The Ins and Outs of Per- and Polyfluoroalkyl Substances in the Great Lakes: The Role of Atmospheric Deposition.

As part of the Integrated Atmospheric Deposition Network, precipitation (n = 207) and air (n = 60) from five sites and water samples (n = 87) from all five Great Lakes were collected in 2021-2023 and analyzed for 41 per- and polyfluoroalkyl substances (PFAS). These measurements were combined with other available data to estimate the mass budget for four representative compounds, PFBA, PFBS, PFOS, and PFOA for the basin. The median Σ41PFAS concentrations in precipitation across the five sites ranged between 2.4 and 4.5 ng/L. The median Σ41PFAS concentration in lake water was highest in Lake Ontario (11 ng/L) and lowest in Lake Superior (1.3 ng/L). The median Σ41PFAS concentration in air samples was highest in Cleveland at 410 pg/m3 and lowest at Sleeping Bear Dunes at 146 pg/m3. The net mass transfer flows were generally negative for Lakes Superior, Michigan, and Huron and positive for Lakes Erie and Ontario, indicating that the three most northern lakes are accumulating PFAS and the other two are eliminating PFAS. Atmospheric deposition is an important source of PFAS, particularly for Lake Superior.

Socio-Economic Factors Impact US Dietary Exposure to Halogenated Flame Retardants.

Although diet is an important route of exposure for brominated flame retardants (BFRs), little is known of their presence in US food. Therefore, we purchased meat, fish, and dairy product samples (n = 72) in Bloomington, IN, from 3 stores representing national retail chains at different price levels. Composite samples (n = 42) were analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), novel BFRs (NBFRs), and dechlorane plus (DP). Concentrations of total halogenated flame retardants (HFRs) ranged between 54 and 1,400 pg/g ww, with PBDEs being the predominant compounds. Concentrations of NBFRs, but not PBDEs, in US food items were significantly impacted by price, raising the issue of environmental justice. Nonorganic food generally had a higher abundance of BDE-209 than organic food items. Estimates of dietary exposure revealed that meat and cheese consumption contribute most to the overall HFR intake and that intakes are highest for children and for non-Hispanic Asians. Taking into account several caveats and limitations of this study, these results as a whole suggest that health burdens from dietary exposure to HFRs have become minimal for US citizens, highlighting the positive impact of regulatory efforts.

The use of silicone wristbands to evaluate personal exposure to semi-volatile organic chemicals (SVOCs) in France and Italy.

In this exploratory study, we measured for the first-time human exposure to about 90 semi-volatile organic chemicals (SVOCs) in France and Italy using silicone wristbands. Participants in France (n = 40) and in Italy (n = 31) wore a silicone wristband for five days during 2018 and 2019. Samples were analyzed for 39 polybrominated diphenyl ethers (PBDEs), 10 novel brominated flame retardants (nBFRs), 25 organophosphate esters (OPEs), and 18 polycyclic aromatic hydrocarbons (PAHs). In both groups, the most commonly detected chemicals were BDE-209, BEHTBP, tris[(2R)-1-chloro-2-propyl] phosphate (TCIPP), and phenanthrene among PBDEs, nBFRs, OPEs, and PAHs, respectively. The concentrations of ∑39 PBDEs, ∑10 nBFRs, ∑25 OPEs, ∑18 PAHs, and of most individual chemicals were generally significantly higher in samples from France than in those from Italy, except for BDE-209 and TCIPP. On a broader scale, the chemical concentrations were generally significantly lower in this study than those measured in the United States in previous studies using the same type of wristbands. Efforts to standardize the protocols for the use of silicone wristbands are still needed but this study shows that wristbands are capable of capturing regional differences in human exposure to a large variety of SVOCs and, therefore, can be used as personal exposure monitor for studies with global coverage.

Per- and polyfluoroalkyl substances in paired dust and carpets from childcare centers.

