Biomarkers of Organophosphate and Polybrominated Diphenyl Ether (PBDE) Flame Retardants of American Workers and Associations with Inhalation and Dermal Exposures.

This study evaluated workers' exposures to flame retardants, including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and other brominated flame retardants (BFRs), in various industries. The study aimed to characterize OPE metabolite urinary concentrations and PBDE serum concentrations among workers from different industries, compare these concentrations between industries and the general population, and evaluate the likely route of exposure (dermal or inhalation). The results showed that workers from chemical manufacturing had significantly higher (p <0.05) urinary concentrations of OPE metabolites compared to other industries. Spray polyurethane foam workers had significantly higher (p <0.05) urinary concentrations of bis(1-chloro-2-propyl) phosphate (BCPP) compared to other industries. Electronic scrap workers had higher serum concentrations of certain PBDE congeners compared to the general population. Correlations were observed between hand wipe samples and air samples containing specific flame-retardant parent chemicals and urinary metabolite concentrations for some industries, suggesting both dermal absorption and inhalation as primary routes of exposure for OPEs. Overall, this study provides insights into occupational exposure to flame retardants in different industries and highlights the need for further research on emerging flame retardants and exposure reduction interventions.

Exposure assessment of polycyclic aromatic hydrocarbons in refined coal tar sealant applications.

BACKGROUND: Refined coal tar sealant (RCTS) emulsions are used to seal the surface of asphalt pavement. Nine of the 22 polycyclic aromatic hydrocarbons (PAHs) evaluated in this study are classified as known, probable, or possible human carcinogens. Exposure assessment research for RCTS workers has not been published previously. OBJECTIVES: The overall objective of this study was to develop a representative occupational exposure assessment of PAH exposure for RCTS workers based on worksite surveys. The specific aims were to: 1) quantify full-shift airborne occupational exposures to PAHs among RCTS workers; 2) quantify workers' dermal exposures to PAHs; 3) quantify biomarkers of PAH exposure in workers' urine; 4) identify specific job titles associated with RCTS exposure; and 5) apply these results to a biological exposure index to assess risk of potential genotoxicity from occupational exposures. METHODS: A total of twenty-one RCTS workers were recruited from three companies. Personal and area air samples were collected using a modification of NIOSH Method 5515. Dermal exposure was assessed by hand and neck wipes before and after shifts. Twenty-two PAHs were quantified via gas chromatography-mass spectrometry selected ion monitoring. Internal dose was estimated by quantifying select PAH metabolites in pre- and post-shift urine samples using on-line solid phase extraction-high performance liquid chromatography-tandem mass spectrometry. RESULTS: PAH levels in the worker breathing zones were highest for naphthalene, acenaphthene, and phenanthrene, with geometric means of 52.1, 11.4, and 9.8 µg/m3, respectively. Hand wipe levels of phenanthrene, fluoranthene and pyrene were the highest among the 22 PAHs with geometric means of 7.9, 7.7, and 5.5 µg/cm2, respectively. Urinary PAH biomarkers for naphthalene, fluorene, phenanthrene, and pyrene were detected in all workers and were higher for post-shift samples than those collected pre-shift. Urinary concentrations of the metabolite 1-hydroxypyrene were greater than the American Conference of Governmental Industrial Hygienists (ACGIH) Biological Exposure Index (BEI) for this metabolite in 89 percent of post-shift samples collected on the final day of the work week or field survey. Statistically significances were found between concentrations of fluorene, naphthalene, and phenanthrene in the breathing zone of workers and their corresponding urinary PAH biomarkers. Workers were placed in two work place exposure groups: applicators and non-applicators. Applicators had higher total PAH concentrations in personal breathing zone (PBZ) air samples than non-applicators and were more likely to have post-shift hand wipe concentrations significantly higher than pre-shift concentrations. Concentrations of post-shift urinary biomarkers were higher, albeit not significantly, for applicators than non-applicators. CONCLUSIONS: The exposure results from RCTS worker samples cannot be explained by proximal factors such as nearby restaurants or construction. Air and skin concentration levels were substantially higher for RCTS workers than previously published levels among asphalt workers for all PAHs. PAH profiles on skin wipes were more consistent with RCTS sealant product than air samples. Last day post-shift urinary concentrations of 1-hydroxypyrene greatly exceeded the ACGIH BEI benchmark of 2.5 µg/L in 25 of 26 samples, which suggests occupational exposure and risk of genotoxicity. When pyrene and benzo[a]pyrene were both detected, concentration ratios from personal exposure samples were used to calculate the adjusted BEI. Concentrations of 1-hydroxypyrene exceeded the adjusted BEIs for air, hand wipes, and neck wipes in most cases. These results indicate the need to increase safety controls and exposure mitigation for RCTS workers.

Assessment of triphenyl phosphate (TPhP) exposure to nail salon workers by air, hand wipe, and urine analysis.

