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1.
Ecotoxicol Environ Saf ; 247: 114227, 2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-36306615

RESUMO

World Health Organization toxic equivalency factors (WHO-TEFs) are recommended for risk management of brominated dioxins in aquatic environments because limited information is available on their toxicity to fish. To validate this approach, we obtained the relative potencies of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans and mixed-halogenated furans (PXDF, X = Cl/Br) against 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) based on their toxicity to the early-life stage of Japanese medaka (Oryzias latipes). 2,3,7,8-substituted brominated dibenzofurans caused typical dioxin exposure effects, such as blue-sac disease. The TCDD-relative potency factors (REPs) of test substances were calculated based on the concentrations in water and eggs that caused 20% lethality on day 28 post-fertilization, and were in the order of: 2-chloro-3,7,8-tribromodibenzofuran (REPwater 3.3, REPegg 4.6) > 2,3,7,8-tetrabromodibenzofuran (0.85, 0.92) > 2,3,4,7,8-pentabromodibenzofuran (0.053, 0.55) > 1,2,3,7,8-pentabromodibenzofuran (0.0091, 0.19). The transfer rate from water to eggs was lower for pentabrominated furans than tetrabrominated congeners, and was expected to decrease with the log Kow of the test substance. Although the REPegg value can be used to compare the toxicity potential of brominated dioxins, REPwater may be more suitable for environmental risk assessment because the uptake potential of these compounds from water should be considered. This study is the first to report higher toxicity of a PXDF congener compared with TCDD in vivo, further investigations of the toxicity of mixed-halogenated dioxins and environmental behavior are necessary for environmental risk assessment.


Assuntos
Dioxinas , Oryzias , Dibenzodioxinas Policloradas , Animais , Dioxinas/toxicidade , Dibenzodioxinas Policloradas/toxicidade , Dibenzofuranos , Medição de Risco , Furanos , Água
2.
Environ Sci Technol ; 55(13): 8691-8699, 2021 07 06.
Artigo em Inglês | MEDLINE | ID: mdl-34100289

RESUMO

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.


Assuntos
Poluentes Ambientais , Hidrocarbonetos Clorados , Bifenilos Policlorados , Aves Predatórias , Animais , Aves , Monitoramento Ambiental , Poluentes Ambientais/análise , Japão , Fígado/química
3.
Environ Sci Technol ; 54(9): 5480-5488, 2020 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-32160746

RESUMO

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 Kow values, indicating their high bioaccumulative potential.


Assuntos
Bivalves , Poluentes Ambientais/análise , Poluentes Químicos da Água/análise , Animais , Baías , Monitoramento Ambiental , Cromatografia Gasosa-Espectrometria de Massas , Japão
4.
Environ Sci Technol ; 53(6): 3010-3017, 2019 03 19.
Artigo em Inglês | MEDLINE | ID: mdl-30793891

RESUMO

The distribution and toxic equivalents (TEQs) of brominated and chlorinated dibenzo- p-dioxins/dibenzofurans (PBDD/Fs and PCDD/Fs) in soils from Agbogbloshie e-waste site (Ghana) were investigated. The composition of brominated/chlorinated dibenzofurans (PXDFs) and diphenyl ethers (PBDEs, PCDEs, and PXDEs) was examined using two-dimensional gas chromatography-time-of-flight mass spectrometry to elucidate possible formation pathways of dioxins from e-waste recycling. The highest concentrations of PCDD/Fs and PBDD/Fs were found, respectively, in the open burning (1.3-380 ng/g dry weight) and dismantling areas (11-1000 ng/g dry weight) and were comparable to the highest reported for informal e-waste sites. PXDFs and PXDEs were detected at up to the range of hundreds of nanograms per gram. The homologue profiles suggest that PXDFs were formed mainly from PBDFs through successive Br-to-Cl exchange. However, monobromo-PCDFs were also derived from de-novo-generated PCDFs in open burning areas. PBDFs contributed similar or higher TEQs (7.9-5400 pg/g dry weight) compared with PCDD/Fs (6.8-5200 pg/g dry weight), whereas PXDFs were also substantial TEQ contributors in open burning areas. The high TEQs of PBDFs in the dismantling area (120-5200 pg/g dry weight) indicate the need to consider brominated dioxins besides chlorinated dioxins in future studies on health implications for e-waste workers and local residents.


