Active-sampling approaches are commonly used for personal monitoring, but are limited by energy usage and data that may not represent an individual’s exposure or bioavailable concentrations. Current passive techniques often involve extensive preparation, or are developed for only a small number of targeted compounds. In this work, we present a novel application for measuring bioavailable exposure with silicone wristbands as personal passive samplers. Laboratory methodology affecting precleaning, infusion, and extraction were developed from commercially available silicone, and chromatographic background interference was reduced after solvent cleanup with good extraction efficiency (>96%). After finalizing laboratory methods, 49 compounds were sequestered during an ambient deployment which encompassed a diverse set of compounds including polycyclic aromatic hydrocarbons (PAHs), consumer products, personal care products, pesticides, phthalates, and other industrial compounds ranging in log Kow from −0.07 (caffeine) to 9.49 (tris(2-ethylhexyl) phosphate). In two hot asphalt occupational settings, silicone personal samplers sequestered 25 PAHs during 8- and 40-h exposures, as well as 2 oxygenated-PAHs (benzofluorenone and fluorenone) suggesting temporal sensitivity over a single work day or week (p < 0.05, power =0.85). Additionally, the amount of PAH sequestered differed between worksites (p < 0.05, power = 0.99), suggesting spatial sensitivity using this novel application.

Wristbands are increasingly used for assessing personal chemical exposures. Unlike some exposure assessment tools, guidelines for wristbands, such as preparation, applicable chemicals, and transport and storage logistics, are lacking. We tested the wristband’s capacity to capture and retain 148 chemicals including polychlorinated biphenyls (PCBs), pesticides, flame retardants, polycyclic aromatic hydrocarbons (PAHs), and volatile organic chemicals (VOCs). The chemicals span a wide range of physical–chemical properties, with log octanol–air partitioning coefficients from 2.1 to 13.7. All chemicals were quantitatively and precisely recovered from initial exposures, averaging 102% recovery with relative SD ≤21%. In simulated transport conditions at +30 °C, SVOCs were stable up to 1 month (average: 104%) and VOC levels were unchanged (average: 99%) for 7 days. During long-term storage at −20 °C up to 3 (VOCs) or 6 months (SVOCs), all chemical levels were stable from chemical degradation or diffusional losses, averaging 110%. Applying a paired wristband/active sampler study with human participants, the first estimates of wristband–air partitioning coefficients for PAHs are presented to aid in environmental air concentration estimates. Extrapolation of these stability results to other chemicals within the same physical–chemical parameters is expected to yield similar results. As we better define wristband characteristics, wristbands can be better integrated in exposure science and epidemiological studies.

Silicone wristbands can be used as passive sampling tools for measuring personal environmental exposure to organic compounds. Due to the lightweight and simple design, the wristband may be a useful technique for measuring children’s exposure. In this study, we tested the stability of flame retardant compounds in silicone wristbands and developed an analytical approach for measuring 41 flame retardants in the silicone wristband in order to evaluate exposure to these compounds in preschool-aged children. To evaluate the robustness of using wristbands to measure flame retardants, we evaluated the stability of 3 polybrominated diphenyl ethers (BDEs), and 2 organophosphate flame retardants (OPFRs) in wristbands over 84 days and did not find any evidence of significant loss over time at either 4 or −20°C (p > 0.16). We recruited a cohort of 92 preschool aged children in Oregon to wear the wristband for 7 days in order to characterize children’s acceptance of the technology, and to characterize their exposure to flame retardants. Seventy-seven parents returned the wristbands for analysis of 35 BDEs, 4 OPFRs, and 2 other brominated flame retardants although 5 were excluded from the exposure assessment due to protocol deviations (n=72). A total of 20 compounds were detected above the limit of quantitation, and 11 compounds including 4 OPFRs and 7 BDEs were detected in over 60% of the samples. Children’s gender, age, race, recruitment site, and family context were not significantly associated with returning wristbands or compliance with protocols. Comparisons between flame retardant data and socio-demographic information revealed significant differences in total exposures to both ΣBDEs and ΣOPFRs based on age of house, vacuuming frequency, and family context. These results demonstrate that preschool children in Oregon are exposed to BDEs that are no longer being produced in the United States and to OPFRs that have been used as an alternative to polybrominated compounds. Silicone wristbands were well tolerated by young children and were useful for characterizing personal exposure to flame retardants that were not bound to particulate matter.

Wildlife from remote locations have been shown to bioaccumulate perfluorinated compounds (PFCs) in their tissues. Twelve PFCs, consisting of perfluorinated carboxylic (PFCA) and sulfonic (PFSA) acids as well as the perfluorooctane sulfonate (PFOS) precursor perfluorooctane sulfonamide (PFOSA), were measured in livers of 68 beluga whales (Delphinapterus leucas) collected from two subpopulations, Cook Inlet and eastern Chukchi Sea, in Alaska between 1989 and 2006. PFOS and PFOSA were the dominant compounds measured in both beluga stock populations, with overall median concentrations of 10.8 ng/g and 22.8 ng/g, respectively. Long-chain perfluorocarboxylates, PFCAs (9 to 14 carbons), were detected in more than 80% of the samples. Perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTriA) made up a large percentage of the PFCAs measured with median concentrations of 8.49 ng/g and 4.38 ng/g, respectively. To compare differences in location, year, sex, and length, backward stepwise multiple regression models of the individual and total PFC concentrations were used. Spatially, the Cook Inlet belugas had higher concentrations of most PFCAs and PFOS (p < 0.05); however, these belugas had a lower median concentration of PFOSA when compared to belugas from the eastern Chukchi Sea (p < 0.05). Temporal trends indicated most PFCAs, PFHxS, PFOS, and PFOSA concentrations increased from 1989 to 2006 (p < 0.05). Males had significantly higher concentrations of PFTriA, ΣPFCA, and PFOS (p < 0.05). Perfluorononanic acid (PFNA) and PFOS showed a significant decrease in concentration with increasing animal length (p < 0.05). These observations suggest the accumulation of PFCs in belugas is influenced by year, location, sex, and length.