Abstract  alpha-, beta-, and gamma-hexabromocyclododecane diastereomers (HBCDs) were measured in house dust from Birmingham, U.K. (n=31, median concentration=730 ng sigmaHBCDs g(-1)); Amarillo/Austin, TX (n=13, 390 ng g(-1)); and Toronto, Canada (n=8, 640 ng g(-1)). Concentrations in dust (n=6, 650 ng g(-1)) from U.K. offices were within the range for UK homes. Concentrations from each country were statistically indistinguishable. In one UK house dust sample, 110,000 ng g(-1) was recorded-the highest recorded in indoor dust to date. While upper bound average U.K. dietary exposures for adults and toddlers, respectively, are 413 and 240 ng sigmaHBCDs day(-1), U.K. adults and toddlers daily ingesting, respectively, 50 and 200 mg of dust contaminated at the 95th percentile concentration are exposed, respectively, to 1100 and 4400 ng sigmaHBCDs day(-1). Normalized to body weight, this high-end exposure scenario estimate for toddlers is within the range reported elsewhere for occupationally exposed adults. While in commercial formulations gamma-HBCD predominates (>80%), alpha-HBCD in dust constitutes 14-67% of sigmaHBCDs (average 32%). Hence the predominance of the alpha-diastereomer in humans may arise partly from dust ingestion, and not solely to in vivo metabolism (when alpha-HBCD is formed from bioisomerization of other diastereomers), or dietary exposure (where alpha-HBCD predominates in most foodstuffs).

Abstract  This paper critically examines indoor exposure to semivolatile organic compounds (SVOCs) via dermal pathways. First, it demonstrates that--in central tendency--an SVOC's abundance on indoor surfaces and in handwipes can be predicted reasonably well from gas-phase concentrations, assuming that thermodynamic equilibrium prevails. Then, equations are developed, based upon idealized mass-transport considerations, to estimate transdermal penetration of an SVOC either from its concentration in skin-surface lipids or its concentration in air. Kinetic constraints limit air-to-skin transport in the case of SVOCs that strongly sorb to skin-surface lipids. Air-to-skin transdermal uptake is estimated to be comparable to or larger than inhalation intake for many SVOCs of current or potential interest indoors, including butylated hydroxytoluene, chlordane, chlorpyrifos, diethyl phthalate, Galaxolide, geranyl acetone, nicotine (in free-base form), PCB28, PCB52, Phantolide, Texanol and Tonalide. Although air-to-skin transdermal uptake is anticipated to be slow for bisphenol A, we find that transdermal permeation may nevertheless be substantial following its transfer to skin via contact with contaminated surfaces. The paper concludes with explorations of the influence of particles and dust on dermal exposure, the role of clothing and bedding as transport vectors, and the potential significance of hair follicles as transport shunts through the epidermis. PRACTICAL IMPLICATIONS: Human exposure to indoor pollutants can occur through dietary and nondietary ingestion, inhalation, and dermal absorption. Many factors influence the relative importance of these pathways, including physical and chemical properties of the pollutants. This paper argues that exposure to indoor semivolatile organic compounds (SVOCs) through the dermal pathway has often been underestimated. Transdermal permeation of SVOCs can be substantially greater than is commonly assumed. Transport of SVOCs from the air to and through the skin is typically not taken into account in exposure assessments. Yet, for certain SVOCs, intake through skin is estimated to be substantially larger than intake through inhalation. Exposure scientists, risk assessors, and public health officials should be mindful of the dermal pathway when estimating exposures to indoor SVOCs. Also, they should recognize that health consequences vary with exposure pathway. For example, an SVOC that enters the blood through the skin does not encounter the same detoxifying enzymes that an ingested SVOC would experience in the stomach, intestines, and liver before it enters the blood.

Abstract  Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and tetrabromobiphenol-A (TBBP-A) were measured in a preliminary study of dust from passenger cabins and trunks of 14 UK cars. Concentrations in cabin dust of HBCDs, TBBP-A, and BDEs 47, 85, 99, 100, 153, 154, 183, 196, 197, 202, 203, 206, 207, 208, and 209 exceeded significantly (p<0.05) those in trunk dust. Sampling cabin dust thus appears to provide a more accurate indicator of human exposure via car dust ingestion than trunk dust. Elevated cabin concentrations are consistent with greater in-cabin use of BFRs. In five cars, while no significant differences (p>0.05) in concentrations of HBCDs and most PBDEs were detected in dust sampled from four different seating areas; concentrations of TBBP-A and of PBDEs 154, 206, 207, 208, and 209 were significantly higher (p<0.05) in dust sampled in the front seats. Possible photodebromination of BDE-209 was indicated by significantly higher (p<0.05) concentrations of BDE-202 in cabin dust. In-vehicle exposure via dust ingestion to PBDEs, HBCDs and TBBP-A exceeded that via inhalation. Comparison with overall exposure via diet, dust ingestion, and inhalation shows while in-vehicle exposure is a minor contributor to overall exposure to BDE-99, ΣHBCDs, and TBBP-A, it is a significant pathway for BDE-209.