Assuntos
Benzofuranos , Dioxinas , Resíduo Eletrônico , Dibenzodioxinas Policloradas , Dibenzofuranos , Dibenzofuranos Policlorados , Gana , Éteres Difenil Halogenados , Humanos , Solo
5.
Plant Cell Physiol ; 58(9): 1486-1493, 2017 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-28922748

RESUMO

Incidents at the Fukushima and Chernobyl nuclear power stations have resulted in widespread environmental contamination by radioactive nuclides. Among them, 137cesium has a 30 year half-life, and its persistence in soil raises serious food security issues. It is therefore important to prevent plants, especially crop plants, from absorbing radiocesium. In Arabidopsis thaliana, cesium ions are transported into root cells by several different potassium transporters such as high-affinity K+ transporter 5 (AtHAK5). Therefore, the cesium uptake pathway is thought to be highly redundant, making it difficult to develop plants with low cesium uptake. Here, we isolated rice mutants with low cesium uptake and reveal that the Oryza sativa potassium transporter OsHAK1, which is expressed on the surfaces of roots, is the main route of cesium influx into rice plants, especially in low potassium conditions. During hydroponic cultivation with low to normal potassium concentrations (0-206 µM: the normal potassium level in soil), cesium influx in OsHAK1-knockout lines was no greater than one-eighth that in the wild type. In field experiments, knockout lines of O. sativa HAK1 (OsHAK1) showed dramatically reduced cesium concentrations in grains and shoots, but their potassium uptake was not greatly affected and their grain yields were similar to that of the wild type. Our results demonstrate that, in rice roots, potassium transport systems other than OsHAK1 make little or no contribution to cesium uptake. These results show that low cesium uptake rice lines can be developed for cultivation in radiocesium-contaminated areas.


Assuntos
Césio/metabolismo , Genes de Plantas , Proteínas de Membrana Transportadoras/genética , Oryza/genética , Oryza/metabolismo , Proteínas de Plantas/genética , Raízes de Plantas/metabolismo , Potássio/metabolismo , Radioisótopos de Césio/metabolismo , Poluição Ambiental , Teste de Complementação Genética , Proteínas de Membrana Transportadoras/metabolismo , Modelos Biológicos , Mutagênese/genética , Mutação/genética , Oryza/efeitos dos fármacos , Fenótipo , Proteínas de Plantas/metabolismo , Raízes de Plantas/efeitos dos fármacos , Potássio/farmacologia , Soluções
6.
Environ Sci Technol ; 51(20): 11771-11779, 2017 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-28925692

RESUMO

In addition to unintentional formation of polychlorinated (PCDD/Fs), polybrominated (PBDD/Fs), and mixed halogenated (PXDD/Fs) dibenzo-p-dioxins/dibenzofurans during industrial activities, recent studies have shown that several PBDD and PXDD congeners can be produced by marine algal species from the coastal environment. However, multiple exposure status of anthropogenic and naturally derived dioxins in marine organisms remains unclear. The present study examined the occurrence, geographical distribution, and potential sources of PCDD/Fs, PBDD/Fs, and PXDD/Fs using mussels and brown algae collected in 2012 from Seto Inland Sea, Japan. The results showed the widespread occurrence of not only PCDD/Fs but also PBDDs and PXDDs in Seto Inland Sea. The geographical distribution pattern of PBDDs was similar to that of PXDDs, which were obviously different from that of PCDDs and PCDFs, and a significant positive correlation was observed between the levels of their predominant congeners, i.e., 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs. Interestingly, potential precursors of 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs, hydroxylated tetrabrominated diphenyl ethers (6-HO-BDE-47 and 2'-HO-BDE-68) and their mixed halogenated analogue (HO-TrBMoCDE), were also identified in the mussel and brown alga samples collected at the same site, by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC-ToFMS) analyses. It is noteworthy that residue levels of 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs in the mussel were 30 times higher than those in the brown alga, suggesting the bioaccumulation of these natural dioxins.


