Abstract
BackgroundIn May 2016, firefighters from the province of Alberta, Canada deployed to a fire that engulfed the urban area of Fort McMurray. During the first days of the fire, firefighters experienced heavy smoke exposures during greatly extended work shifts. Urinary samples were collected post-deployment from three fire services for estimation of 1-hydroxypyrene (1-HP) concentration, reflecting exposure to polycyclic aromatic hydrocarbons (PAHs), to determine the effects of respiratory protective equipment (RPE) and skin hygiene in reducing internal doseMethodsUrine samples from one fire service (n = 62) were analyzed for 1-HP by two laboratories, using different assays (LC-MS/MS: GC-MS): remaining samples were analyzed just by LC-MS/MS. A Skin Exposure Mitigation Index (SEMI) was computed from questions on opportunities for changing clothing, showering, and washing during breaks. Regression analyses, using 1-HP ng/g creatinine as the dependent variable, assessed the effect of RPE and skin factors on PAH absorption, allowing for environmental exposure and potential confounders. Stratification identified key groups with equal delay in sample collection.Results1-HP was detected in 71.0% of 62 samples by LC-MS/MS and 98.4% by GC-MS, with good mutual agreement between the methods. In 171 post-fire samples, 1-HP corrected for creatinine was related to current cigarette smoking and recent barbeque. Among those with samples collected within 48 h, urinary 1-HP was correlated with estimated exposure(r = 0.53, P < 0.001). In those with only one rotation before urine sample collection, no effect was seen of RPE use but I-HP was significantly lower (P = 0.003) in those with those with a high score on the SEMI scale, indicating better access to factors mitigating skin absorption.ConclusionSkin exposure to PAHs is an important route of absorption in firefighters, which can be mitigated by good skin hygiene.
Highlights
LC-MS/MS analysis was performed using an Agilent 1200 high performance liquid chromatograph (Agilent Technologies, Santa Clara, CA, USA) coupled with a Sciex 5500 Q-trap mass spectrometer (AB Sciex, Concord, Ontario, Canada)
The injection volume was 10 μL and the column was kept at room temperature
The mass spectrometer was operated in negative MRM mode
Summary
Reagents, including acetonitrile (HPLC grade), sodium acetate (reagent grade, >99%), L-Ascorbic acid (≥99%), Glacial acetic acid (HPLC grade), Potassium dihydrogen phosphate (ACS reagent, ≥99%), Surine® negative urine, and β-glucuronidase (from Helix pomatia, Type HP-2, aqueous solution, >100,000 units/ mL) were purchased from Sigma-Aldrich (Canada). 1-hydroxypyrene (1-OH-pyrene), and 1hydroxypyrene-d9 (1-OH-pyrene-d9) were purchased from Toronto Research Chemicals Inc. (Canada). Reagents, including acetonitrile (HPLC grade), sodium acetate (reagent grade, >99%), L-Ascorbic acid (≥99%), Glacial acetic acid (HPLC grade), Potassium dihydrogen phosphate (ACS reagent, ≥99%), Surine® negative urine, and β-glucuronidase (from Helix pomatia, Type HP-2, aqueous solution, >100,000 units/ mL) were purchased from Sigma-Aldrich (Canada). To an aliquot of 1 mL of urine, 5 μL of ascorbic acid (1.5M), 10 μL of internal standard (1-OH-pyrene-d9, 100 ng/mL), 200 μL of pH5.2 buffer and 10 μL of diluted β-glucuronidase/sulfatase were added. The mixture was incubated on a shaking water bath for 2 hours at 60 °C and cooled to room temperature. 100 μL of hydrolyzed sample was aliquoted and further diluted with 5uL of ascorbic acid and 900 μL of elution solvent (ACN/pH6 buffer, 0.1M, 2:1)). The mixture was vortexed and centrifuged at 4000 rpm for 10 min. The supernatant was transferred to a 2 mL silanized autosampler vial for LC-MS/MS analysis
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