Carpets can be a significant source of per- and polyfluoroalkyl substances (PFASs) in the indoor environment and may be an especially important source of exposure for children and toddlers. Most previous studies focused on measuring indoor dust only. In this study, we measured PFAS concentrations in paired carpet and dust samples from 18 California childcare centers in 2018 to investigate carpet as a contributor to PFASs in dust. Median total PFAS concentrations (∑PFASs) in carpets and dust were 471 ng/g and 523 ng/g, respectively. 6:2 FTOH and 6:2 FTSA were the two dominant PFASs, collectively accounting for over 50% of the ∑PFASs in both media. Other frequently detected PFASs included C4-C14 perfluoroalkylcarboxylic acids, C4-C8 perfluoroalkylsulfonic acids, PFDS, 4:2 FTSA, 8:2 FTSA, FOSA, MeFOSE, EtFOSE, 8:2 FTOH, and 10:2 FTOH. We found strong associations between PFAS levels in carpet and dust pairs, suggesting that carpets can be a source and a sink for PFASs. The estimated total perfluoroalkyl acids (PFAA) intake via dust ingestion for children was 0.023, 0.096, and 1.9 ng/kg body weight/day in the low-, intermediate-, and high-exposure scenarios, respectively. Our data suggest that PFASs of emerging concern are playing an increasingly important role in indoor exposure to PFASs.

Association between Thyroid Function and Exposures to Brominated and Organophosphate Flame Retardants in Rural Central Appalachia.

Exposure to flame retardants (FRs) is associated with adverse effects on human health. Focusing on three FR groups, including polybrominated diphenyl ethers (PBDEs), organophosphate FRs (OPFRs), and novel brominated FRs (nBFRs), we determined the levels of these chemicals in indoor air in homes in rural Central Appalachia using passive air samplers and personal exposures in the residents of these homes using silicone wristbands. We also investigated the relationships between the FR levels in wristbands and the thyroid function. The median total concentrations of PBDEs, OPFRs, and nBFRs were 210, 25 000, and 69 pg/m3 in indoor air, and 49, 670, and 110 ng/g in wristbands, respectively. The most abundant chemicals in both air and wristbands were BDE-47 and -99 among PBDEs, tris[(2R)-1-chloro-2-propyl] phosphate among OPFRs, and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate and bis(2-ethylhexyl) tetrabromophthalate among nBFRs. In gender-specific regression models that were controlled for age and smoking, significant associations were observed between BDE-99, BDE-197, and 2-ethylhexyldiphenyl phosphate (EHDP) and free thyroxine (FT4), between BDE-100 and free triiodothyronine (FT3), and between anti-Dechlorane Plus (DP) and thyroid-stimulating hormone (TSH). In particular, most penta-BDE congeners were significantly or marginally significantly associated with FT4 and FT3 for both females and males. Our results suggest that wristbands can be used as suitable exposure monitors for evaluating human exposure to FRs.

Personal exposure to polycyclic aromatic hydrocarbons in Appalachian mining communities.

Coal mining activities may increase residential exposure to polycyclic aromatic hydrocarbons (PAHs), but personal PAH exposures have not been studied in mining areas. We used silicone wristbands as passive personal samplers to estimate PAH exposures in coal mining communities in Central Appalachia in the United States. Adults (N = 101) wore wristbands for one week; 51 resided in communities within approximately three miles of surface mining sites, and 50 resided 10 or more miles from mining sites. Passive indoor polyurethane foam (PUF) sampling was conducted in residents' homes, and a sample of 16 outdoor PUF samples were also collected. Nine PAH congeners were commonly detected in wristbands (mean ±â€¯standard deviation), including phenanthrene (50.2 ±â€¯68.7 ng/g), benz[a]anthracene (20.2 ±â€¯58.2 ng/g), fluoranthene (19.4 ±â€¯24.1 ng/g) and pyrene (15.2 ±â€¯18.2 ng/g). Controlling for participant characteristics and season, participants living closer to mining sites had significantly higher levels of phenanthrene, fluorene, fluoranthene, pyrene and ∑PAHs in wristbands compared to participants living farther from mining. Indoor air showed no significant group differences except for pyrene, but outdoor air showed significant or marginally significant differences for phenanthrene, fluorene, pyrene and ∑PAHs. The results suggest that mining community residents face exposure to outdoor mining-related pollutants, and demonstrate that personal silicone wristbands can be deployed as effective passive sampling devices.

