Polybrominated diphenyl ether (PBDE) concentrations in house dust are related to hormone levels in men

Despite documented widespread human exposure to polybrominated diphenyl ethers (PBDEs) through dietary intake and contact with or inhalation of indoor dust, along with growing laboratory evidence for altered endocrine function following exposure, human studies of PBDE exposure and endocrine effects remain limited. We conducted a preliminary study within an ongoing study on the impact of environmental exposures on male reproductive health. We measured serum hormone levels and PBDE concentrations (BDE 47, 99 and 100) in house dust from 24 men recruited through a US infertility clinic. BDE 47 and 99 were detected in 100% of dust samples, and BDE 100 was detected in 67% of dust samples, at concentrations similar to those reported in previous US studies. In multivariable regression models adjusted for age and BMI, there was a statistically significant inverse relationship between dust PBDE concentrations and free androgen index. Dust PBDE concentrations were also strongly and inversely associated with luteinizing hormone (LH) and follicle stimulating hormone (FSH), and positively associated with inhibin B and sex hormone binding globulin (SHBG). Finally, consistent with limited recent human studies of adults, PBDEs were positively associated with free T4. In conclusion, the present study provides compelling evidence of altered hormone levels in relation to PBDE exposures estimated as concentrations in house dust, and that house dust is an important source of human PBDE exposure, but more research is urgently needed.     

Exposure to organophosphate and polybrominated diphenyl ether flame retardants via indoor dust and childhood asthma

Although the ubiquitous detection of polybrominated diphenyl ether (PBDE) and organophosphate flame retardants (PFRs) in indoor dust has raised health concerns, only very few epidemiological studies have assessed their impact on human health. Inhalation of dust is one of the exposure routes of FRs, especially in children and can be hazardous for the respiratory health. Moreover, PFRs are structurally similar to organophosphate pesticides, which have been associated with allergic asthma. Thus, we investigated whether the concentrations of PFRs and PBDEs in indoor dust are associated with the development of childhood asthma. We selected 110 children who developed asthma at 4 or at 8 years old and 110 matched controls from a large prospective birth cohort (BAMSE – Barn, Allergy, Milieu Stockholm Epidemiology). We analyzed the concentrations of 7 PFRs and 21 PBDEs in dust collected around 2 months after birth from the mother's mattress. The abundance rank in dust was as follows: TBOEP?TPHP>mmp‐TMPP>EHDPHP~TDCIPP>TCEP~TCIPP~BDE‐209?BDE‐99>BDE‐47>BDE‐153>BDE‐183>BDE‐100. There was no positive association between the FRs in mattress dust and the development of childhood asthma. In contrast, dust collected from mattresses of the mothers of children who would develop asthma contained significant lower levels of TPHP and mmp‐TMPP. This study provides data on a wide range of PFRs and PBDEs in dust samples and development of asthma in children.     

Polybrominated diphenyl ether (PBDE) concentrations and resulting exposure in homes in California: relationships among passive air,surface wipe and dust concentrations,and temporal variability

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in furniture foam, electronics, and other home furnishings. A field study was conducted that enrolled 139 households from California, which has had more stringent flame retardant requirements than other countries and areas. The study collected passive air, floor and indoor window surface wipes, and dust samples (investigator collected using an HVS3 and vacuum cleaner) in each home. PentaBDE and BDE209 were detected in the majority of the dust samples and many floor wipe samples, but the detection in air and window wipe samples was relatively low. Concentrations of each PBDE congener in different indoor environmental media were moderately correlated, with correlation coefficients ranging between 0.42 and 0.68. Correlation coefficients with blood levels were up to 0.65 and varied between environmental media and age group. Both investigator‐collected dust and floor wipes were correlated with serum levels for a wide range of congeners. These two sample types also had a relatively high fraction of samples with adequate mass for reliable quantification. In 42 homes, PBDE levels measured in the same environmental media in the same home 1 year apart were statistically correlated (correlation coefficients: 0.57–0.90), with the exception of BDE209 which was not well correlated longitudinally.     

Water-resistant flame retardants for preventing forest fires

The authors examined and tested the possibility of encapsulating flame-retardant inorganic salts to prevent them from being dissolved by rainfall when used in forests. They question the practicality of the end product and introduce another approach currently under study.     

