Partitioning Of Polybrominated Diphenyl Ethers Research Articles

Characteristics of halogenated flame retardants in the atmosphere of Dalian, China

Samples of gas and fine particulate matter (PM2.5) were collected in Dalian, China, a typical coastal city, to determine the concentrations, seasonal variations, influential factors, sources, and gas-PM2.5 partitioning of polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and dechlorane plus (DPs) in the ambient air. Annual average concentrations of Σ7PBDEs, BDE209, Σ6NBFRs, and DPs were 4.40 ± 2.93, 1460 ± 2500, 7.81 ± 6.85, and 0.15 ± 0.14 pg/m3 for the gas phase, and 2.68 ± 1.64, 4291 ± 4306, 13.6 ± 23.4, and 0.31 ± 0.22 pg/m3 for the fine particle phase, respectively. BDE209 was the dominant congener, followed by HBB and BEH-TEBP, and seasonal variations in air concentrations were apparent for BFRs, especially those in the gas phase. Moreover, meteorological parameters and criteria air pollutants revealed significant positive correlations between temperature and less-brominated BFRs in the gas phase, and between PM2.5 and highly-brominated BFRs in the particle phase. This suggests that the presence of these compounds in ambient air may largely result from combustion-related processes. Furthermore, an analysis of the gas-PM2.5 partitioning of BFRs and DPs suggested that BFRs and DPs mostly attained equilibrium, except for some NBFRs. Due to the ban of commercial penta-, octa-, and deca-BDEs by the Stockholm Convention, emissions from historical use and combustion are becoming the important sources of PBDEs in China.

Occurrence, air-sea exchange, and gas-particle partitioning of atmospheric polybrominated diphenyl ethers from East Asia to the Northwest Pacific Ocean

The occurrence, air–sea exchange, and gas–particle partitioning of polybrominated diphenyl ethers (PBDEs) were analyzed during a 2015 research expedition from the East China Sea (ECS) to the open Northwest Pacific Ocean (NWP). The sum of 13 PBDEs (Σ13PBDEs) in air and surface seawater varied in the range of 0.54–14.5.pg m−3 and 0.60–13.5 pg L−1, respectively, with the highest concentrations observed in the ECS. The Clausius–Clapeyron approach and air mass origin analysis indicated that continued primary emissions of PBDEs, particularly BDE-209, from East Asian sources governed the spatial variability of air PBDEs over the NWP through long-range atmospheric transport (LRAT). Net air-to-seawater gas deposition of PBDEs was evidenced based on the fugacity calculation with sum fluxes of seven selected PBDEs ranging from −45 to −582 pg m−2 d−1. Following the substantial advection of aerosol phase BDE-209 over the ECS, dry particle deposition dominated the input pathway of PBDEs into the ECS, whereas in the open NWP, relatively free from the influence of the land emissions, fluxes in PBDE absorption and in dry particle deposition were comparable. This suggests an impact of continental outflow on the fate of atmospheric PBDEs over the NWP. Regarding gas–particle partitioning, PBDEs over the NWP were obviously absorbed into continental organic aerosols during atmospheric transport, except for BDE-209, which tended to remain within the steady state.

Characterization of polybrominated diphenyl ethers (PBDEs) in various aqueous samples in Taiwan

In this study, 20 groundwater samples and 7 surface water samples were collected and analyzed by HRGC-HRMS to evaluate the levels, congener distributions, and dissolved/solid partitioning of polybrominated diphenyl ethers (PBDEs) in water matrix as well as the removal efficiency of a typical water treatment plant (WTP). The results indicated that the level of PBDEs concentrations ranging from 18.51 to 4212 pg/L and 30.24 to 1021 pg/L were found in groundwater and surface water, respectively. BDE-209 predominated and contributed over 90% of total PBDEs concentrations for all samples analyzed. In addition, the dissolved/solid distribution indicated that 60–80% of PBDEs were measured in solid phase. 97% of total PBDEs was removed in a WTP. Positive matrix factorization (PMF) analysis was conducted for groundwater samples and the results indicated that 3% and 41% of PBDEs were attributed to octa and deca-BDEs commercial mixtures, respectively, while 56% resulted from anaerobic microorganism debromination process. Understanding the PBDEs occurrences, distribution and debromination process as well as their removal efficiency of water treatment plant could provide valuable information on the fate of those compounds in environment.