Assuntos
Dioxinas , Monitoramento Ambiental , Animais , Benzofuranos , Bivalves , Japão
7.
Breed Sci ; 67(3): 173-180, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28744170

RESUMO

In this study, we investigated the genetic basis of seed shattering and dormancy in Hokuriku 193 and bred an NIL improved these traits. Analysis of an F3 population from Hokuriku 193 × Koshihikari revealed a general correspondence between seed shattering and genotypes at the qSH1 locus, suggesting a strong influence of this locus on the seed shattering in Hokuriku 193. An F2 population from [ms-bo] Nekken 2 × Hokuriku 193 was also analyzed to identify quantitative trait loci (QTLs) for seed dormancy as measured by germination rate in the first December and March after seed harvest. The results revealed a concurrence QTLs of on chromosomes 1, 3, and 6 (qSDo1, qSDo3, qSDo6). In particular, qSDo1 and qSDo6 were considered regions worthy of active modification because they were QTL regions that promoted seed dormancy when carrying Hokuriku 193 genome regions around. SSDo_NIL, a near isogenic line (NIL) derived from Hokuriku 193 by introgressing Nekken 2 alleles only at the qSH1 locus and qSDo1, did not shatter, and its germination rate was significantly higher than that of Hokuriku 193. Yield performance was similar between SSDo_NIL and Hokuriku 193, suggesting that improvement of seed shattering and dormancy does not affect yield.

8.
Breed Sci ; 67(2): 159-164, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-28588393

RESUMO

To investigate the genetic background responsible for blast resistance in Oryza sativa L. 'Hokuriku 193', QTL analysis was conducted using the F3 lines from the cross [ms-bo] Nekken 2 × Hokuriku 193 that were artificially infected with rice blast fungus (Magnaporthe grisea). QTLs were detected on chromosomes 1, 4, 6 and 12 that correlated with greater blast resistance in the Hokuriku 193-type lines. Notably, the QTL on chromosome 12 had a major effect and localized to the same region where Pi20(t), a broad-spectrum blast resistance gene, is positioned, suggesting strongly that the blast resistance of Hokuriku 193 was controlled by Pi20(t). Also, QTL analysis of the lines found to have no Pi20(t) detected two QTLs on chromosome 4 (qBR4-1 and qBR4-2) and one QTL on chromosome 6 (qBR6), of which qBR4-2 and qBR6 correlated with higher percentages of resistant plants in the Hokuriku 193-type lines. The blast susceptibility of BR_NIL (a NIL of Hokuriku 193 from which Pi20(t) was eliminated) was greater than that of Hokuriku 193, suggesting that elimination of Pi20(t) may markedly increase blast susceptibility. The disease severity of BR_NIL was mild, which might be the effect of qBR4-2 and/or qBR6.

9.
Toxics ; 12(9)2024 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-39330584

RESUMO

Polybrominated dibenzofurans (PBDFs) are major brominated dioxins in the environment, but information on their bioaccumulation potential and toxicokinetics is limited. This study conducted oral exposure experiments with C57BL/6J mice to investigate the uptake ratios, distribution in the liver, plasma and brain, metabolism, and elimination kinetics of four bromine/chlorine-substituted dibenzofurans (TrBDF: 2,3,8-tribromo, TeBDF: 2,3,7,8-tetrabromo, PeBDF: 1,2,3,7,8-pentabromo, TrBCDF: 2,3,7-tribromo-8-chloro) in comparison with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The hepatic uptake ratios of 2,3,7,8-substituted dibenzofurans were lower than that of TCDD (up to 84% of the administered doses) and decreased with the number of Br substitutions (42%, 33%, and 29% for TrBCDF, TeBDF, and PeBDF, respectively). The brain uptake ratios of these dibenzofurans were less than 0.05%, and the plasma-to-brain transfer ratio also decreased with the Br number. All 2,3,7,8-substituted compounds were eliminated from the liver following first-order kinetics, with half-times in the order of TrBCDF (5.6 days) < TeBDF (8.8 days) ≈ TCDD (8.7 days) < PeBDF (13 days). The non-2,3,7,8-substituted TrBDF was poorly retained in the liver (<0.01% of the dose at 1 day) and rapidly eliminated following two-phase kinetics. All dibenzofurans were metabolised into monohydroxylated products in the liver, but the contribution of this metabolic pathway to hepatic elimination was only significant for TrBDF. As the toxic effects of dioxin-like compounds are influenced by their biological persistence, the slow elimination of TrBCDF, TeBDF, and PeBDF observed in this study suggests that exposure risk of brominated dibenzofurans may be underestimated using the toxic equivalency factors of the less persistent chlorinated analogues.

