout the seacoast of Okinawa, Japan and their geographic distribution. PCBs, DDTs, CHLs, PBDEs and HBCDs were detected in almost all the oyster samples analyzed and higher concentrations of PCBs, DDTs and CHLs were found in oysters from southwestern populated areas. On the other hand, HBCDs in oysters showed similar levels throughout Okinawa and the highest concentration in a northern rural site with less human and industrial activities, although oyster concentrations of PBDEs were relatively lower. When POPs in expanded polystyrene (EPS) buoys and polystyrene foam debris floated and drifted on coastal seawater were analyzed, extremely high concentrations of HBCDs were detected in some of these EPS buoys and polystyrene foam debris but other POPs were below the limit of detection in all the samples. To evaluate the specific exposure route of HBCDs for oysters, we further analyzed HBCD diastereomers, and PCB congeners by way of comparison, in seawater and sediment samples collected at an urban site and a rural site and estimated their biota (oyster)-sediment accumulation factors (BSAF) and bioaccumulation factors (BAF). Interestingly, the highest log BAF values were found for α-HBCD despite its lower log Kow than those of γ-HBCD and PCB congeners, although log BSAF values for HBCDs were lower than those for PCBs. Considering that α-HBCD was detected in a few polystyrene foam samples as the predominant diastereomer, oysters inhabiting the coastal region of Okinawa might be frequently exposed to micronized polystyrene foam particles containing HBCDs.
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•A coastal biomonitoring survey on POPs was conducted using oysters from Okinawa.•Concentrations of PCBs, DDTs and CHLs were higher in oysters from populated areas.•The highest concentration of HBCDs was found in oysters from a northern rural site.•Elevated HBCD levels were detected in EPS buoys and polystyrene foam debris.•Polystyrene foam might be a potential source of HBCDs in the Okinawa's coast.
•A rapid analytical method was developed for 72 PPCPs in fish tissues.•Acidification with acetate buffer improved absolute recovery rates.•Oasis HLB and HybridSPE-Phospholipid Ultra cartridges were ...assessed.•Zirconia-coated silica cartridge efficiently removed analytical interferences.•The developed method is highly useful for comprehensive evaluation of PPCPs in fish.
The presence of pharmaceuticals and personal care products (PPCPs) in aquatic systems has raised concern about their potential adverse effects on aquatic organisms. Considering the fact that the physiological/biological effects of PPCPs are triggered when their concentrations in the organism exceeds the respective threshold values, it is important to understand the bioconcentration and toxicokinetics of PPCPs in aquatic organisms. In the present study, we developed a convenient analytical method for the determination of 65 pharmaceuticals and 7 personal care products (log Kow = 0.14–6.04) in plasma and whole-body tissues of fish. The analytical method consists of ultrasound-assisted extraction in methanol/acetonitrile (1:1, v/v,) acidified with acetic acid-ammonium acetate buffer (pH 4), cleanup on a HybridSPE®-Phospholipid cartridge (zirconia-coated silica cartridge), and quantification with liquid chromatography-tandem mass spectrometry (LC–MS/MS). Acceptable accuracy (internal standard-corrected recovery: 70%–120%) and intra- and inter-day precision (coefficient of variation: <15%) were obtained for both plasma and whole-body tissue samples. In addition, low method detection limits were achieved for both plasma (0.0077 to 0.93 ng mL−1) and whole-body tissue (0.022 to 4.3 ng g − 1 wet weight), although the developed method is simple and fast ― a batch of 24 samples can be prepared within 6 h, excluding the time for measurement with LC–MS/MS. The developed method was successfully applied to the analysis of PPCPs in plasma and whole-body tissue samples of fish collected in a treated wastewater-dominated stream, for a comprehensive evaluation of their bioconcentration properties. The analytical method developed in the present study is sufficiently accurate, sensitive, and rapid, and thus highly useful for the comprehensive evaluation of PPCP residues in fish and would aid in future exposome and risk assessment.