Distribution and partitioning of polybrominated diphenyl ethers in sediments from the Pearl River Delta and Guiyu, South China.

Polybrominated diphenyl ethers (PBDEs) were investigated by GC-NCI-MS in sediments collected from the Pearl River Delta (PRD) and Guiyu town, South China. The concentrations of ∑39PBDEs and BDE 209 were in the ranges of 0.31-38.9 ng g-1 and 12.2-488 ng g-1 in the PRD, and 2.57-21,207 ng g-1 and 7.02-66,573 ng g-1 in Guiyu, respectively. The levels of PBDEs in Dongjiang River (DJ), Zhujiang River (ZJ), and Beijiang River (BJ), and Guiyu (GY) followed the order: GY > DJ > ZJ > BJ. The very high PBDE concentration (87,779 ng g-1) was detected at G1 sediment in Guiyu compared with those in sediments from other regions around the world. The PBDE mixtures detected were mainly comprised of penta-, octa-, and deca-BDEs, in which deca-BDE was the dominant constituent. The abundant congeners, excluding BDE-209, were BDE-47, BDE-99, and BDE-183, suggesting the diverse use of commercial products containing these congeners in this region. The concentrations of major congeners were significantly correlated with total organic carbon (TOC) contents (p < .01). A good regression between the logarithmic TOC-normalized BDE average concentrations and their log Kow confirmed that the sorption of PBDEs on sediment organic matter governed their spatial distribution, transport, and fate in the sediments. Furthermore, risk quotients (RQs) derived from concentrations of PBDEs in sediments from our study may pose high ecological risks to exposure of benthic organisms.

In silico investigation of gas/particle partitioning equilibrium of polybrominated diphenyl ethers (PBDEs)

Polybrominated diphenyl ethers (PBDEs), a group of typical brominated flame retardants (BFRs), have drawn an increasing concern due to their widespread manufacture, usage and disposal around the world and the frequent detection in a variety of environmental media. In the present study, we investigated the molecular mechanism of the partitioning equilibrium of PBDEs between gas and atmospheric particles, and developed a new temperature-dependent predictive model for the gas/particle partition coefficient (KP) of these chemicals. Quantum chemical computations were implemented at B3LYP/6-31G (d,p) level of theory based on the neutral electronic ground state of PBDE congeners by Gaussian 09 software package. The model performance was assessed by different validation strategies and the application domain was defined by Williams Plot. Mechanism analysis indicated that the interactions of dispersion, electrostatic and hydrogen bond play crucial roles in the partitioning of PBDEs between the two phases. The developed model can be used to estimate the KP values of PBDEs for which experimental measurements are restricted. Therefore, this work provides an alternative method in a regulatory context of PBDEs.

Polybrominated Diphenyl Ethers in Human Milk and Serum from the U.S. EPA MAMA Study: Modeled Predictions of Infant Exposure and Considerations for Risk Assessment.

