Go Suzuki

Flame retardants in indoor dust and air of a hotel in Japan

Occurrence of flame retardants (FRs) in the indoor environment of highly flame-retarded public facilities is an important concern from the viewpoint of exposure because it is likely that FRs are used to a greater degree in these facilities than in homes. For this study, brominated flame-retardants (BFRs) and organophosphate flame-retardants and plasticizers (OPs), and brominated dibenzo-p-dioxins/furans (PBDD/DFs) were measured in eight floor dust samples taken from a Japanese commercial hotel that was assumed to have many flame-retardant materials. Concentrations of polybrominated diphenylethers (PBDEs) and hexabromocyclododecanes (HBCDs) varied by about two orders of magnitude, from 9.8-1700 ng/g (median of 1200 ng/g) and from 72-1300 ng/g (median of 740 ng/g), respectively. Concentrations of the two types of BFRs described above were most dominant among the investigated BFRs in the dust samples. It is inferred that BFR and PBDD/DF concentrations are on the same level as those in house and office dust samples reported based on past studies. Regarding concentrations of 11 OPs, 7 OPs were detected on the order of micrograms per gram, which are equivalent to or exceed the BFR concentrations such as PBDEs and HBCDs. Concentrations of the investigated compounds were not uniform among dust samples collected throughout the hotel: concentrations differed among floors, suggesting that localization of source products is associated with FR concentrations in dust. Passive air sampling was also conducted to monitor BFRs in the indoor air of hotel rooms: the performance of an air cleaner placed in the room was evaluated in terms of reducing airborne BFR concentrations. Monitoring results suggest that operation of an appropriate air cleaner can reduce both gaseous and particulate BFRs in indoor air.

Transfer of brominated flame retardants from components into dust inside television cabinets

Television (TV) set components are highly flame resistant, with their added brominated compounds such as polybrominated diphenyl ethers (PBDEs). These compounds might be released indoors via dust, which presents a potential exposure pathway for humans in the home environment. In this study, we collected dust from inside TV sets and TV set component samples (parts of housing front cabinets, rear cabinets and circuit boards) of five sets used in Japan. We measured BFRs (i.e., PBDEs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs)) and polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/DFs). Analytical results of the TV components showed that the concentrations of PBDEs, TBBPA and PBDFs (48,000 microg/g, 19,000 microg/g and 9600 ng/g as mean values, respectively) were all highest in the rear cabinets. The SigmaPBDD concentrations (460 ng/g as a mean value) detected were highest in the circuit board samples. The respective SigmaPBDE and SigmaPBDF concentrations in the dust samples were 67-500 microg/g (mean 300 microg/g) and 180-650 ng/g (mean 410 ng/g). Such concentrations were 2-3 orders of magnitude higher than those previously reported for house dust samples, which suggests that the brominated compounds are transferred from TV components into dust. Comparison of congener patterns of the brominated compounds in the dust identified the components as the source of these BFRs.

Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites

This study investigated the occurrence of polychlorinated biphenyls (PCBs), and several additive brominated flame retardants (BFRs) in indoor dust and air from two Vietnamese informal e-waste recycling sites (EWRSs) and an urban site in order to assess the relevance of these media for human exposure. The levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in settled house dust from the EWRSs (130-12,000, 5.4-400, 5.2-620 and 31-1400 ng g(-1), respectively) were significantly higher than in urban house dust but the levels of PCBs (4.8-320 ng g(-1)) were not higher. The levels of PCBs and PBDEs in air at e-waste recycling houses (1000-1800 and 620-720 pg m(-3), respectively), determined using passive sampling, were also higher compared with non-e-waste houses. The composition of BFRs in EWRS samples suggests the influence from high-temperature processes and occurrence of waste materials containing older BFR formulations. Results of daily intake estimation for e-waste recycling workers are in good agreement with the accumulation patterns previously observed in human milk and indicate that dust ingestion contributes a large portion of the PBDE intake (60%-88%), and air inhalation to the low-chlorinated PCB intake (>80% for triCBs) due to their high levels in dust and air, respectively. Further investigation of both indoor dust and air as the exposure media for other e-waste recycling-related contaminants and assessment of health risk associated with exposure to these contaminant mixtures is necessary.

Optimization and prevalidation of the in vitro ERα CALUX method to test estrogenic and antiestrogenic activity of compounds

Estrogenicity of chemicals has received significant attention and is linked to endocrine-disrupting activities. However, there is a paucity of validated methods to assess estrogenicity in vitro. We have established a robust method to test estrogenic and antiestrogenic activity of compounds in vitro, as an alternative to using animal models such as the uterotrophic assay. To this end we optimized protocols to be used in combination with CALUX reporter gene assays and carried out an in house prevalidation, followed by two rounds of tests to establish transferability. Problems in the initial test with transferability were solved by isolation of a novel cell clone of the ERalpha CALUX line with greatly improved stability and luciferase levels. This cell line proved to be a very suitable and reliable predictor of estrogenicity of chemicals and was able to readily rank a range of chemicals on the basis of their EC50 values.

Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alternatives for PBDEs

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 6.6-14000 ng/g-dry, <2-1500 ng/g-dry, 11-3300 ng/g-dry, <5-2900 ng/g-dry, and 67-9200 ng/g-dry in surface soils, and 4.4-78 ng/g-dry, <2-20 ng/g-dry, 7.3-38 ng/g-dry, 6.0-44 ng/g-dry and 100-350 ng/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 <2-190 ng/g-dry, <2-69 ng/g-dry, <3-51 ng/g-dry and 1.7-67 ng/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.

Evaluation of Dioxin-Like Activities in Settled House Dust from Vietnamese E-Waste Recycling Sites: Relevance of Polychlorinated/ Brominated Dibenzo-p-Dioxin/Furans and Dioxin-Like PCBs

Few studies have investigated the human exposure to the ensemble of dioxin-related compounds (DRCs) released from uncontrolled e-waste recycling, especially from a toxic effect standpoint. This study evaluated the TCDD toxic equivalents (TEQs) in persistent extracts of settled house dust from two Vietnamese e-waste recycling sites (EWRSs) using the Dioxin-Responsive Chemically Activated LUciferase gene eXpression assay (DR-CALUX), combined with chemical analysis of PCDD/Fs, DL-PCBs, PBDD/Fs, and monobromo PCDD/Fs to determine their TEQ contribution. The CALUX-TEQ levels in house dust ranged from 370 to 1000 pg g(-1) in the EWRSs, approximately 3.5-fold higher than in the urban control site. In EWRS house dust, the concentrations of the unregulated PBDFs were 7.7-63 ng g(-1), an order of magnitude higher than those of regulated DRCs (PCDD/Fs and DL-PCBs), and PBDFs were also principal CALUX-TEQ contributors (4.2-22%), comparable to PCDD/Fs (8.1-29%). The CALUX-TEQ contribution of DRCs varied, possibly depending on thermal processing activities (higher PCDD/F-TEQs) and PBDE content in the waste (higher PBDF-TEQs). However, the percentage of unknown dioxin-like activities was high in all dust samples, indicating large contribution from unidentified DRCs and/or synergy among contaminants. Estimates of TEQ intake from dust ingestion suggest that children in the EWRSs may be adversely affected by DRCs from dust.

Dioxin-like activity in Japanese indoor dusts evaluated by means of in vitro bioassay and instrumental analysis: brominated dibenzofurans are an important contributor.

In our previous study, we demonstrated that dioxin-like activity in sulfuric-acid-treated extracts of Japanese indoor dust was higher than the activity in contaminated sediments. In the current study, we used high-performance liquid chromatography (HPLC) fractionation in combination with the dioxin-responsive chemical-activated luciferase gene expression (DR-CALUX) assay and gas chromatography-high-resolution mass spectrometry (GC-HRMS) to quantitatively evaluate dioxin-like compounds in indoor dusts. Selected four sulfuric-acid-treated extracts of indoor dusts were fractionated into seven fractions by means of HPLC with a nitrophenylpropylsilica column, and the activity in the first fraction of each extract was much higher than the activities in the other fractions. Therefore, each of the first fractions was further fractionated into 90 fractions by HPLC with an octadecylsilica column, and all the fractions were analyzed by means of the DR-CALUX assay. On the basis of elution characteristics, the active compounds in the fractions showing high activity were determined to be polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (Co-PCBs), and polychlorinated naphthalenes (PCNs), or supposed to be polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). These compounds in the 33 dusts extracts were quantified by means of GC-HRMS, and their median-based contributions of the theoretical CALUX-TEQs [2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-tetraCDD) equivalent] chemically calculated for PBDFs, PCDDs, PCDFs, non-ortho Co-PCBs, PCNs, and mono-ortho Co-PCBs to the experimental values (38-1400 pg/g, median 160 pg/g) were 17%, 14%, 8.8%, 0.98%, 0.10%, and 0.019%, respectively. Our results indicate that PBDFs, which are not internationally regulated dioxins, were important contributors to dioxin-like activity in Japanese dust and that further analysis of PBDFs in indoor dust is required so that the risk of exposure to these compounds via dust can be assessed.

Test chamber and forensic microscopy investigation of the transfer of brominated flame retardants into indoor dust via abrasion of source materials.