Abstract  Environmental and human exposures to brominated flame retardants (BFR) have been of emerging concern since some BFR are persistent and bioaccumulative compounds. Among those, polybrominated diphenyl ethers (PBDE) have frequently been reported in low to high ng/g concentrations in human blood around the world while hexabromocyclododecane (HBCDD) only occasionally has been reported and then in the low ppb concentrations in human blood. The present study concerns PBDE congener and HBCDD concentrations in human milk from Stockholm from 1980 to 2004. HBCDD concentrations has increased four to five times since 1980 until 2002 but seems to have stabilized at this concentration in the last years (2003/04). Similarly, BDE-153 has continued to increase at least to 2001, after which it has stabilized in the mother's milk. Other PBDE congeners with four to five bromine substituents peaked 5 years earlier (1995) and are all decreasing. DecaBDE (BDE-209) is not a suitable biomarker for time trend studies according to the present results, showing no changes over time. This is likely due to its short apparent half-life in humans and poor transfer from blood to milk.

Abstract  A study was performed to assess exposure of the Belgian population to HBCD diastereoisomers. Measurements of HBCD were performed by UPLC-MS/MS, on 45 composite samples from 5 major food groups: dairy (products), meat (products), eggs, fish (products) and a group of "other" products. The medium bound estimated average daily intake (EDI) of ΣHBCD in the Belgian population was 0.99 ng kg(-1)bw d(-1). The diastereoisomer contribution to the mean EDI showed a predominance of γ-HBCD at 67%, followed by α-HBCD at 25% and 8% for β-HBCD. These results are consistent with the pattern found in the two food groups contributing the most to the EDI: meat (products) and the group of "other" products. Anyway, it has to be noted that diastereomeric distribution of HBCD can change due to bioisomerisation in biological material. Levels of HBCD diastereoisomers found in Belgian food samples of animal origin were low in comparison with those found in other EU countries and the resulting EDI was substantially below the proposed thresholds.

Abstract  BACKGROUND: Flame retardant chemicals are used in materials on airplanes to slow the propagation of fire. These chemicals migrate from their source products and can be found in the dust of airplanes, creating the potential for exposure.

METHODS: To characterize exposure to flame retardant chemicals in airplane dust, we collected dust samples from locations inside 19 commercial airplanes parked overnight at airport gates. In addition, hand-wipe samples were also collected from 9 flight attendants and 1 passenger who had just taken a cross-country (USA) flight. The samples were analyzed for a suite of flame retardant chemicals. To identify the possible sources for the brominated flame retardants, we used a portable XRF analyzer to quantify bromine concentrations in materials inside the airplanes.

RESULTS: A wide range of flame retardant compounds were detected in 100% of the dust samples collected from airplanes, including BDEs 47, 99, 153, 183 and 209, tris(1,3-dichloro-isopropyl)phosphate (TDCPP), hexabromocyclododecane (HBCD) and bis-(2-ethylhexyl)-tetrabromo-phthalate (TBPH). Airplane dust contained elevated concentrations of BDE 209 (GM: 500 ug/g; range: 2,600 ug/g) relative to other indoor environments, such as residential and commercial buildings, and the hands of participants after a cross-country flight contained elevated BDE 209 concentrations relative to the general population. TDCPP, a known carcinogen that was removed from use in children's pajamas in the 1970's although still used today in other consumer products, was detected on 100% of airplanes in concentrations similar to those found in residential and commercial locations.

CONCLUSION: This study adds to the limited body of knowledge regarding exposure to flame retardants on commercial aircraft, an environment long hypothesized to be at risk for maximum exposures due to strict flame retardant standards for aircraft materials. Our findings indicate that flame retardants are widely used in many airplane components and all airplane types, as expected. Most flame retardants, including TDCPP, were detected in 100% of dust samples collected from the airplanes. The concentrations of BDE 209 were elevated by orders of magnitude relative to residential and office environments.

Abstract  Some brominated flame retardants, for example poly brominated diphenyl ethers (PBDEs) have been identified as ubiquitous environmental contaminants. The use of the technical PentaBDE product in the European Union has been drastically reduced in the last years and is banned from 2004, while another brominated flame retardant, hexabromocyclododecane (HBCD), continues to be used. In addition to the commercial BFR products, methoxylated PBDEs (MeO-PBDEs) have been identified in biota in the aquatic environment. The origin of the MeO-PBDEs is under discussion. To our knowledge, neither OH-PBDEs nor MeO-PBDEs are commercially produced, nor have they been reported as impurities in brominated technical products or formed as byproducts in any industrial process. However, MeO-PBDEs has been reported to be natural products formed in the marine environment. As regards MeO-PBDEs detected in Baltic fish several factors points in the direction of a natural origin. On the other hand, certain MeO-PBDEs detected in environmental samples could also be metabolites/environmental transformation products of PBDEs. Knowledge of the spatial and temporal trends of the flame retardants in biota can be very useful in identifying sources of emission to the environment and in evaluating the impacts of voluntary restrictions / bans (PBDEs) and ongoing use (HBCD) on environmental contamination. In addition, this knowledge could provide valuable help in identifying the origin of the MeO-PBDEs. To this end, the Swedish Environmental Monitoring Programme on Contaminants in Biota (SEMPC) has incorporated these 3 substance groups into its monitoring of organic contaminants in herring (Clupea harengus). In this contribution we report on the results of the first 4 years