Silicone wristbands integrate dermal and inhalation exposures to semi-volatile organic compounds (SVOCs).

Silicone wristbands are being increasingly used to assess human exposure to semi-volatile organic compounds (SVOCs). However, it is unclear what exposure pathways wristbands integrate. To test the hypothesis that wristbands integrate inhalation and dermal exposures, we measured 38 chemicals from four compound groups (PAHs, PBDEs, nBFRs, and OPEs) in silicone wristbands and brooches, active air samples (Occupational Safety and Health Administration Versatile Sampler or OVS cartridge), and hand wipes from 10 adults during a 72-hour period. Phenanthrene, BDE-47, 2­ethylhexyl 2,3,4,5­tetrabromobenzoate (EHTBB), tris[(2R)­1­chloro­2­propyl] phosphate (TCIPP), and tris(1,3­dichloro­2­propyl) phosphate (TDCIPP) were the predominant compounds in all four matrices. In a linear regression analysis, the compound levels in OVS were positively associated with those in wristbands and brooches for nBFRs and OPEs, but not for PAHs and PBDEs. The compound levels in wristbands were positively associated with those in hand wipes and brooches for all chemicals. The regressions between the levels in wristbands and OVS or brooches combined with the levels in hand wipes showed stronger, supporting the hypothesis that wristbands captured inhalation and dermal exposure pathways.

Exposure of Canadian electronic waste dismantlers to flame retardants.

Exposure of e-waste workers to eight halogenated and five organophosphate ester flame retardant chemicals (FRs) was studied at a Canadian e-waste dismantling facility. FR concentrations were measured in air and dust samples collected at a central location and at four work benches over five-24 hour periods spanning two weeks. The highest concentrations in air from workbenches were of BDE-209 (median 156 ng m-3), followed by Tris(2-chloroethyl) phosphate (TCEP, median 59 ng m-3). Dust concentrations at the workbenches were higher than those measured at the central location, consistent with the release of contaminated dust during dismantling. Dust concentrations from the workbenches were also dominated by BDE-209 (median 96,300 ng g-1), followed by Triphenyl phosphate (TPhP, median 47,000 ng g-1). Most FRs were in coarse particles 5.6-18 µm diameter and ~30% were in respirable particles (<~3 µm). Exposure estimates indicated that dust ingestion accounted for 63% of total FR exposure; inhalation and dermal absorption contributed 35 and 2%, respectively. Some air and dust concentrations as well as some estimated exposures in this formal facility in a high-income country exceeded those from informal e-waste facilities located in low and middle income countries. Although there is demonstrated toxicity of some FRs, FR exposure in the e-waste industry has received minimal attention and occupational limits do not exist for most FRs.

Atmospheric Occurrence of Legacy Pesticides, Current Use Pesticides, and Flame Retardants in and around Protected Areas in Costa Rica and Uganda.

