Determination of parent and hydroxy PAHs in personal PM2.5 and urine samples collected during Native American fish smoking activities

Abstract

A method was developed for the measurement of 19 parent PAHs (PAHs) and 34 hydroxylated PAHs (OH-PAHs) in urine and personal air samples of particulate matter less than 2.5 um in diameter (PM2.5) using GC-MS and validated using NIST SRM 3672 (Organic Contaminants in Smoker’s Urine) and SRM 3673 (Organic Contaminants in Nonsmoker’s Urine). The method was used to measure PAHs and OH-PAHs in urine and personal PM2.5 samples collected from the operators of two different fish smoking facilities (tipi and smoke shed) burning two different wood types (alder and apple) on the Confederated Tribes of Umatilla Indian Reservation (CTUIR) while they smoked salmon. Urine samples were spiked with β-glucuronidase/arylsulfatase to hydrolyze the conjugates of OH-PAHs and the PAHs and OH-PAHs were extracted using Plexa and C18 solid phases, in series. The 34OH-PAHs were derivatized using MTBSTFA, and the mixture was measured by GC-MS. The personal PM2.5samples were extracted using pressurized liquid extraction, derivatized with MTBSTFA and analyzed by GC-MS for PAHs and OH-PAHs. Fourteen isotopically labeled surrogates were added to accurately quantify PAHs and OH-PAHs in the urine and PM2.5 samples and three isotopically labeled internal standards were used to calculate the recovery of the surrogates. Estimated detection limits in urine ranged from 6.0 to 181 pg/ml for OH-PAHs and from 3.0 to 90 pg/ml for PAHs, and, in PM2.5, they ranged from 5.2 to 155 pg/m3 for OH-PAHs and from 2.5 to 77 pg/m3 for PAHs. The results showed an increase in OH-PAH concentrations in urine after 6 hours offish smoking and an increase in PAH concentrations in air within each smoking facility. In general, the PAH exposure in the smoke shed was higher than in the tipi and the PAH exposure from burning apple wood was higher than burning alder.

Metabolism and excretion rates of parent and hydroxy-PAHs in urine collected after consumption of traditionally smoked salmon for Native American volunteers

“…Table S3 shows the median, highest and lowest PAH and OH-PAH concentrations for all participants and Figure 2 shows the comparison of these concentrations to the concentrations we measured in urine for our previous study on the inhalation of PAH from PM 2.5 during fish smoking (Motorykin et al, 2015) and the 2008 National Health and Nutrition Examination Survey (NHANES) values (Centers for Disease Control and Prevention (CDC), 2013). The mean OH-PAH pre-exposure concentrations ranged from 6.9 μg/g creatinine for 2-OH-Nap to 56 ng/g creatinine for 2-OH-Phen, and were in the range of the 25 th to 75 th percentile of NHANES concentrations.…”

“…We compared the results from this study to the results of our previous study, where the inhalation exposure to the smoke while smoking salmon was investigated (Motorykin et al, 2015) (Figure 2). The route of exposure was different between these two studies (inhalation vs ingestion), but both involved a traditional activity (smoking salmon and eating smoked salmon).…”

“…The analytical method developed for the determination of PAH and OH-PAH in urine is shown in Figure S1 and described in Motorykin et al (2015). Briefly, a 3 ml aliquot of urine was taken and mixed with 5 mL of acetate buffer (pH=5.5).…”

“…The OH-PAH fraction was solvent-exchanged to acetonitrile (addition of 100 μl and evaporation to ~20 μl) and 30 μl of MTBSTFA was added to it. The OH-PAH fraction was then incubated at 65 °C for 25 minutes and both fractions were analyzed separately by GC-MS (Motorykin et al, 2015). All urine samples were extracted and analyzed in triplicate.…”

“…They are formed during incomplete combustion of any carbon-based matter, such as wood (Li et al, 2011), coal (Simoneit et al, 2007), meat (barbequing, charcoaling, grilling) (Akpambang et al, 2009; Alomirah et al, 2011), and others (Baek et al, 1991). Humans are exposed to PAHs mainly through ingestion or inhalation (Motorykin et al, 2015; Suzuki and Yoshinaga, 2007; Wang et al, 2012; Zhang et al, 2014), but dermal exposure is also possible (McClean et al, 2004). Once PAHs are inside the human body, they are metabolized by the family of CYP-450 enzymes to more water-soluble hydroxy-PAHs (OH-PAHs) and excreted via urine (Guo et al, 2013; Jacob and Seidel, 2002; Ramesh et al, 2004).…”