Recent screening surveys have shown the presence of unknown halogenated compounds in the marine environment at comparable levels to persistent organic pollutants (POPs). However, their exposure ...levels and profiles in marine organisms and bioaccumulative potentials remain unclear. The present study performed nontarget/target screening of organohalogen compounds (OHCs) in mussel and sediment samples collected from Hiroshima Bay, Japan, in 2012 and 2018 by using integrated analyses of two-dimensional gas chromatography–high resolution time-of-flight mass spectrometry (GC×GC–HRToFMS) and magnetic sector GC–HRMS. Nontarget analysis by GC×GC–HRToFMS revealed the detection of approximately 60 OHCs including unknown mixed halogenated compounds (UHC-Br3–5Cl) with molecular formulae of C9H6Br3ClO, C9H5Br4ClO, and C9H4Br5ClO in the mussel. Interestingly, UHC-Br3–5Cl concentrations in the mussel samples, which were semi-quantified by GC–HRMS, were comparable to or higher than those of POPs at all the locations surveyed, and their geographical distribution patterns differed from those of other OHCs. These results suggest that UHC-Br3–5Cl are ubiquitous in coastal waters of Hiroshima Bay and derived from a specific source(s). The biota-sediment accumulation factors (BSAFs) of UHC-Br3–5Cl, estimated for a paired sample set of mussel (ng/g lw) and sediment (ng/g TOC), were 1 order of magnitude higher than those for POPs with similar log K ow values, indicating their high bioaccumulative potential.
•Soils at open burning areas in Agbogbloshie had high PBDD/F and PCDD/F concentrations.•PXDFs were more abundant than PCDFs in open burning soils.•Median WHO-TEQ in open burning soils was 7 times ...higher than the U.S. action level.•WHO-TEQ contributors were in the order of PBDFs>>PCDD/Fs>PXDFs.
Although complex mixtures of dioxin-related compounds (DRCs) can be released from informal e-waste recycling, DRC contamination in African e-waste recycling sites has not been investigated. This study examined the concentrations of DRCs including chlorinated, brominated, mixed halogenated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs, PBDD/Fs, PXDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in surface soil samples from the Agbogbloshie e-waste recycling site in Ghana. PCDD/F and PBDD/F concentrations in open burning areas (18–520 and 83–3800ng/g dry, respectively) were among the highest reported in soils from informal e-waste sites. The concentrations of PCDFs and PBDFs were higher than those of the respective dibenzo-p-dioxins, suggesting combustion and PBDE-containing plastics as principal sources. PXDFs were found as more abundant than PCDFs, and higher brominated analogues occurred at higher concentrations. The median total WHO toxic equivalent (TEQ) concentration in open burning soils was 7 times higher than the U.S. action level (1000pg/g), with TEQ contributors in the order of PBDFs>>PCDD/Fs>PXDFs. DRC emission to soils over the e-waste site as of 2010 was estimated, from surface soil lightness based on the correlations between concentrations and lightness, at 200mg (95% confidence interval 93–540mg) WHO-TEQ over three years. People living in Agbogbloshie are potentially exposed to high levels of not only chlorinated but also brominated DRCs, and human health implications need to be assessed in future studies.
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In this study, the concentrations of 10 organophosphorus flame retardants (PFRs) were determined in 89 human breast milk samples collected from Japan, the Philippines and Vietnam. ...Among the targeted PFRs, tris(2-chloroexyl) phosphate (TCEP) and triphenyl phosphate (TPHP) were the predominant compounds and were detected in more than 60% of samples in all three countries. The concentrations of PFRs in human breast milk were significantly higher (p<0.05) in the Philippines (median 70ngg−1lipidwt.) than those in Japan (median 22ngg−1lipidwt.) and Vietnam (median 10ngg−1lipidwt.). The present results suggest that the usage of products containing PFRs in the Philippines is higher than those of Japan and Vietnam. Comparing with a previous literature survey in Sweden, the levels of PFRs in human breast milk from the Philippines were 1.5–2 times higher, whereas levels in Japan and Vietnam were 4–20 times lower, suggesting that these differences might be due to their variation in the usage of flame-retarded products utilized in each country. When daily intake of PFRs to infants via human breast milk was estimated, some individuals accumulated tris(2-butoxyethyl) phosphate (TBOEP) and TCEP were close to reference dose (RfD). This is the first report to identify PFRs in human breast milk samples from Asian countries.