Protected areas have developed alongside intensive changes in land use and human settlements in the neighboring landscape. Here, we investigated the occurrence of 21 organochlorine pesticides (OCPs), 14 current use pesticides (CUPs), 47 halogenated flame retardants (HFRs), and 19 organophosphate esters (OPEs) in air around Las Cruces (LC) and La Selva (LS) Biological Stations, Costa Rica, and Kibale National Park (KNP), Uganda using passive air samplers (PAS) with polyurethane foam (PUF) discs (PAS-PUF). Significantly higher concentrations of CUPs were observed around LS, while LC had a higher concentration of OCPs. Land use analysis indicated that LS had a higher fraction of agriculture than LC (33% vs 14%), suggesting the higher CUPs concentration at LS was related to pesticide intensive crops, while higher OCPs concentration at LC may be attributed to the area's long agricultural history characterized by small-scale subsistence farming or long-range transport. In Uganda, CUPs and OCPs were generally lower than in Costa Rica, but high concentrations of HFRs were observed inside KNP, possibly due to human activity at research camps near the protected forest. This is the first study that documented the occurrence of anthropogenic chemicals in the air at protected areas with tropical forests.

Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility.

Here we report on the concentrations of 79 flame retardants (FRs) and plasticizers, including 34 polybrominated diphenyl ethers or PBDE congeners, 17 "novel" brominated FRs (NBFRs), 15 dechloranes, and 13 organophosphate esters (OPEs) in air (n = 9) and dust (n = 24) samples from an active waste electrical and electronic equipment (WEEE) dismantling facility in Ontario, Canada, collected in February-March 2017. This is the first study of its kind in North America. The facility processes a range of WEEE including monitors, computers, printers, phones, and toys. Of the 79 target compounds, at least 60 were detected at a frequency of at least 50% in both air and dust. Dust and air concentrations were dominated by three compounds: BDE-209 (median 110,000 ng/g and 100 ng/m3, respectively), DBDPE (median 41,000 ng/g and 41 ng/m3), and TPhP (median 42,000 ng/g and 27 ng/m3). Levels of PBDEs, NBFRs, and dechloranes were close to two orders-of-magnitude higher in dust from the dismantling facility than in residential homes, while OPEs were one order-of-magnitude higher. Congener profiles of PBDEs indicated debromination of BDE-209. We calculated that a total mass of 44 ±â€¯1 mg day-1 of 79 target analytes were released to air from WEEE processed in the dismantling hall and a further 270 ±â€¯91 mg day-1 were released to dust. It is clear that WEEE dismantling facilities are a serious concern as a source of emissions for a wide range of FRs at relatively high concentrations to both workers and the immediate environment.

Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers.

For the first time, we present an analytical method to simultaneously extract, fractionate, and quantify four groups of semi-volatile organic compounds (SVOCs) in silicone wristbands, including 35 polybrominated diphenyl ethers (PBDEs), 10 novel flame retardants (NFRs), 19 organophosphate esters (OPEs), and 13 polycyclic aromatic hydrocarbons (PAHs). Wristbands were extracted using ultrasonication, and cleaned and fractionated on two multi-layer columns: one consisting of neutral alumina, neutral silica and Florisil, and the other consisting of neutral alumina, neutral silica, and acidic silica. Method accuracy and precision were validated using spiked wristband samples (n = 8) and procedural blanks (n = 7). Average matrix spike percent recoveries for all target analytes were within 57-107% with relative standard errors < 20%, with a few exceptions. This method was applied to analyze thirteen wristbands worn by ten participants for seven days; three participants wore two wristbands to evaluate duplicate samples. Percent recoveries of surrogate standards for all four groups of analytes in these wristbands were all within the 80-120% range with a few exceptions: recoveries for 13C12BDE-209 and for 13C12-triphenyl phosphate ranged from 35 to 62% and 69-176%, respectively. The majority of target analytes were detected in at least half of worn wristbands. The levels of total PBDEs, NFRs, OPEs and PAHs in deployed wristbands ranged from 28.4 to 412 ng, 40.7 to 625 ng, 2440 to 9580 ng, and 76.2 to 1240 ng, respectively.

Tri(2,4-di- t-butylphenyl) Phosphate: A Previously Unrecognized, Abundant, Ubiquitous Pollutant in the Built and Natural Environment.