Indoor organophosphate and polybrominated flame retardants in Tokyo

In Japan, organophosphate and polybrominated flame retardants are used in building materials and electric appliances to protect them from fire hazards. In this study, to identify the emission sources of these flame retardants to indoor air, the migration rates (flux) of organophosphate and polybrominated flame retardants from building materials and electrical appliances to solid extraction disks that were placed in contact with the interior surfaces were measured. In addition to the migration test, indoor air and outdoor air concentrations of these flame retardants were investigated. With regard to building materials in a newly built house, triethylphosphate (TEP) and tributylphosphate (TBP) were detected in the wall and ceiling coverings, and tris(2-butoxyethyl)phosphate (TBEP) was detected in the wooden flooring cleaned with a floor polish agent. With regard to electrical appliances, triphenylphosphate (TPHP) was predominantly detected in computer monitors and tris(2-chloroethyl) phosphate (TCEP) in television (TV) sets, with the highest median levels. Among the polybrominated compounds, only 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) was detected from a few old TV sets manufactured before 1995. In an indoor and outdoor air survey, nine organophosphates and nine polybrominated flame retardants were detected from indoor air. In outdoor air, only four organophosphate flame retardants were detected. The maximum level of indoor organophosphate compounds was 1260 ng/m(3) with tris(2-chloro-1-methylethyl) phosphate (TCPP), and that of polybrominated compounds was 29.5 ng/m(3) with hexabromocyclododecane (HBCD). Tetrabromobisphenol A (TBBPA) was not detected in this study, although it has the largest demand among flame retardants in Japan. The results of the migration test and the indoor air survey revealed that in indoor air, organophosphate compounds were more predominant than polybrominated compounds in Tokyo. PRACTICAL IMPLICATIONS: Polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE) are commonly used as flame retardants in plastics. The use of these two compounds in electric appliances will be banned in 2007 by the EU Directives on waste electrical and electronic equipment (WEEE) and on the restriction of the use of certain hazardous substances (RoHS) in electrical and electronic equipment. In Japan, the use of PBB was banned and that of PBDE diminished in the early 1990s by the self-imposed controls of the Japanese Flame Retardants Conference (Akutu and Hori, 2004). In Japan, the predominantly used organic flame retardants were tetrabromobisphenol A and organophosphate compounds. Tetrabromobisphenol A has been reported to disrupt endocrine systems (Kitamura et al., 2005), and some organophosphate flame retardants were recently reported to have neurochemical hazardous effects. Furthermore, organophosphate compounds were suspected to cause endocrine-disrupting effects (Fang et al., 2003; Ohyama et al., 2005) or attention deficit hyperactivity disorder (ADHD) (Winrow et al., 2003). In this study, organophosphate and polybrominated flame retardants were surveyed in indoor environments in Tokyo.     

Using in vitro to in vivo extrapolation (IVIVE) to develop toxicity metrics for human health risk assessment of polybrominated diphenyl ethers (PBDE)

Polybrominated diphenyl ethers (PBDE) are flame retardants found in many industrial components, such as furniture foam, consumer electronics, plastics, and textiles and levels have increased in human beings over the past few decades. PBDE (1) produce adverse neurotoxic effects in mice, (2) are lipophilic, and (3) bioaccumulate in fish. Consequently, PBDE biomagnification may occur, which may be transferred to human beings in amounts that may exert adverse health effects. This investigation uses in vitro models to calculate bioassay-based reference doses in order to develop a human health risk assessment based on the consumption of PBDE-contaminated fish, using in vitro to in vivo extrapolation. The toxicity effects of 10 PBDE congeners were examined and compared among those developed using traditional in vivo mouse studies and in vitro models in this investigation employing rat (Clone-9), HEPG2 and zebrafish liver cells to determine the feasibility of using alternative approaches to develop toxicity metrics to evaluate human health risk.     

Levels of brominated flame retardants and methoxylated polybrominated diphenyl ethers in eggs of white-tailed sea eagles breeding in different regions of Sweden

