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.

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.

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.

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.

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.