10.
Sci Total Environ ; 926: 172045, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38554968

RESUMO

Bioaccessibility of halogenated flame retardants (HFRs) and organophosphorus esters (OPEs) is necessarily investigated to provide more accurate risk assessment and information about absorption behavior of these pollutants. In this study, total and bioaccessible concentrations of HFRs (including legacy and alternative substances) and OPEs were determined in settled dust samples collected from Vietnamese e-waste and end-of-life vehicle (ELV) processing areas. Concentrations of both HFRs and OPEs were significantly higher in the e-waste dust than ELV dust. Bioavailability of HFRs and OPEs in dust was determined by using an in vitro assay with human-simulated digestive fluids, dialysis membrane, and Tenax® TA sorptive sink. Bioaccessibility of HFRs was markedly lower than that of OPEs, which could be largely due to higher hydrophobicity of HFRs compared to OPEs. Bioaccessibility of almost hydrophobic compounds were markedly lower in the e-waste dust (containing micronized plastic debris) than in the ELV dust (containing oily materials), suggesting the influence of specific dust matrices on pollutant bioaccessibility. Although the daily uptake doses of selected HFRs and OPEs from dust were markedly higher in the e-waste sites compared to the ELV sites, the direct exposure risk was not significant. Our results suggest that bioaccessibility can partly explain the differences between dust and uptake profiles, which may relate to accumulation profiles of HFRs and OPEs in human samples.


Assuntos
Poluição do Ar em Ambientes Fechados , Resíduo Eletrônico , Poluentes Ambientais , Retardadores de Chama , Humanos , Poeira/análise , Monitoramento Ambiental/métodos , Retardadores de Chama/análise , Vietnã , Resíduo Eletrônico/análise , Poluição do Ar em Ambientes Fechados/análise , Organofosfatos/análise , Ésteres/análise , China
12.
Environ Pollut ; 310: 119809, 2022 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-35931384

RESUMO

Information about the co-occurrence of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) in the environment of informal waste processing areas is still limited, especially in emerging and developing countries. In this study, OPEs and HFRs including polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and chlorinated flame retardants (CFRs) were determined in settled dust from Vietnamese e-waste recycling (WR) and vehicle processing (VP) workshops. Pollutant concentrations decreased in the order: OPEs (median 1500; range 230-410,000 ng/g) ≈ PBDEs (1200; 58-250,000) > NBFRs (140; not detected - 250,000) > CFRs (13; 0.39-2200). HFR and OPE levels in the WR workshops for e-waste and obsolete plastic were significantly higher than in the VP workshops. Decabromodiphenyl ether and decabromodiphenyl ethane are major HFRs, accounting for 60 ± 26% and 25 ± 29% of total HFRs, respectively. Triphenyl phosphate, tris(2-chloroisopropyl) phosphate, and tris(1,3-dichloroisopropyl) phosphate dominated the OPE profiles, accounting for 30 ± 25%, 25 ± 16%, and 24 ± 18% of total OPEs, respectively. The OPE profiles differed between WR and VP dust samples, implying different usage patterns of these substances in polymer materials for electric/electronic appliance and automotive industries. Human health risk related to dust-bound HFRs and OPEs in the study areas was low.