Using high-resolution mass spectrometry, we identified tri(2,4-di- t-butylphenyl) phosphate (TDTBPP) in e-waste dust. This is a previously unsuspected pollutant that had not been reported before in the environment. To assess its abundance in the environment, we measured its concentration in e-waste dust, house dust, sediment from the Chicago Ship and Sanitary Canal, Indiana Harbor water filters, and filters from high-volume air samplers deployed in Chicago, IL. To provide a context for interpreting these quantitative results, we also measured the concentrations of triphenyl phosphate (TPhP), a structurally similar compound, in these samples. Median concentrations of TDTBPP and TPhP were 14 400 and 41 500 ng/g, respectively, in e-waste dust and 4900 and 2100 ng/g, respectively, in house dust. TDTBPP was detected in sediment, water, and air with median concentrations of 527 ng/g, 3700 pg/L, and 149 pg/m3, respectively. TDTBPP concentrations were generally higher or comparable to those of TPhP in all media analyzed, except for the e-waste dust. Exposure from dust ingestion and dermal absorption in the e-waste recycling facility and in homes was calculated. TDTBPP exposure was 571 ng/kg bw/day in the e-waste recycling facility (pro-rated for an 8-h shift), and 536 ng/kg bw and 7550 ng/kg bw/day for adults and toddlers, respectively, in residential environments.

PCBs and organochlorine pesticides in indoor environments - A comparison of indoor contamination in Canada and Czech Republic.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are restricted compounds that are ubiquitously detected in the environment, including indoor matrices such as air and residential dust. We report concentrations of PCBs and selected OCPs in indoor air and dust from homes in Canada (23 homes) and Czech Republic (20 homes). Indoor air concentrations of PCBs and OCPs were ∼10 times higher than that outdoors. PCB concentrations of ∼450 ng/m3 were similar in both countries, higher in homes built before the restrictions on PCBs, and had congener profiles consistent with PCB mixtures manufactured or used in each country. All OCP air concentrations were higher in the Czech Republic than in the Canadian samples, suggesting greater indoor use of, for example, DDT and HCH. These data emphasize the persistence of these organochlorine compounds indoors and their presence in homes even decades after new usage was prohibited. Indoor levels of these legacy POPs remain at similar concentrations to compounds of current concern, such as brominated flame retardants and perfluorinated alkyl substances, emphasizing that they deserve ongoing attention in view of knowledge of PCB and OCP toxicity.

Accumulation of flame retardants in paired eggs and plasma of bald eagles.

In this study, we measured the concentrations of 58 flame retardants (and related compounds) in bald eagle (Haliaeetus leucocephalus) egg and plasma samples from the Michigan. These analytes include polybrominated diphenyl ethers (PBDEs), novel flame retardants (nFRs), Dechlorane-related compounds (Decs), and organophosphate esters (OPEs). A total of 24 paired eaglet plasma and egg samples were collected from inland (IN, N = 13) and the Great Lakes (GL, N = 11) breeding areas from 2000 to 2012. PBDEs were the most abundant chemical group with a geometric mean of 181 ng/g wet weight (ww) in egg and 5.31 ng/g ww in plasma. Decs were barely found in plasma samples, but they were frequently found in eggs (geometric mean 23.5 ng/g ww). OPE levels were comparable to those of PBDEs in the plasma but lower than those of PBDEs in eggs. Dec and PBDE concentrations were significantly higher in GL than in IN (p < 0.05). The ratio of egg to plasma concentrations (lipid normalized) varied with chemicals and correlated with the chemical's octanol-water partition coefficient. The lipid normalized bald eagle egg and plasma concentrations from Lake Superior and Huron were one to three orders of magnitude higher than concentrations measured in composite lake trout (Salvelinus namaycush) from the same lake, implying that they biomagnify in the environment.

Alternative Flame Retardant, 2,4,6-Tris(2,4,6-tribromophenoxy)-1,3,5-triazine, in an E-waste Recycling Facility and House Dust in North America.