Forty-four unhatched eggs from white-tailed sea eagle (Haliaeetus albicilla), collected in four regions in Sweden in 1992-2005, were analysed for contents of polybrominated diphenyl ethers (PBDEs), polybrominated biphenyl (PBB), hexabromocyclododecane (HBCD) and naturally occurring methoxylated polybrominated diphenyl ethers (MeO-PBDEs). Two freshwater areas—Lapland in the arctic zone (LAP) and inland lakes in central and southern Sweden (INL), and two brackish marine areas in the Baltic Sea—the south Bothnian Sea (SB) and the Baltic Proper (BP)—were chosen for comparison of the concentrations and congener distributions in white-tailed sea eagles with different diet and migratory patterns. The geometric mean (GM) concentrations (ng/g lipid weight (l.w.)) of ∑₅PBDE (BDE-47, -99, -100, -153, and -154) were 720 (LAP), 1500 (INL), 4 100 (SB) and 4 300 (BP), whereas BDE-209 was not detectable in any of the samples. The GM concentrations for HBCD content in LAP, INL, SB and BP were 60, 90, 150 and 140 ng/g l.w., respectively, whereas the corresponding values for BB-153 were 20, 30, 100 and 120 ng/g l.w. In general, the eggs from all four regions demonstrated similar patterns of PBDE congeners, with concentrations in descending order of BDE-47, -100, -99, -153 and -154. The ∑₃-MeO-BDEs (6-MeO-BDE47, 2′-MeO-BDE68, 5-Cl-6-MeO-BDE47) for these same regions (as above) were 80, 40, 340 and 240 ng/g l.w., respectively. ∑₃-MeO-BDEs for LAP and INL (freshwaters) were significantly different, whereas those for SB and BP were not. The presence of MeO-PBDEs in all of the inland samples indicates that there is an as-yet-unidentified source of these compounds in the freshwater ecosystem. Between the two more contaminated subpopulations from the Baltic Sea coast, SB showed significantly lower productivity than BP, but no correlation was found between productivity and PBDE, PBB and HBCD at the concentrations found in this study.     

Levels of brominated flame retardants in Northern Fulmar (Fulmarus glacialis) eggs from the Faroe Islands

Eggs from Northern Fulmars (Fulmarus glacialis) were sampled in the Faroe Islands. The content of the brominated flame retardants tri- to decabromodiphenyl ethers (BDEs) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were determined in nine samples in concentrations ranging from non-detectable to 7 ng g-1(l.w.). The BDE levels were similar as in an earlier study of BDE levels in the fulmar eggs from the Faroe Islands but 10-1000 times lower compared to studies of eggs from seabirds and birds of prey from Europe. The two hexaBDEs #153 and #154 were the most abundant congeners, which represented around 50% of the total mean BDE concentration. The levels of BDE #209 were below the limit of detection (1.24 ng g-1 l.w.) except for one sample, which showed a concentration of 7.18 ng g-1 l.w. BTBPE was detected in eight samples and the mean level was 0.11 ng g-1 l.w. This concentration was 150 times lower than the average total BDE concentration (including BDEs #28, #47, #100, #99, #154, #153, #183, #209). BTBPE has only been detected once before in biota. Also other bromo-containing compounds were detected in the fulmar eggs. One group identified was the polybrominated biphenyls (PBBs), but because of the absence of reference standards in the lab, these could not be quantified.     

阻燃剂和阻燃材料应用中的环境问题探究

阻燃材料已被广泛采用。目前阻燃剂应用于大部分天然和合成材料、纸张、纸板、室内及室外装饰用木材等，但材料通过化学反应产生有毒气体和焦油等物质。根据国内外研究资料和实验数据，主要讨论阻燃剂、阻燃材料使用中所产生的环境问题及新型阻燃剂的发展前景。此类问题的研究会对阻燃剂的合理使用起到极其重要的作用。     

螺环磷酸芳酯阻燃剂热降解特性

阐述螺环磷酸芳酯阻燃剂的概要、作用机理和热降解情况,探讨螺环磷酸酯作为阻燃剂的特性和应用.实验研究其热降解特性,对其热降解特性进行探讨,并对其阻燃能力进行讨论.     

建筑用高分子保温材料阻燃剂的研究

介绍了几种新型阻燃剂,并对阻燃机理进行了分析,综述了常用阻燃剂性能测试方法,提出了阻燃剂的发展方向。     

Polybrominated diphenyl ethers in fish and sediment from river polluted by electronic waste

The present study investigated contamination of polybrominated diphenyl ethers (PBDEs) in sediment and fish samples collected from rivers in Guiyu, China where electronic waste (e-waste) is recycled and disposed. PBDE congeners with mono-to hepta-brominated and deca-brominated substitutions were detected using (13)C(12) isotope dilution GC/MS/MS and GC/MS methods, respectively. The total PBDE concentrations ranged from 4434 to 16088 ng/g (dry weight) in Nanyang River bank sediment, from 55 to 445 ng/g in Nanyang River bottom sediment and 51.3 to 365 ng/g in Lianjiang River bottom sediment in Guiyu compared with those from 16.1 to 21.4 ng/g in wastewater discharged from a vehicle repairing workshop in Lo Uk Tsuen in Hong Kong. No PBDE congeners were detected in bottom sediment and fish from Mai Po Marshes in Hong Kong. The mean concentrations of total PBDEs in mixed muscles of tilapia (Oreochromis spp) from Lianjiang River were 115 ng/g wet weight (ww) and from wastewater in Hong Kong were 4.1 ng/g ww. Highest mean PBDE concentration was obtained in liver (2687 ng/g ww), followed by abdomen muscle (1088 ng/g ww) of bighead carp (Aristichthys nobilis) collected from Nanyang River. A significant correlation of concentration of each PBDE congener between sediment and muscle from Guiyu was observed. The present results of total PBDEs in sediment and fish were 10 and 1000 times higher than other studies. Open burning and dumping of e-waste are the major causes of PBDE contamination.     