Assuntos
Resíduo Eletrônico , Retardadores de Chama , Humanos , Poeira , Monitoramento Ambiental , Ésteres , Éteres Difenil Halogenados , Organofosfatos , Medição de Risco , Vietnã
13.
Front Plant Sci ; 13: 998803, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36582650

RESUMO

Unmanned aerial vehicles (UAVs) are powerful tools for monitoring crops for high-throughput phenotyping. Time-series aerial photography of fields can record the whole process of crop growth. Canopy height (CH), which is vertical plant growth, has been used as an indicator for the evaluation of lodging tolerance and the prediction of biomass and yield. However, there have been few attempts to use UAV-derived time-series CH data for field testing of crop lines. Here we provide a novel framework for trait prediction using CH data in rice. We generated UAV-based digital surface models of crops to extract CH data of 30 Japanese rice cultivars in 2019, 2020, and 2021. CH-related parameters were calculated in a non-linear time-series model as an S-shaped plant growth curve. The maximum saturation CH value was the most important predictor for culm length. The time point at the maximum CH contributed to the prediction of days to heading, and was able to predict stem and leaf weight and aboveground weight, possibly reflecting the association of biomass with duration of vegetative growth. These results indicate that the CH-related parameters acquired by UAV can be useful as predictors of traits typically measured by hand.

14.
Environ Sci Pollut Res Int ; 28(1): 1018-1028, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-32829428

RESUMO

Persistent organochlorine chemicals (OCs), including chlordane compounds (CHLs), DDTs, PCBs, and chlorinated dioxins and related compounds (DRCs), were examined in the adipose tissue and liver from 33 specimens of habu (Protobothrops flavoviridis), a species of venomous pit viper endemic to the Japanese Southwest Islands. The median concentrations of CHLs, DDTs, and PCBs in adipose tissue of 22 habus collected from an urban area were 4400 ng g-1 lipid weight (lw), 610 ng g-1 lw, and 1600 ng g-1 lw, respectively. Their DDT and PCB concentrations were higher in comparison with the specimens from a rural area. Liver of 10 specimens from the urban area were subjected to DRCs analysis, and PCDDs, PCDFs, and DL-PCBs were detected with median values of 1300, 350, and 150,000 pg g-1 lw, respectively. Among PCDD/F congeners, octa-CDD was detected at the highest concentrations in seven liver samples, but considerable concentrations of penta- and hexa-CDD/Fs were found in two samples. Relatively higher concentrations of PCB, DDTs, and PCDD/Fs were found in habus collected within 1 km of the boundary of military facilities, suggesting that OCs from some unknown sources of these OCs inside and/or around some of the facilities accumulated in habus.


Assuntos
Poluentes Ambientais , Hidrocarbonetos Clorados , Bifenilos Policlorados , Dibenzodioxinas Policloradas , Trimeresurus , Animais , Dibenzofuranos , Monitoramento Ambiental , Poluentes Ambientais/análise , Ilhas , Japão , Bifenilos Policlorados/análise
15.
J Chromatogr A ; 1657: 462571, 2021 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-34614469

RESUMO

The development of highly selective and sensitive analytical methods for the nontarget screening of persistent organic pollutants such as halogenated compounds in environmental samples is a challenging task. Soft ionization mass spectrometry has emerged as a powerful technique for obtaining essential molecular information, and it is expected to reveal compounds that remain hidden with conventional fragmentation techniques such as electron ionization (EI). In this study, a soft ionization method based on electron capture negative ionization using an inert gas was developed for the nontarget screening of chlorinated aromatics in environmental samples and was applied to comprehensive two-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (GC × GC-HRToFMS). In particular, argon (Ar) and helium (He) were evaluated as inert moderating gases, and were compared against the conventional methane (CH4). The optimal ionization conditions, including the flow rate and ion source temperature, were investigated based on the molecular ion intensities of highly chlorinated aromatics decachlorobiphenyl and octachlorodibenzofuran. Ar-mediated soft ionization provided the best sensitivity to molecular ions among the three gases at a low flow rate (0.1 mL min-1) and low ion source temperature, and more selective detection of molecular ions (i.e., less fragmentation) was obtained with the inert gases than with CH4. This method is also applicable to other chlorinated aromatics such as tetra- to nonachlorobiphenyls, tetra- to heptachlorinated dibenzofurans, pentachlorobenzene, and hexachlorobenzene. To demonstrate the applicability of the proposed method to a wide range of chlorinated aromatics in environmental samples, both Ar-mediated soft ionization and conventional EI were applied to GC × GC-HRToFMS for analysis of a crude extract of house dust. Soft ionization enabled the selective and sensitive detection of molecular ions for minor amounts of chlorinated aromatics, even in complex matrices. Furthermore, the extracted ion chromatograms of halide anions (Cl- or Br-) were useful for screening other chlorinated or brominated compounds in the environmental samples. The results suggest that combining information on halide anions obtained by soft ionization and the structural information provided by EI would constitute a powerful approach for the comprehensive identification of chlorinated aromatics.