Background:Serum concentrations of polybrominated diphenyl ethers (PBDEs) in U.S. women are believed to be among the world’s highest; however, little information exists on the partitioning of PBDEs between serum and breast milk and how this may affect infant exposure.Objectives:Paired milk and serum samples were measured for PBDE concentrations in 34 women who participated in the U.S. EPA MAMA Study. Computational models for predicting milk PBDE concentrations from serum were evaluated.Methods:Samples were analyzed using gas chromatography isotope-dilution high-resolution mass spectrometry. Observed milk PBDE concentrations were compared with model predictions, and models were applied to NHANES serum data to predict milk PBDE concentrations and infant intakes for the U.S. population.Results:Serum and milk samples had detectable concentrations of most PBDEs. BDE-47 was found in the highest concentrations (median serum: 18.6; milk: 31.5 ng/g lipid) and BDE-28 had the highest milk:serum partitioning ratio (2.1 ± 0.2). No evidence of depuration was found. Models demonstrated high reliability and, as of 2007–2008, predicted U.S. milk concentrations of BDE-47, BDE-99, and BDE-100 appear to be declining but BDE-153 may be rising. Predicted infant intakes (ng/kg/day) were below threshold reference doses (RfDs) for BDE-99 and BDE-153 but above the suggested RfD for BDE-47.Conclusions:Concentrations and partitioning ratios of PBDEs in milk and serum from women in the U.S. EPA MAMA Study are presented for the first time; modeled predictions of milk PBDE concentrations using serum concentrations appear to be a valid method for estimating PBDE exposure in U.S. infants.Citation:Marchitti SA, Fenton SE, Mendola P, Kenneke JF, Hines EP. 2017. Polybrominated diphenyl ethers in human milk and serum from the U.S. EPA MAMA Study: modeled predictions of infant exposure and considerations for risk assessment. Environ Health Perspect 125:706–713; http://dx.doi.org/10.1289/EHP332

Atmospheric occurrence and gas-particle partitioning of PBDEs at industrial, urban and suburban sites of Thessaloniki, northern Greece: Implications for human health

Air samples were collected during the cold and the warm period of the year 2012 and 2013 at three sites in the major Thessaloniki area, northern Greece (urban-industrial, urban-traffic and urban-background) in order to evaluate the occurrence, profiles, seasonal variation and gas/particle partitioning of polybrominated diphenyl ethers (PBDEs). The mean total concentrations of particle phase ∑12PBDE in the cold season were 28.7, 19.5 and 3.87 pg m−3 at the industrial, urban-traffic and urban-background site, respectively, dropping slightly in the warm season (23.7, 17.5 and 3.14 pg m−3), respectively. The corresponding levels of gas-phase ∑12PBDE were 14.4, 7.15 and 4.73 pg m−3 in the cold season and 21.2, 11.1 and 6.27 pg m−3 in the warm season, respectively. In all samples, BDE-47 and BDE-99 were the dominant congeners. Absorption of PBDEs in the organic matter of particles appeared to drive their gas/particle partitioning, particularly in the cold season. The estimated average outdoor workday inhalation exposure to ∑12PBDE in the cold and the warm period followed the order: industrial site (288 and 299 pg day−1) > urban-traffic site (178 and 191 pg day−1) > urban-background site (58 and 63 pg day−1). The exposures to BDE-47, BDE-99, BDE-153 and ∑3PBDE via inhalation, for children outdoor worker and seniors were several orders of magnitude lower than their corresponding oral RfD values.

Prediction of gas/particle partitioning of polybrominated diphenyl ethers (PBDEs) in global air: A theoretical study

Abstract. Gas/particle (G/P) partitioning of semi-volatile organic compounds (SVOCs) is an important process that primarily governs their atmospheric fate, long-range atmospheric transport, and their routes of entering the human body. All previous studies on this issue are hypothetically based on equilibrium conditions, the results of which do not predict results from monitoring studies well in most cases. In this study, a steady-state model instead of an equilibrium-state model for the investigation of the G/P partitioning behavior of polybrominated diphenyl ethers (PBDEs) was established, and an equation for calculating the partition coefficients under steady state (KPS) of PBDEs (log KPS = log KPE + logα) was developed in which an equilibrium term (log KPE = log KOA + logfOM −11.91 where fOM is organic matter content of the particles) and a non-equilibrium term (log α, caused by dry and wet depositions of particles), both being functions of log KOA (octanol–air partition coefficient), are included. It was found that the equilibrium is a special case of steady state when the non-equilibrium term equals zero. A criterion to classify the equilibrium and non-equilibrium status of PBDEs was also established using two threshold values of log KOA, log KOA1, and log KOA2, which divide the range of log KOA into three domains: equilibrium, non-equilibrium, and maximum partition domain. Accordingly, two threshold values of temperature t, tTH1 when log KOA = log KOA1 and tTH2 when log KOA = log KOA2, were identified, which divide the range of temperature also into the same three domains for each PBDE congener. We predicted the existence of the maximum partition domain (the values of log KPS reach a maximum constant of −1.53) that every PBDE congener can reach when log KOA ≥ log KOA2, or t ≤ tTH2. The novel equation developed in this study was applied to predict the G/P partition coefficients of PBDEs for our Chinese persistent organic pollutants (POPs) Soil and Air Monitoring Program, Phase 2 (China-SAMP-II) program and other monitoring programs worldwide, including in Asia, Europe, North America, and the Arctic, and the results matched well with all the monitoring data, except those obtained at e-waste sites due to the unpredictable PBDE emissions at these sites. This study provided evidence that the newly developed steady-state-based equation is superior to the equilibrium-state-based equation that has been used in describing the G/P partitioning behavior over decades. We suggest that the investigation on G/P partitioning behavior for PBDEs should be based onsteady-state, not equilibrium state, and equilibrium is just a special case of steady-state when non-equilibrium factors can be ignored. We also believe that our new equation provides a useful tool for environmental scientists in both monitoring and modeling research on G/P partitioning of PBDEs and can be extended to predict G/P partitioning behavior for other SVOCs as well.