Effect of nitrogen phosphorus flame retardants on thermal degradation of wood

The effects of flame retardant action of wood treated with flame retardants that were obtained from phosphorus acid, pentaerythritol, urea, and triethanolamine through copolycondensation were studied in this research. Flame retardancy was characterized by limiting oxygen index (LOI), and the Broido method was used to evaluate the kinetics of thermal decomposition on untreated and treated wood. The effectiveness of these flame retardants was also investigated using scanning electron microscope (SEM) images of char formed after LOI tests. The results showed that adding the flame retardant decreases the thermal activation energy at a high degree of degradation, leading to the increase of LOI values. SEM images of chars showed the formation of protective polymeric coatings on char surfaces, and such coatings protected the substrate from damaging, resulting the integrity of wood fiber morphology and improvement of flame retardancy of wood during burning process.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in indoor dust in Durban,South Africa

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in indoor dust of three microenvironments in Durban, South Africa. The sum of eight PBDEs and three PCBs were quantified by gas chromatography with mass spectral detection. The mean concentrations of ∑_n = 8 PBDEs and ∑_n = 3 PCBs in 10 homes, 11 offices, and 13 university students’ computer laboratories were 1710, 1520, and 818 ng/g, and 891, 923, and 1880 ng/g for PBDEs and PCBs, respectively. The concentration of PCBs found in homes was independent (P = 0.0625) of building construction year. Similarly, no relationship was observed between PCB concentrations and floor type. The concentrations of PBDEs correlated (r = 0.60) with PCB concentrations in homes, thus assuming similar sources. The elevated concentrations of PBDEs and PCBs may have significant implications for human exposure.     

Elimination of organophosphate ester flame retardants and plasticizers in drinking water purification

Organophosphate ester flame retardants and plasticizers like tris-(2-chloro-, 1-methyl-ethyl)phosphate (TCPP), tris-(2-chloro-, 1-chloromethyl-ethyl)phosphate (TDCP), tris-(2-chloroethyl)phosphate (TCEP), tributylphosphates, triphenylphosphate (TPP), ethylhexyldiphenylphosphate (EHDPP) and tris-(butoxyethyl)phosphate (TBEP) have been studied in diverse processes for drinking water purification. The elimination efficiency of these different treatment processes, e.g., biological active slow underground passage, soil passage and technical treatment processes such as ozonization or multilayer and activated carbon filtration have been studied in three waterworks in the catchment area of the river Ruhr. In the untreated surface water the concentrations of the chlorinated organophosphates ranged 50-150 ng L(-1) TCPP, 10-130 ng L(-1) TCEP and 10-40 ng L(-1) TDCP. The amounts of the non-chlorinated alkylphosphates were in the same order of magnitude (40 ng L(-1) of the tributylphosphates, 170 ng L(-1) of TBEP and 10 ng L(-1) TPP) depending on weather and water flow. EHDPP was detected in the range of 1 ng L(-1). After the drinking water purification process in all waterworks in this study, the concentrations of the selected substances were below the respective limit of quantification (0.3-3 ng L(-1)). While activated carbon filtration as well as extended passage through soil (10-15 days residence time) were effective in eliminating all selected compounds, ozonization and multilayer filtration did not contribute to the elimination of the chlorinated compounds. The elimination effect of slow underground passage combined with soil passage concerning the halogenated compounds seemed to depend on the hydraulic residence time.     

Brominated flame retardants in Belgian home-produced eggs: levels and contamination sources