Assuntos
Poeira , Gases Nobres , Cromatografia Gasosa-Espectrometria de Massas , Espectrometria de Massas
16.
J Hazard Mater ; 403: 123878, 2021 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-33264949

RESUMO

Brominated aromatic compounds are unintentionally generated during various thermal processes, including municipal solid waste incineration, electric-waste open burning, and secondary copper smelting. Copper (Cu) plays an important role in the formation of brominated aromatic compounds. In the present study, the thermochemical behaviors of Cu and Br in model samples, including copper bromide (CuBr2) and activated carbon, were studied using in situ X-ray absorption near-edge structure (XANES) and thermogravimetry. Quantification of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) was also conducted by gas chromatograph-high resolution mass spectrometer. Three key reactions were identified: (i) the reduction of CuBr2 to CuBr (room temperature to 300 °C), (ii) the generation of Br bonded with aromatic carbon (150-350 °C), and (iii) the oxidation of copper (>350 °C). Maximum amounts of PBDD/Fs were found in residual solid phase after heating at 300 °C. The analytical results indicated the direct bromination of aromatic carbon by the debromination of copper bromides (I, II) and that CuBr and CuO acted as catalysts in the oxidation of the carbon matrix. The bromination mechanisms revealed in this study are essential to the de novo formation of PBDD/Fs and other brominated aromatic compounds.

17.
Chemosphere ; 269: 129401, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33385672

RESUMO

The present study determined recent accumulation levels of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), polychlorinated diphenyl ethers (PCDEs), methoxylated-PBDEs (MeO-PBDEs) and 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) in the blubber of melon-headed whales (Peponocephala electra) stranded along the Japanese coastal waters in 2015 and examined temporal trends of these organohalogen compound (OHC) levels by analyzing blubber samples of this species archived in the environmental specimen bank which were collected in 1982, 2001, 2002, 2006, 2010 and 2011. The median concentrations in melon-headed whales stranded recently were in the order of DDTs ≈ PCBs > HBCDDs > Q1 > CHLs > MeO-PBDEs > PBDEs > HCB > HCHs > PCDEs, indicating that considerable amounts of HBCDDs, in addition to DDTs and PCBs, have been transported to tropical and subtropical waters of the open ocean and pelagic whale species might be exposed to relatively high levels of these OHCs. Temporal trend analyses of OHC levels in the blubber of melon-headed whales revealed significant decrease for anthropogenic OCs such as DDTs, PCBs, HCB, HCHs and PCDEs, and significant increase for CHLs, PBDEs, HBCDDs, MeO-PBDEs and Q1 since 1982. Besides, the analyses from 2001 to 2015 showed no decreasing trends (unchanged) for some PCB congeners, p,p'-DDE, cis- and trans-nonachlors, Q1, BDE-47, -100 and -154, and significantly increasing trends for α-HBCDD and 6MeO-BDE47, suggesting their chronic exposure for this pelagic whale species.