Atmospheric Occurrence and Gas-Particle Partitioning of PBDEs in an Industrialised and Urban Area of Florence, Italy

Air samples were collected both at an urban and an industrial area of Florence (Italy) in order to evaluate the occurrence, profiles, seasonal variation and gas/particle partitioning of polybrominated diphenyl ethers (PBDEs). The mean total (gas + particle phase) PBDE concentrations were 42.8 ± 7.8 and 89.0 ± 21.1 pg/m3 in the urban and industrial sites, respectively. In all samples, BDE-209 was the most abundant congener, followed by BDE-47 and BDE-153 in the industrial site, and by BDE-99 in the urban site. The Σ6PBDE (sum of BDE-28, -47, -99, -100, 153, -154) concentrations in the urban (12.1–27.9 pg/m3) and industrialised (21.4–44.3 pg/m3) sites were comparable to, or slightly lower than measured at other sites. The partition coefficient of PBDEs between the gas and particle phases (Kp) was well correlated with the subcooled liquid vapor pressure (P°L) for all samples. The measured particulate sorption of PBDEs was compared to the predictions from Junge-Pankow (J/P) model and KOA absorption model. While the Junge-Pankow model tends to overestimate the particulate sorption, the KOA based model seemed to fit the PBDE data.

PBDEs in leachates from municipal solid waste dumping sites in tropical Asian countries: phase distribution and debromination

Polybrominated diphenyl ethers (PBDEs) are extensively used as flame retardants in many consumer products, and leachates from landfills have been identified as one of the possible sources of PBDEs in the environment. Meanwhile, the unprecedented economic and population growths of some Asian countries over the last decade have led to significant increases in the amount of waste containing PBDEs in that region. This study investigates the status of PBDEs in leachates from municipal solid waste dumping sites (MSWDS) in tropical Asian countries. A total of 46 PBDE congeners were measured, both in the adsorbed (n=24) and dissolved (n=16) phases, in leachate samples collected, from 2002 to 2010, from ten MSWDS distributed among the eight countries of Lao PDR, Cambodia, Vietnam, India, Indonesia, Thailand, the Philippines, and Malaysia. PBDEs were predominantly found in the adsorbed phase. Partitioning of PBDEs in the dissolved phase was associated with the presence of dissolved organic matter; the apparent organic carbon-normalized partition coefficients (K'oc) of the BDE congeners were lower by two to four orders of magnitude than the K oc predicted from the octanol-water partition coefficients (K ow). The total PBDE concentrations from mono- to deca-BDEs ranged from 3.7 to 133,000 ng/L, and showed a trend toward higher concentrations in the more populous and industrialized Asian countries. The congener profiles in the leachates basically reflected the composition of PBDE technical mixtures. The occurrence of congeners not contained, or in trace concentrations, in technical products (e.g., BDEs 208, 207, 206, 202, 188, 179, 49, 17/25, 8, 1) was observed in most of the leachate samples, suggesting the debromination of technical mixtures, including BDE-209, in the MSWDS of tropical Asian countries. Moreover, the temporal trend indicated the reduction of BDE-209 over time, with a corresponding increase in and/or emergence of lower brominated PBDE congeners. The results indicated that MSWDS of tropical Asian countries are potential sources of environmental PBDEs, which may be transported to the aquatic environment via dissolution with dissolved organic matter. MSWDS could be amplifiers of PBDE toxicity in the environment, possibly through debromination.