A high molecular weight compound, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ), was detected during the analysis of brominated flame retardants in dust samples collected from an electrical and electronic waste (e-waste) recycling facility in Ontario, Canada. Gas chromatography coupled with both high-resolution and low-resolution mass spectrometry (MS) was used to determine TTBP-TAZ's chemical structure and concentrations. To date, TTBP-TAZ has only been detected in plastic casings of electrical and electronic equipment and house dust from The Netherlands. Here we report on the concentrations of TTBP-TAZ in selected samples from North America: e-waste dust ( n = 7) and air ( n = 4), residential dust ( n = 30), and selected outdoor air ( n = 146), precipitation ( n = 19), sediment ( n = 11) and water ( n = 2) samples from the Great Lakes environment. TTBP-TAZ was detected in all the e-waste dust and air samples, and in 70% of residential dust samples. The median concentrations of TTBP-TAZ in these three types of samples were 5540 ng/g, 5.75 ng/m3 and 6.76 ng/g, respectively. The flame retardants 2,4,6-tribromophenol, tris(2,3-dibromopropyl) isocyanurate, and 3,3',5,5'-tetrabromobisphenol A bis(2,3-dibromopropyl) ether, BDE-47 and BDE-209 were also measured for comparison. None of these other flame retardants concentrations was significantly correlated with those of TTBP-TAZ in any of the sample types suggesting different sources. TTBP-TAZ was not detected in any of the outdoor environmental samples, which may relate to its application history and physicochemical properties. This is the first report of TTBP-TAZ in North America.

Updated Polychlorinated Biphenyl Mass Budget for Lake Michigan.

This study revisits and updates the Lake Michigan Mass Balance Project (LMMBP) for polychlorinated biphenyls (PCBs) that was conducted in 1994-1995. This work uses recent concentrations of PCBs in tributary and open lake water, air, and sediment to calculate an updated mass budget. Five of the 11 LMMBP tributaries were revisited in 2015. In these five tributaries, the geometric mean concentrations of ∑PCBs (sum of 85 congeners) ranged from 1.52 to 22.4 ng L-1. The highest concentrations of PCBs were generally found in the Lower Fox River and in the Indiana Harbor and Ship Canal. The input flows of ∑PCBs from wet deposition, dry deposition, tributary loading, and air to water exchange, and the output flows due to sediment burial, volatilization from water to air, and transport to Lake Huron and through the Chicago Diversion were calculated, as well as flows related to the internal processes of settling, resuspension, and sediment-water diffusion. The net transfer of ∑PCBs is 1240 ± 531 kg yr-1 out of the lake. This net transfer is 46% lower than that estimated in 1994-1995. PCB concentrations in most matrices in the lake are decreasing, which drove the decline of all the individual input and output flows. Atmospheric deposition has become negligible, while volatilization from the water surface is still a major route of loss, releasing PCBs from the lake into the air. Large masses of PCBs remain in the water column and surface sediments and are likely to contribute to the future efflux of PCBs from the lake to the air.

Current-Use Flame Retardants in the Water of Lake Michigan Tributaries.

In this study, we measured the concentrations of 65 flame retardants in water samples from five Lake Michigan tributaries. These flame retardants included organophosphate esters (OPEs), brominated flame retardants (BFRs), and Dechlorane-related compounds. A total of 59 samples, including both the particulate and the dissolved phases, were collected from the Grand, Kalamazoo, Saint Joseph, and Lower Fox rivers and from the Indiana Harbor and Ship Canal (IHSC) in 2015. OPEs were the most abundant among the targeted compounds with geometric mean concentrations ranging from 20 to 54 ng/L; OPE concentrations were comparable among the five tributaries. BFR concentrations were about 1 ng/L, and the most-abundant compounds were bis(2-ethylhexyl) tetrabromophthalate, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate, and decabromodiphenyl ether. The highest BFR concentrations were measured in either the IHSC or the Saint Joseph River. The dechlorane-related compounds were detected at low concentrations (<1 pg/L). The fraction of target compounds in the particulate phase relative to the dissolved phase varied by chemical and tended to increase with their octanol-water partition coefficient. The chemical loading from all the five tributaries into Lake Michigan were <10 kg/year for the BFRs and about 500 kg/year for the OPEs.