Assuntos
Golfinhos , Hidrocarbonetos Clorados , Bifenilos Policlorados , Animais , Monitoramento Ambiental , Éteres Difenil Halogenados/análise , Hexaclorobenzeno/análise , Hidrocarbonetos Clorados/análise , Japão , Bifenilos Policlorados/análise
18.
Sci Total Environ ; 739: 140049, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-32758951

RESUMO

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.


Assuntos
Poluentes Ambientais , Retardadores de Chama/análise , Hidrocarbonetos Bromados/análise , Ostreidae , Bifenilos Policlorados/análise , Poluentes Químicos da Água/análise , Animais , Monitoramento Biológico , Monitoramento Ambiental , Éteres Difenil Halogenados/análise , Humanos , Japão , Poliestirenos , Inquéritos e Questionários
19.
Sci Total Environ ; 599-600: 340-347, 2017 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-28478363

RESUMO

The present study examined the occurrence and potential sources of mono- to octa-brominated dibenzo-p-dioxins/dibenzofurans (Mo-OBDD/Fs) in Tokyo Bay, Japan, using surface sediments and 210Pb-dated sediment cores (covering the period 1895-2000) collected in 2002. The results showed a clear difference in the spatio-temporal trend between PBDFs and PBDDs. The spatial distribution of PBDF concentrations in the surface sediments showed a decreasing trend from the head to the mouth of the bay, which was similar to that of polybrominated diphenyl ethers (PBDEs) reported previously for the same sediment samples. In the sediment cores, PBDF and PBDE concentrations increased drastically after the 1960s and reached the highest levels in the late 1990s. In addition, a significant positive correlation was observed between the concentrations of their predominant congeners, 1,2,3,4,6,7,8-HpBDF and BDE-209. These results indicate that main contamination sources of PBDFs were technical PBDE formulations, especially DecaBDE. In contrast, total PBDDs in the surface sediments were rather uniform in the whole area of the bay. Furthermore, in the sediment cores, PBDD levels showed marginal fluctuation over the past century, with the predominance of 2,7-/2,8-DiBDDs and 1,3,7-/1,3,8-TrBDDs in all the sediment layers. It is noteworthy that these PBDD congeners were also found in the sediment layers corresponding to the pre-industrial era, supporting their natural formation in the coastal environment.

20.
Sci Rep ; 7(1): 2432, 2017 05 25.
Artigo em Inglês | MEDLINE | ID: mdl-28546542

RESUMO

In Japan, radiocesium contamination in foods has become of great concern and it is a primary issue to reduce grain radiocesium concentration in rice (Oryza sativa L.). Here, we report a low-cesium rice mutant 1 (lcs1) with the radiocesium concentration in grain about half that in the wild-type cultivar. Genetic analyses revealed that a mutation in OsSOS2, which encodes a serine/threonine-protein kinase required for the salt overly sensitive (SOS) pathway in plants, is responsible for the decreased cesium (Cs) concentrations in lcs1. Physiological analyses showed that Cs+ uptake by lcs1 roots was significantly decreased under low-potassium (K+) conditions in the presence of sodium (Na+) (low K+/Na+). The transcript levels of several K+ and Na+ transporter genes, such as OsHAK1, OsHAK5, OsAKT1, and OsHKT2;1 were significantly down-regulated in lcs1 grown at low K+/Na+. The decreased Cs+ uptake in lcs1 might be closely related to the lower expression of these genes due to the K+/Na+ imbalance in the lcs1 roots caused by the OsSOS2 mutation. Since the lcs1 plant had no significant negative effects on agronomic traits when grown in radiocesium-contaminated paddy fields, this mutant could be used directly in agriculture for reducing radiocesium in rice grains.


Assuntos
Césio/análise , Mutação , Oryza/química , Oryza/genética , Proteínas Serina-Treonina Quinases/genética , Proteínas de Transporte de Cátions/genética , Proteínas de Transporte de Cátions/metabolismo , Radioisótopos de Césio/análise , Análise Mutacional de DNA , Regulação da Expressão Gênica de Plantas , Loci Gênicos , Fenótipo , Proteínas Serina-Treonina Quinases/metabolismo , Sódio/metabolismo , Poluentes Radioativos do Solo/análise
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