Liposome and protein–water partitioning of polybrominated diphenyl ethers (PBDEs)

Bioaccumulation of polybrominated diphenyl ethers (PBDEs) in marine and terrestrial organisms is of great environmental concern. Understanding the partitioning of PBDEs to biological phases is crucial for elucidating their bioaccumulation behavior. In this study, partitioning coefficients of PBDEs from water to phospholipid liposomes (Klipw) and to bovine serum albumin (BSA) (KBSAw) were measured using a polymer depletion method. Klipw values measured in two laboratories are in an excellent agreement (within 0.14 log units), indicating a high method repeatability. The values of log Klipw and log KBSAw are in the range of 6.3–8.2 and 5.1–7.0, respectively, representing the highest of these partition coefficients measured to date. Log Klipw values for PBDEs are similar to the log of the octanol–water partition coefficients (Kow) (log Klipw−log Kow=−0.06±0.23; mean±SD of 7 congeners), consistent with the data of chlorobenzenes and polychlorinated biphenyls (PCBs) reported in the literature. No hydrophobicity cutoff was observed for partitioning to the liposome membrane. Log KBSAw values for PBDEs increase linearly with log Kow and do not follow the non-linear trend observed for polycyclic aromatic hydrocarbons (PAHs). This difference between PBDEs and PAHs suggests specific binding mechanisms to serum albumin even for hydrophobic compounds.

Levels, compositions, and gas-particle partitioning of polybrominated diphenyl ethers and dechlorane plus in air in a Chinese northeastern city

Air samples were collected using a HiVol air sampler for 24 hours every week from September 2008 to August 2009 in the city of Dalian, a typical coast city in Northeast China. 12 polybrominated diphenyl ethers (PBDEs) congeners (BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183 and -209) and Dechlorane Plus (DP) were measured and analyzed. Annual arithmetic mean concentrations of ∑12PBDEs (gas+particle phase) and DP (Particle phase) in air samples were 104±95pgm−3 and 3±6pgm−3, respectively. BDE-209 was the dominating congener in all seasons with the contribution of 56±21% of ∑12PBDEs, followed by BDE-28, -47 and -99. The mean fractional abundance of the syn-DP isomer (fsyn) in all samples was 0.31±0.14, lower than the value reported for technical DP mixture produced in China (fsyn=0.4), indicating depletion of syn-DP in Chinese air. A year monitoring of PBDE in air produced a large dataset that provided a gas-particle partitioning analysis based on a wide temperature range and also individual PBDE congeners. The values of the portion of PBDEs in particle phase to the whole PBDEs in air had a general trend that became higher with the increasing number of bromine atoms at the same temperature and with decreasing temperature for the same congener. The result of PBDEs gas-particle partitioning analysis indicated that PBDEs in gas and particle phases were closer to equilibrium at higher temperature periods. For the first time, the KOA-based absorption model was evaluated for individual PBDE congeners. The results showed that, the model is more suitable for predicting low brominated congeners than high brominated ones, and the accuracy of model predictions decreases along with decrease of temperatures for individual PBDE congeners.