The extent and the sources of contamination with brominated flame retardants (BFRs), such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), in home-produced eggs from free-foraging chicken of Belgian private owners were investigated. Various factors, such as seasonal variability, exposure of chickens through diet (kitchen waste) and soil, and elimination of BFRs through eggs and faeces were assessed. PBDEs were more important than HBCD in terms of concentrations and detection frequency. Concentrations of PBDEs and HBCD in Belgian home-produced eggs were relatively low and comparable with reported levels from other European countries and the US. The concentrations of PBDEs (sum of 13 congeners, including BDE 209) ranged between not detected and 32 ng/g lipid weight (lw), with medians of 3.0 and < 2.0 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively. When present, BDE 209 was the major PBDE congener (45% of sum PBDEs). When BDE 209 was not detected, the PBDE profile was composed of PentaBDE (BDE 99 and BDE 47), with, in some cases, higher contribution of OctaBDE (BDE 183 and BDE 153). HBCD was also detected (< 0.4 and 2.9 ng/g lw for the autumn 2006 and spring 2007 campaigns, respectively), but at lower detection frequency. The highest HBCD value was 62 ng/g lw. The similarity between profiles and seasonal variations in the concentrations of BFRs in soil and eggs indicate that soil is an important source, but not the sole source, for eggs laid by free-foraging chicken. The contamination of eggs with PBDEs and HBCD appears to be of low concern for public health and the contribution of eggs to the total daily intake of PBDEs appears to be limited (10% for chicken owners and 5% for the average Belgian consumer).     

含溴材料热解过程溴化氢释放特性

利用热分析技术及卤酸气逸出装置,实验研究了含溴材料热解过程中溴化氢的逸出规律,结果表明:当升温速率为20℃/min时,2.4.6-三溴苯醚、八溴醚和十溴二苯乙烷在40mL/min的氮气气氛下分两个阶段进行热分解,而四溴双酚A、十溴二苯醚和溴化环氧树脂只有一个较明显的热分解阶段。6种含溴材料热解后有2.0%～20.7%的残余。随着停留时间的延长、升温速率的增加和氧含量的减少,溴化氢释放量呈线性增长。而热解温度的升高和空气流量的增加在一定范围内会使溴化氢的释放量增加,超过一定值后又会抑制溴化氢的逸出。     

Polybrominated diphenyl ethers in sewage sludge and treated biosolids: Effect factors and mass balance

Polybrominated diphenyl ether (PBDE) flame retardants have been consistently detected in sewage sludge and treated biosolids. Two hundred and eighty-eight samples including primary sludge (PS), waste biological sludge (WBS) and treated biosolids from fifteen wastewater treatment plants (WWTPs) in Canada were analyzed to investigate the factors affecting accumulation of PBDEs in sludge and biosolids. Factors examined included environmental/sewershed conditions and operational parameters of the WWTPs. PBDE concentrations in PS, WBS and treated biosolids were 230–82,000 ng/g, 530–8800 ng/g and 420–6000 ng/g, respectively; BDE-209,-99, and -47 were the predominant congeners. Concentrations were influenced by industrial input, leachate, and temperature. Several examinations including the measurement of BDE-202 indicated minimal debromination during wastewater treatment. Estimated solids-liquid distribution coefficients were moderately correlated to hydraulic retention time, solids loading rate, mixed liquor suspended solids, solids retention time, and removal of organic solids, indicating that PBDE partitioning to solids can be optimized by WWTPs' operational conditions. Solids treatment type strongly affected PBDE levels in biosolids: 1.5 times increase after solids digestion, therefore, digestion efficiency could be a potential factor for variability of PBDEs concentration. In contrast, alkaline treatment reduced PBDE concentrations in biosolids. Overall, mass balance approaches confirmed that PBDEs were removed from the liquid stream through partitioning to solids. Variability of PBDE levels in biosolids could result in different PBDEs burdens to agricultural land, and different exposure levels to soil organisms.     

Temporal trends of decabromodiphenyl ether and emerging brominated flame retardants in dust,air and window surfaces of newly built low‐energy preschools

The envelope of low‐energy buildings is generally constructed with significant amounts of plastics, sealants and insulation materials that are known to contain various chemical additives to improve specific functionalities. A commonly used group of additives are flame retardants to prevent the spread of fire. In this study, decabromodiphenyl ether (BDE‐209) and fourteen emerging brominated flame retardants (BFRs) were analyzed in indoor dust, air and on the window surface of newly built low‐energy preschools to study their occurrence and distribution. BDE‐209 and decabromodiphenyl ethane (DBDPE) were frequently detected in the indoor dust (BDE‐209: <4.1‐1200 ng/g, DBDPE: <2.2‐420 ng/g) and on window surfaces (BDE‐209: <1000‐20 000 pg/m², DBDPE: <34‐5900 pg/m²) while the other thirteen BFRs were found in low levels (dust: <0.0020‐5.2 ng/g, window surface: 0.0078‐35 pg/m²). In addition, the detection frequencies of BFRs in the indoor air were low in all preschools. Interestingly, the dust levels of BDE‐209 and DBDPE were found to be lower in the environmentally certified low‐energy preschools, which could be attributed to stricter requirements on the chemical content in building materials and products. However, an increase of some BFR levels in dust was observed which could imply continuous emissions or introduction of new sources.