Brominated flame retardants (BFRs) have been detected in indoor dust in many studies, at concentrations spanning several orders of magnitude. Limited information is available on the pathways via which BFRs migrate from treated products into dust, yet the different mechanisms hypothesized to date may provide an explanation for the range of reported concentrations. In particular, transfer of BFRs to dust via abrasion of particles or fibers from treated products may explain elevated concentrations (up to 210 mg g(-1)) of low volatility BFRs like decabromodiphenyl ether (BDE-209). In this study, an indoor dust sample containing a low concentration of hexabromocyclododecane, or HBCD, (110 ng g(-1) ΣHBCDs) was placed on the floor of an in-house test chamber. A fabric curtain treated with HBCDs was placed on a mesh shelf 3 cm above the chamber floor and abrasion induced using a stirrer bar. This induced abrasion generated fibers of the curtain, which contaminated the dust, and ΣHBCD concentrations in the dust increased to between 4020 and 52 500 ng g(-1) for four different abrasion experiment times. The highly contaminated dust (ΣHBCD at 52 500 ng g(-1)) together with three archived dust samples from various UK microenvironments, were investigated with forensic microscopy techniques. These techniques included Micro X-ray fluorescent spectroscopy, scanning emission microscopy coupled with an energy dispersive X-ray spectrometer, Fourier transform infrared spectroscopy with further BFR analysis on LC-MS/MS. Using these techniques, fibers or particles abraded from a product treated with BFRs were identified in all dust samples, thereby accounting for the elevated concentrations detected in the original dust (3500 to 88 800 ng g(-1) ΣHBCD and 24 000 to 1,438 000 ng g(-1) for BDE-209). This study shows how test chamber experiments alongside forensic microscopy techniques, can provide valuable insights into the pathways via which BFRs contaminate indoor dust.

Dioxin-related compounds in house dust from New York State: Occurrence, in vitro toxic evaluation and implications for indoor exposure

This study analysed sulphuric-acid-treated extracts of house dust from New York State with DR-CALUX assay and HRGC-HRMS to elucidate the total dioxin-like (DL) activities, the occurrence of various dioxin-related compounds (DRCs), including PBDD/Fs, and their toxic contribution. The DL activities were 30-8000, median 210 pg CALUX-TEQ/g. PCDD/Fs, PBDD/Fs and DL-PCBs were detected with a large variation in concentrations (0.12-80, 0.33-150, 0.46-35, medians 1.7, 2.1 and 5.6 ng/g, respectively) and profiles, indicating the existence of multiple contamination sources in homes. PCDD/Fs, PBDD/Fs and DL-PCBs with known potency theoretically contributed <1%-130%, <1%-21% and <1%-6.8%, respectively, of the measured CALUX-TEQs. These results and those from DR-CALUX assays with fractionated dust extracts indicated that a substantial portion of the CALUX-TEQs could be caused by unknown dust contaminants. Considering that the DRC intake from indoor dust ingestion can be significant, identification of unknown DL contaminants in indoor dust is necessary.

Aryl hydrocarbon receptor mediated activities in road dust from a metropolitan area, Hanoi-Vietnam: contribution of polycyclic aromatic hydrocarbons (PAHs) and human risk assessment.

Dioxin-Responsive Chemical-Activated LUciferase gene eXpression assay (DR-CALUX) was applied to assess the total toxic activity of the mixture of PAHs and related compounds as well as dioxin-related compounds in road dust from urban areas of Hanoi, Vietnam. Road dust from Hanoi contained significantly higher DR-CALUX activities (3 to 39, mean 20 ng CALUX-TEQ/g dw) than those from a rural site (2 to 13, mean 5 ng CALUX-TEQ/g dw). The total concentrations of 24 major PAHs (Σ24PAHs) in urban road dust (0.1 to 5.5, mean 2.5 μg/g dw) were also 6 times higher than those in rural road dust (0.08 to 1.5, mean 0.4 μg/g dw). Diagnostic ratios of PAHs indicated vehicular engine combustion as the major PAH emission source in both sites. PAHs accounted for 0.8 to 60% (mean 10%) and 2 to 76% (mean 20%) of the measured CALUX-TEQs in road dust for Hanoi the rural site, respectively. Benzo[b]-/benzo[k]fluoranthenes were the major TEQ contributors among PAHs, whereas DRCs contributed <0.1% to CALUX-TEQs for both rural and urban sites. These results suggest TEQ contribution of other aryl hydrocarbon receptor agonists in road dust. Significant PAH concentrations in urban dust indicated high mutagenic and carcinogenic potencies. Estimated results of incremental life time cancer risk (ILCR) indicated that Vietnamese populations, especially those in urban areas such as Hanoi, are potentially exposed to high cancer risk via both dust ingestion and dermal contact. This is the first study on the exposure risk of AhR agonists, including PAHs and DRCs, in urban road dust from a developing country using a combined bio-chemical analytical approach.