Phase partitioning, concentration variation and risk assessment of polybrominated diphenyl ethers (PBDEs) in the atmosphere of an e-waste recycling site

The daytime and nighttime air samples were collected from an e-waste recycling site in Guiyu (GY) and its upwind and downwind direction sites in Chendian (CD) and Gurao (GR), respectively, during September and December 2005 to determine the phase partitioning, seasonal and diurnal variation of polybrominated diphenyl ethers (PBDEs). The three sites showed similar congener compositions with BDEs-28, −47, −99, −207 and −209 as the dominant congeners. The gas phase contribution ranged from 42.1% ± 17.1% of the total PBDEs in summer to 9.0% ± 8.6% in winter. Partitioning of PBDEs between gas and particulate phases was well correlated with the subcooled liquid vapor pressure ( P L 0 ) for all samples. Both Junge–Pankow adsorption model and K OA-based absorption model fitted well the PBDEs data in winter but overestimated the sorption of PBDEs in summer. The mean atmospheric concentrations of BDEs-47 (2748 pg m −3 in summer and 6146 pg m −3 in winter) and -99 (1656 pg m −3 in summer and 4911 pg m −3 in winter) in GY were much higher than those from other places around the world. Additionally, the time series of PBDEs in GY demonstrated a pronounced diurnal variation pattern, but not CD and GR, where PBDEs appeared partly associated with regional accumulation. Source characterization from local emissions may be the major factor controlling the diurnal variation of PBDEs in GY air. The risk assessment showed that the total daily intakes of BDE-99 in GY was 9.0–34.9 ng kg −1-bw d −1, which is higher than the maximal allowed intake level (0.26 ng kg −1-bw d −1) with factors of 35–135, indicating possible health risk for GY residents with exposure to PBDEs.

The factors controlling the partitioning of polybrominated diphenyl ethers and polychlorinated biphenyls in the water-column of the Pearl River Estuary in South China

In this study, the distribution and partition of polybrominateddiphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in water from the Pearl River Estuary were investigated. A seasonal dependence for dissolved and particle phase PCB and PBDE levels was observed. A high dissolved phase level occurred in the dry season. The positive correlation between POC content in the particles and phase distribution coefficients (Kp) suggested that POC may play an important role in determining the partition of PBDEs and PCBs. A linear correlation between the observed log KOC and log KOW for PBDEs and PCBs was found with slopes less than one. The observed log KOC values were lower than the predicted log KOC values for PBDEs (except for BDE28). The log KOC values were higher than the predicted values for PCBs. A combination of sorption to colloids (10–98% for PBDEs and less than 25% for PCBs) and adsorption to BC was responsible for this observation.

Levels, fluxes and time trends of persistent organic pollutants in Lake Thun, Switzerland: Combining trace analysis and multimedia modeling

Levels, mass fluxes, and time trends of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Lake Thun, a peri-Alpine lake, are investigated. We present measurements of PBDEs and PCBs in air, lake water, lake sediment, and tributary water. These measurements are combined with a multimedia fate model, based on site-specific environmental parameters from the lake catchment. Measured loadings of PBDEs and PCBs in air and tributaries were used to drive the model. The model satisfactorily reproduces PBDE and PCB congener patterns in water and sediment, but it tends to yield concentrations in water below the measurements and concentrations in sediment exceeding the measurements. A sensitivity analysis reveals that partitioning of PBDEs and PCBs between the aqueous dissolved phase and suspended particulate matter in the water column strongly affects the model results, in particular the concentrations in water and sediment. For lower-brominated PBDEs, approximately 70% and 30% of input into the lake stems from atmospheric deposition and from tributaries, respectively. For heavier PBDEs and all PCBs, rivers appear to deliver the major load (64–92%). Waste water effluents are of minor importance. 50–90% of the total input is buried in the permanent sediment. Sediment burial makes PBDEs and PCBs less available for recycling in the environment, and reduces concentrations in the outflowing river. If use of deca-BDE increases in the future, levels in Lake Thun will follow the same trend. If the use and resulting environmental emissions decrease, concentrations in water will rapidly decline, according to our calculations, while sediment levels will decrease at a considerably slower rate.