Abstract  Current monitoring of polybrominated di phenyl ethers (PBDEs) has shown that concentrations are increasing in the environment very rapidly with doubling times as short as three to five years. North America consumes a large percentage of the global market demand for PBDEs, and as a result, concentrations of PBDEs in human milk and serum are an order of magnitude higher in women from North America relative to Europe. Within sampled populations, PBDE levels in human serum have been shown to range over an order of magnitude, and high levels cannot always be attributed to occupational exposure, age or diet. One source that may be responsible for these observations is exposure in the home. These compounds are liberally applied to many common household items such as furniture, mattresses, computers and TVs to retard or hinder the outbreak of fire. Over time, these flame retardants may leach out into the home environment, where they may be inhaled or ingested, resulting in elevated levels in human serum. Very few studies have examined PBDE levels within the home and only one study has measured the concentrations of two PBDE congeners in house dust. The present study was undertaken to measure a suite PBDE congeners in house dust from a variety of homes and to assess the contribution of the three commercial PBDE mixtures (penta-, octa- and decaBDE) to the house dust composition. In addition, we also measured the concentrations of hexabromocyclododecane (HBCDD), another flame retardant. Correlations with properties of the houses such as year of construction, square footage, carpeting coverage and number of computers in the house were also examined for any positive influences.

Abstract  This article is concerned with the general theory of expansion, manufacturing processes, properties, and applications of foamed (cellular) plastics. The high strength-to-weight ratio, excellent insulating properties, and cushioning properties of cellular plastics have contributed to the development and growth of the broad range of cellular plastics in use. The total usage of foamed plastics in the United States has risen from 441 thousand metric tons in 1967 to 1.6 million metric tons in 1982 and has been projected to rise to about 2.8 million metric tons in 1995. The manufacturing processes for cellular polymers are described in terms of three classified methods based on the cell growth and stabilization processes. The properties of cellular plastics including mechanical, thermal, electrical, and environmental aging properties, are summarized. A general discussion is given on the properties of cellular plastic necessary in many applications such as the comfort cushioning, thermal insulation, packaging, structural components, buoyancy, electrical insulation, and space-filling markets. A brief discussion is also given on the process economics, raw materials, and energy considerations for the commercial products of primary importance.

Abstract  PCDD/Fs and PCBs have earlier been risk assessed and tolerable limit values were established by the Scientific Committee on Food (SCF) in 2001. The tolerable weekly intake (TWI) was set to 14 pg WHO-TEQ/kg bw. The last years estimated average dietary intake by the European population of PCDD/Fs and non-ortho PCBs is 1-3 pg TEQ/kg bw and day, which indicates that a large group of people exceeds the TWI. It has been estimated that about 1/10 of the general population, and in addition newborns and some fish consumers exceed the SCF TWI. United Kingdom followed up a risk assessment of the BDE-209 from 2002 and in May 2004 a final draft was published, but still the human health risk assessment part is missing. The Swedish Chemical Inspectorate has just finished their risk assessment of HBCDD as rapporteur to EU. The human health risk characterisation urged for more information before decisions regarding management can be made. Studies have shown that the placenta constitute an insufficient barrier for mother-foetus transfer of several POPs, such as PCB and PCB metabolites, PBDEs (including DecaBDE) and HBCDD. Exposure to POPs is above all an issue considering foetuses, infants and young children, which have a high exposure and are in a particular susceptible stage of life. Significant intake of brominated flame retardants via dust have been reported in toddlers, which means that the high exposure continues up to adulthood. It is not yet clear how this may affects the individual development. The objectives of this paper are to report a summary of present human exposure levels of a few POPs reported in Europe, and to put these levels into a risk assessment perspective. An attempt to assess risk to newborns is presented.

Abstract  Hexabromocyclododecane (HBCDD) belongs to the c lass of cycloaliphatic brominated name retardants (BFRs) and is used primarily in the building industry as a thermal insulator additive in polystyrene foam. Secondary uses arc in upholstery textiles. HBCDD is synthesized industrially by the addition of bromine to cis-trans-trans-1,5,9-cyclododecatriene. The resulting technical mixture contains three diastereoisomers (a, p. y. Figure 1) existing in proportions of approximately 6. 8 and 80%, respectively. together with other lower brominated impurities. In 2001, the global market demand for HBCDD was 16700 tonnes. The demand for HBCDD is now second to the deca-BDEs. The physical chemical properties of HBCDD are similar to those of PBDEs and other persistent organic pollutants, including polychlorinated biphenyls (PCBs), which are known to be persistent, bioaccumulative and toxic. This study examine the biomagnification of a and y- HBCDD congeners in a Lake Ontario food web. Samples were analyzed by liquid chromatography tandem mass spectrometry (LC/MS/M).