Triphenyl phosphate (TPP or TPhP) is commonly used as an additive plasticizer or organophosphate flame retardant (OPFR) in consumer products including nail polish. We evaluated exposure to TPhP from 12 nail salon technicians working at four nail salons located in California over a period of two work days. Bulk samples of 15 nail polishes and other nail products were collected. Study participants also provided two personal air samples, two hand wipe samples (pre- and post-shift on day two), and two urine samples (pre-shift day one and post-shift day two). The geometric mean (GM) of TPhP air sampling concentrations was 7.39 ng/m3. Post-shift TPhP hand wipe concentrations (GM 1.35 µg/sample) were significantly higher (p = 0.024) than pre-shift hand wipe concentrations (GM 0.29 µg/sample). Diphenyl phosphate (DPP or DPhP), a urinary metabolite of TPhP used in this study as a biomarker of exposure, was detected in all post-shift urine samples and 75% of urine pre-shift samples. DPhP post-shift concentrations (GM 1.35 µg/g creatinine) were significantly higher than pre-shift concentrations (GM 0.84 µg/g creatinine; p = 0.012). In addition, DPhP post-shift concentrations were correlated with TPhP post-shift hand wipe concentrations, suggesting dermal contact may be a relevant exposure pathway for nail salon workers.

Worker exposure to flame retardants in manufacturing, construction and service industries.

Workers in several industries are occupationally exposed to flame retardants. This study characterizes flame retardant exposure for nine industries through air and hand wipe measures for 105 workers. Specifically, we analyzed 24 analytes from three chemical classes: organophosphate flame retardants (OFRs), polybrominated diphenyl ethers (PBDEs), and non-PBDE brominated flame retardants (NPBFRs). The industries were: carpet installation, chemical manufacturing, foam manufacturing, electronic scrap, gymnastics, rigid board installation, nail salons, roofing, and spray polyurethane foam. Workers wore personal air samplers for two entire workdays and provided hand wipe samples before and after the second work day. Bulk products were also analyzed. The air, hand wipe and bulk samples were evaluated for relevant flame retardants. Spray polyurethane foam workers' tris(1-chloro-2-propyl) phosphate air (geometric mean = 48,500 ng/m3) and hand wipe (geometric mean = 83,500 ng per sample) concentrations had the highest mean industry concentration of any flame retardant analyzed in this study, followed by triphenyl phosphate air concentration and tris(1,3-dichloro-2-propyl) phosphate hand wipe concentration from chemical manufacturers. Overall, OFR air and hand wipe concentrations were higher and more prevalent than PBDEs or non-PBDE brominated flame retardants. Some industries including spray polyurethane foam application, chemical manufacturing, foam manufacturing, nail salons, roofing, and rigid polyiso board installation had high potential for both air and hand exposure to OFRs. Carpet installers, electronic scrap workers, and gymnastic workers had exposures to all three classes of flame retardants including PBDEs, which were phased out of production in 2013. Air and dermal exposures to OFRs are prevalent in many industries and are replacing PBDEs in some industries.

Assessment of spray polyurethane foam worker exposure to organophosphate flame retardants through measures in air, hand wipes, and urine.

Tris(1-chloro-2-propyl) phosphate (TCPP, also referenced as TCIPP), a flame retardant used in spray polyurethane foam insulation, increases cell toxicity and affects fetal development. Spray polyurethane foam workers have the potential to be exposed to TCPP during application. In this study, we determined exposure to TCPP and concentrations of the urinary biomarker bis(1-chloro-2-propyl) phosphate (BCPP) among 29 spray polyurethane foam workers over 2 work days. Work was conducted at residential or commercial facilities using both open-cell (low density) and closed-cell (high density) foam. Study participants provided two personal air samples (Day 1 and Day 2), two hand wipe samples (Pre-shift Day 2 and Post-shift Day 2), and two spot urine samples (Pre-shift Day 1 and Post-shift Day 2). Bulk samples of cured spray foam were also analyzed. Sprayers were found to have significantly higher TCPP geometric mean (GM) concentration in personal air samples (87.1 µg/m3), compared to helpers (30.2 µg/m3; p = 0.025). A statistically significant difference was observed between TCPP pre- and post-shift hand wipe GM concentrations (p = 0.004). Specifically, TCPP GM concentration in post-shift hand wipe samples of helpers (106,000 ng/sample) was significantly greater than pre-shift (27,300 ng/sample; p < 0.001). The GM concentration of the urinary biomarker BCPP (23.8 µg/g creatinine) was notably higher than the adult male general population (0.159 µg/g creatinine, p < 0.001). Urinary BCPP GM concentration increased significantly from Pre-shift Day 1 to Post-shift Day 2 for sprayers (p = 0.013) and helpers (p = 0.009). Among bulk samples, cured open-cell foam had a TCPP GM concentration of 9.23% by weight while closed-cell foam was 1.68%. Overall, post-shift BCPP urine concentrations were observed to be associated with TCPP air and hand wipe concentrations, as well as job position (sprayer vs. helper). Spray polyurethane foam workers should wear personal protective equipment including air-supplied respirators, coveralls, and gloves during application.