Partitioning of polybrominated diphenyl ethers (PBDEs) in serum and milk from the same mothers

We and others have previously described partitioning of chemicals, including polychlorinated- p-dioxins, dibenzofurans, and biphenyls in different types of human tissues and fluids, including blood and milk. Additionally, we previously reported the blood to milk partitioning of polybrominated diphenyl ethers (PBDEs) in a group of 11 women. Partitioning is of importance in understanding the toxicokinetics of these compounds and also in clinical medicine in improving estimates of levels in different matrices including blood and milk. In this study we extend these findings, describing the levels of PBDEs detected in the serum and milk of 29 women from Texas. The median sum of the levels of the four most detected congeners (BDE 47, 99, 100, and 153) in serum was 27.8 ng g −1 lipid (range 6.7–501.6 ng g −1 lipid). In milk, the median sum of the levels of the same congeners was 39.7 ng g −1 lipid (range 12.9–580.3 ng g −1 lipid). The levels detected in breast milk in this study are similar to those we reported in 2003, where a median total PBDE level of 34 ng g −1 lipid was reported. When congener specific blood to milk partitioning ratios were calculated for BDEs 47, 99, 100, and 153, the relatively small tetrabrominated congener, BDE 47, was found in higher concentrations in milk compared to blood, while the higher molecular weight hexabrominated congener, BDE 153, was found in approximately equal quantities in blood and milk, on a lipid normalized basis. The reason for the differential partitioning of PBDE congeners in milk and blood could be due to variation in toxicokinetics, specifically distribution based on molecular size or molecular weight.

Water‐column concentrations and partitioning of polybrominated diphenyl ethers in the New York/New Jersey Harbor, USA

AbstractDespite the emerging concern regarding polybrominated diphenyl ethers (BDEs), very few measurements of BDE concentrations in ambient water have been published. In the present study, BDEs were measured in water samples from the New York/New Jersey Harbor (USA). Samples were taken in Raritan Bay west of Sandy Hook during four intensive sampling campaigns in 2000 and 2001. Congeners 17, 47, 99, 100, 153, 154, 183, and 209 were detected. Total BDE (σBDE) concentrations (average ± standard deviation) were 175 ± 75 ng/g in the particle phase and 110 ± 72 pg/L in the apparent dissolved phase. The deca‐congener, BDE 209, constituted 85 and 9% of σBDEs in the particle and apparent dissolved phases, respectively. The σBDE levels are significantly higher than those measured in Lake Ontario, USA, and in The Netherlands, but they are similar to concentrations measured in Lake Michigan and San Francisco Bay (both USA). Calculated values of the organic carbon‐water partition coefficient (KOC) were strongly correlated with literature values of the octanol‐water partition coefficient (KOW). The data suggest that sorption of BDEs to colloids is important in this system, although quantifying the extent of colloid sorption is difficult.

Atmospheric concentrations and phase partitioning of polybrominated diphenyl ethers (PBDEs) in Izmir, Turkey

Atmospheric concentrations of 7 PBDE congeners (BDE-28, -47, -99, -100, -153, -154 and -209) were determined at four sites (i.e. Suburban, Urban 1, Urban 2, Industrial) in Izmir, Turkey and their gas/particle partitioning was investigated. Total PBDE (∑ 7PBDE) concentrations ranged between 11 (Urban 1) and 149 pg m −3 (Industrial) in summer, while in winter, they ranged from 6 (Suburban) to 81 pg m −3 (Industrial). BDE-209 was the dominant congener at all sites, followed by BDE-99 and -47. Investigation of source profiles indicated that the air samples were dominated by congeners of the penta and deca-technical BDE mixtures. The measured PBDE particle fractions were compared to the predictions of the K OA (octanol-air partition coefficient)-based equilibrium partitioning model and to the dynamic uptake model developed by others for passive samplers, which was adapted to model gas-particle partitioning in this study. For BDE-28, good agreement was observed between the experimental particle fractions and those predicted by the equilibrium partitioning model. However, this model overestimated the particle fractions of other congeners. The predictions of the dynamic uptake model supported the hypothesis that the unexpectedly high partitioning of BDEs (except BDE-28) to the gas-phase is due to their departure from equilibrium partitioning. When congeners with very large octanol-air partition coefficients (i.e. BDE-100, -99, -154, -153, and -209) are emitted from their sources in the gas-phase, they may remain in that phase for several months before reaching equilibrium with atmospheric particles. This may also have important implications for the transport of atmospheric PBDEs. For example, in addition to particle-bound transport, the gas-phase transport of highly brominated congeners (i.e. BDE-209) may also be important.