Nontarget screening studies have recently revealed the accumulation of typically unmonitored organohalogen compounds (OHCs) in various marine animals, but information for terrestrial food chains is ...still lacking. This study investigated the accumulation profiles of known and unknown OHCs in the liver of representative wild bird specimens from Osaka, Japan using nontarget analysis based on two-dimensional gas chromatography–time-of-flight mass spectrometry. A large number of unmonitored OHCs were identified, including anthropogenic contaminants and marine halogenated natural products (HNPs), and their accumulation profiles were considered to be influenced by terrestrial and brackish water-based diets. Anthropogenic OHCs were highly accumulated in terrestrial predator species (peregrine falcon, hawks, and black kite), and some unmonitored highly chlorinated contaminants reached the levels of microgram per gram lipid in the liver, i.e., C10-/C15-based chlordane related compounds (CHLs) and their epoxides, dichlorodiphenyldichloroethylene (DDE) homologues, and polychlorinated terphenyls (PCTs). In contrast, HNPs were accumulated at higher levels in piscivorous birds (gray heron and common cormorant). Considering the enrichment of the unmonitored C10-/C15-based CHLs, PCTs, and DDE homologues relative to structurally similar persistent organic pollutants (POPs) in high trophic-level species such as raptors, further studies are needed to elucidate their environmental levels, behavior in terrestrial food chains, and ecotoxicological impacts.
Three oligomeric organophosphorus flame retardants (o-PFRs), eight monomeric PFRs (m-PFRs), tetrabromobisphenol A (TBBPA), and polybrominated diphenyl ethers (PBDEs) were identified and quantified in ...surface soils and river sediments around the e-waste recycling area in Bui Dau, northern Vietnam. Around the e-waste recycling workshops, 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), triphenyl phosphate (TPHP), TBBPA, and PBDEs were dominant among the investigated flame retardants (FRs). The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were 6.6–14000ng/g-dry, <2–1500ng/g-dry, 11–3300ng/g-dry, <5–2900ng/g-dry, and 67–9200ng/g-dry in surface soils, and 4.4–78ng/g-dry, <2–20ng/g-dry, 7.3–38ng/g-dry, 6.0–44ng/g-dry and 100–350ng/g-dry in river sediments. Near the open burning site of e-waste, tris(methylphenyl) phosphate (TMPP), (2-ethylhexyl)diphenyl phosphate (EHDPP), TPHP, and the total PBDEs were abundantly with respective concentrations of <2–190ng/g-dry, <2–69ng/g-dry, <3–51ng/g-dry and 1.7–67ng/g-dry in surface soils. Open storage and burning of e-waste have been determined to be important factors contributing to the emissions of FRs. The environmental occurrence of emerging FRs, especially o-PFRs, indicates that the alternation of FRs addition in electronic products is shifting in response to domestic and international regulations of PBDEs. The emissions of alternatives from open storage and burning of e-waste might become greater than those of PBDEs in the following years. The presence and environmental effects of alternatives should be regarded as a risk factor along with e-waste recycling.
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•Open storage and burning of e-waste contributed to emission of FRs.•Types of FRs currently in emission are shifting in response to regulations of PBDEs.•Emerging PFRs were detected in soils and sediments around e-waste recycling area.•Presence of alternatives for PBDEs should be regarded as a risk factor.
