A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing.

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K(EVA-W) partition coefficients correlate well (r(2) = 0.87) with Log K(OW) values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K(EVA-W) = 1.04 Log K(OW) + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.

A significant downturn in levels of hexabromocyclododecane in the blubber of harbor porpoises (Phocoena phocoena) stranded or bycaught in the UK: an update to 2006.

In an earlier paper, we reported data indicating a sharp increase in hexabromocyclododecane concentrations in the blubber of 85 harbor porpoises from the UK, from about 2001 onward. That time trend was evaluated using data from 1994-2003, generated on a diastereoisomer basis using LC-MS. In this paper we report additional data for 138 animals collected during 2003-2006. SigmaHBCD concentrations ranged from <10 to 11,500 microg kg(-1) wet weight (up to 12,800 microg kg(-1) lipid weight) and TBBP-A was not detected in any samples. The maximum SigmaHBCD concentration observed in this study was about half that seen in the earlier study (21,400 microg kg(-1) lipid weight) and, in both studies, the highest concentration was for an animal stranded or bycaught in 2003. Investigation of time trends confirmed a statistically significant increase between 2000 and 2001 (p < 0.01) and a statistically significant decrease between 2003 and 2004 (p < 0.05). Neither trend was confounded by age, sex, nutritional status, or location. Possible contributory factors to the observed decrease include the closure in 2003 of an HBCD manufacturing plant in NE England which had considerable emissions up to 2003, and two voluntary schemes intended to reduce emissions of HBCD to the environment from industry which, however, did not formally begin until 2006.

Decabromodiphenyl ether (deca-BDE) commercial mixture components, and other PBDEs, in airborne particles at a UK site.

The occurrence of the major components of the decabromodiphenyl ether (deca-BDE) flame retardant and other PBDEs was investigated in daily air particulate samples from 17th April to 20th May 2004 at a semi-rural site in north-west England. BDE-209 was found at between <0.49 and 100 pg m(-3) (median 13 pg m(-3)), and other higher-brominated PBDE congeners were also found, particularly the nona-BDEs (e.g. BDE-207: <0.042-79 pg m(-3), median 2.5 pg m(-3)). Deca- and nona-BDEs dominated the median particulate sample congener profile: 60% BDE-209, 16% BDE-207, 6% BDE-208 and 4% BDE-206. Nona-BDEs were greatly enriched, relative to BDE-209, compared to the deca-BDE commercial mixture, which may suggest degradation of BDE-209 between source and sampling site, or release from older deca-BDE commercial mixtures, which may have contained higher proportions of nona-BDEs. The highest PBDE concentrations occurred when air-masses passed over urban and industrial areas to the SSW-SW, though small local influences may also be seen. PBDE concentrations appear to have been influenced mainly by particle levels: 1-3 microm diameter particles for BDE-153, and 3-10 microm particles for BDEs with 7-10 Br atoms. BDE-153 may either be released from combustion sources, or re-condense onto small particles after emission, whereas BDE-209 and nona-BDEs appear to be associated with larger dust particles from industrial or domestic sources.

Polybrominated diphenyl ethers in indoor dust in Ottawa, Canada: implications for sources and exposure.

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants in plastics, soft furnishings, electrical and electronic equipment, and insulation in the indoor environment, and may be released indoors via volatilization or as dusts. The penta-and octa-brominated mixes are now banned in most parts of Europe, and phasing out of their use has recently begun in North America. This study follows a previous investigation into indoor air levels of PBDEs. House dust was analyzed from the family vacuum cleaners of 68 of the same 74 randomly selected homes, in Ottawa, Canada during the winter of 2002-2003. PBDEs, comprising on average 42% BDE-209, were found in all samples. The levels were log-normally distributed with a geometric mean sigmaPBDE of 2000 ng g(-1), and a median of 1800 ng g(-1) dust. The levels in dust did not correlate with questionnaire information on house characteristics. Correlations were found between pentamix congener levels in dust and in air from the same homes, but not for congeners of the more highly brominated mixes. Exposure scenarios are presented for mean and high dust ingestion rates, and compared against exposures from other pathways, for both adults and toddlers (6 months-2 years). Assuming a mean dust ingestion rate and median dust and air concentrations, adults would be exposed to ca. 7.5 ng sigmaPBDE d(-1) via the dust ingestion pathway, which represents approximately 14% of total daily exposure when compared to diet (82%) and inhalation (4%). However, for toddlers the equivalent intakes would be 99 ng d(-1), representing 80% of their daily PBDE exposure. At high dust ingestion rates these values increase to 180 ng d(-1) (80% daily intake) for adults and 360 ng d(-1) (89% daily intake) for toddlers. The data give a clearer picture of sources of PBDE exposure in the home environment and suggest that dust could be a significant exposure pathway for some individuals, particularly children.