Organophosphate esters flame retardants in the indoor environment.

Concentrations of 13 organophosphate ester flame retardants (OPEs) were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013 to look for abundances, differences among regions, and partitioning behavior. In general, we observed the highest concentrations for halogenated OPEs, particularly TCEP, TCIPP and TDCIPP, and also non-halogenated TPHP. Differences between regions strongly depended on the matrix. The concentrations of OPEs in dust were significantly higher in the US than in Canada (CAN) and Czech Republic (CZ). CZ had the highest concentrations in window film and CAN in air. ΣOPE concentrations were 2-3 and 1-2 orders of magnitude greater than ΣBFRs in air, and dust and window films, respectively. We found a significant relationship between the concentrations in dust and air, and between the concentrations in window film and air for OPEs with log KOA values <12, suggesting that equilibrium was reached for these compounds but not for those with log KOA>12. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for OPEs with log KOA values >12.

Identification of Marbon in the Indiana Harbor and Ship Canal.

Marbon is isomeric with Dechlorane Plus (DP). Both are produced by the Diels-Alder condensation of hexachlorocyclopentadiene with cyclic dienes, and both have elemental compositions of C18H12Cl12. Dechlorane Plus is commonly found in the environment throughout the world, but Marbon has, so far, only been detected at low levels in one sediment core collected near the mouth of the Niagara River in Lake Ontario. Here we report on the concentrations of Marbon and anti-DP in 59 water samples from five Lake Michigan tributaries [the Grand, Kalamazoo, St. Joseph, and Lower Fox Rivers, and the Indiana Harbor and Ship Canal (IHSC)], 10 surface sediment samples from the IHSC, and 2 surface sediment samples from the Chicago Sanitary and Ship Canal. Three Marbon diastereomers were detected in the water and sediment samples from the IHSC, which is far from the location of its previous detection in Lake Ontario. The sum of the concentrations of the three Marbons was greater in the water from the IHSC (N = 11, median =150 pg/L) compared to those in water from the other four tributaries (N = 11-13, medians =0.9-2.0 pg/L). Marbon concentrations in sediment samples from the IHSC were up to 450 ng/g dry weight. Anti-DP was also measured for comparison. Its concentrations were not significantly different among the water samples, but its sediment concentrations in the IHSC were significantly correlated with those of Marbon. The source of Marbon contamination in the IHSC is not clear.

Brominated flame retardants in the indoor environment - Comparative study of indoor contamination from three countries.

Concentrations of more than 20 brominated flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs) and emerging FRs, were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013. Among the PBDEs, the highest concentrations were generally BDE-209 in all three matrices, followed by Penta-BDEs. Among alternative FRs, EHTBB and BEHTBP were detected at the highest concentrations. DBDPE was also a major alternative FR detected in dust and air. Bromobenzenes were detected at lower levels than PBDEs and other alternative FRs; among the bromobenzenes, HBB and PBEB were the most abundant compounds. In general, FR levels were highest in the US and lowest in the Czech Republic - a geographic trend that reflects the flame retardants' market. No statistically significant differences were detected between bedroom and living room FR concentrations in the same house (n=10), suggesting that sources of FRs are widespread indoors and mixing between rooms. The concentrations of FRs in air, dust, and window film were significantly correlated, especially for PBDEs. We found a significant relationship between the concentrations in dust and window film and in the gas phase for FRs with log KOA values <14, suggesting that equilibrium was reached for these but not compounds with log KOA values >14. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for FRs with log KOA values >14.