Perfluorinated sulfonamides in indoor and outdoor air and indoor dust: occurrence, partitioning, and human exposure.

Perfluorinated alkyl sulfonamides (PFASs) which are used in a variety of consumer products for surface protection were investigated through a comprehensive survey of indoor air, house dust, and outdoor air in the city of Ottawa, Canada. This study revealed new information regarding the occurrence and indoor air source strength of several PFASs including N-methylperfluorooctane sulfonamidoethanol (MeFOSE), N-ethylperfluorooctane sulfonamidoethanol (EtFOSE), N-ethylperfluorooctane sulfonamide (EtFOSA), and N-methylperfluorooctane sulfonamidethylacrylate (MeFOSEA). Passive air samplers consisting of polyurethane foam disks were calibrated and used to conduct the indoor and outdoor survey. Indoor air concentrations for MeFOSE and EtFOSE (1490 and 740 pg m(-3), respectively) were about 10-20 times greater than outdoor concentrations, establishing indoor air as an important source to the outside environment. EtFOSA and MeFOSEA concentrations were lower in indoor air (40 and 29 pg m(-3) respectively) and below detection in outdoor air samples. For indoor dust, highest concentrations were recorded for MeFOSE and EtFOSE with geometric mean concentrations of 110 and 120 ng g(-1), while concentrations for EtFOSA and MeFOSEA were below detection and 7.9 ng g(-1) respectively. MeFOSE and EtFOSE concentrations in house dust followed levels in indoor air. However, resolution of the coupled air and dust data (for the same homes) was not successful using existing KoA-based models for surface-air exchange. The partitioning to house dust was greatly underpredicted. The difficulties with existing models may be due to the high activity coefficient of PFASs in octanol and/or a situation where the dust is greatly oversaturated with respect to the air due to components of the dust being contaminated with PFASs. A human exposure assessment based on median air and dust concentrations revealed that human exposure through inhalation (100% absorption assumed) and dust ingestion were approximately 40 and approximately 20 ng d(-1), respectively. However, for children the dust ingestion pathway was dominant and accounted for approximately 44 ng d(-1).

Is house dust the missing exposure pathway for PBDEs? An analysis of the urban fate and human exposure to PBDEs.

Polybrominated diphenyl ether (PBDE) body burdens in North America are 20 times that of Europeans and some "high accumulation" individuals have burdens up to 1-2 orders of magnitude higher than median values, the reasons for which are not known. We estimated emissions and fate of sigma PBDEs (minus BDE-209) in a 470 km2 area of Toronto, Canada, using the Multi-media Urban Model (MUM-Fate). Using a combination of measured and modeled concentrations for indoor and outdoor air, soil, and dust plus measured concentrations in food, we estimated exposure to sigma PBDEs via soil, dust, and dietary ingestion and indoor and outdoor inhalation pathways. Fate calculations indicate that 57-85% of PBDE emissions to the outdoor environment originate from within Toronto and that the dominant removal process is advection by air to downwind locations. Inadvertent ingestion of house dust is the largest contributor to exposure of toddlers through to adults and is thus the main exposure pathway for all life stages other than the infant, including the nursing mother, who transfers PBDEs to her infant via human milk. The next major exposure pathway is dietary ingestion of animal and dairy products. Infant consumption of human milk is the largest contributor to lifetime exposure. Inadvertent ingestion of dust is the main exposure pathway for a scenario of occupational exposure in a computer recycling facility and a fish eater. Ingestion of dust can lead to almost 100-fold higher exposure than "average" for a toddler with a high dust intake rate living in a home in which PBDE concentrations are elevated.

Passive sampling survey of polybrominated diphenyl ether flame retardants in indoor and outdoor air in Ottawa, Canada: implications for sources and exposure.

The polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in plastics of soft furnishings, TV sets and computers, and insulation in the indoor environment. The penta-BDEs--now banned in most parts of Europe but still used in North America--are additive flame retardants that may be released to the indoor environment via volatilization or as dusts. In this study, to investigate general population PBDE exposure, air was sampled in 74 randomly selected homes in Ottawa, Canada and at seven outdoor sites during the winter of 2002--3, using polyurethane foam (PUF) disk passive air samplers. The passive sampling rate (2.5 m3 day(-1)) was determined through a pilot study employing active and passive samplers side-by-side at selected indoor locations. Indoor air concentrations of PBDEs were log-normally distributed with a geometric mean of 120 pg m(-3) and a median of 100 pg m(-3), approximately 50 times higher than the range of outdoor air concentrations (<0.1-4.4 pg m(-3)). The maximum daily human exposure via the inhalation pathway based on median PBDE levels found in this survey was estimated to be 1.9 ng day(-1) (female) and 2.0 ng day(-1) (male), representing 4.1% (f) and 4.4% (m) of overall daily intake.