Urinary carboxylic acid metabolites as possible novel biomarkers of exposures to alkylated polycyclic aromatic hydrocarbons.

Previous studies have found that alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) were more abundant in petrogenic sources (e.g., crude oil and its refined products) than pyrogenic sources of incomplete combustion. While urinary hydroxylated metabolites of unsubstituted PAHs have been widely used as biomarkers of PAHs exposures, little information is available as to the occurrence of alkyl-PAH metabolites. In this study, we have detected carboxylic acid metabolites of alkyl-naphthalene (2-NAPCA) and alkyl-phenanthrene (2-PHECA) in 314 urine samples repeatedly collected from 45 Los Angeles residents before, during, and after they spent ten weeks in Beijing in summers of 2014-2017. We found that traveling from Los Angeles to Beijing led to 348% (95% CI: 243 to 485%) and 209% (95% CI: 149 to 282%) increases in 2-NAPCA and 2-PHECA concentrations, respectively, which returned to baseline levels after participants came back to Los Angeles. The concentration ratio between 2-PHECA and hydroxy-phenanthrenes was significantly (p < 0.05) lower in Beijing (median: 0.40, IQR: 0.27-0.53) than in Los Angeles (median: 0.51, IQR: 0.32-0.77), where more than 5,000 active gas and oil wells were located. From 2014 to 2017, the concentration ratio of 2-PHECA to hydroxy-phenanthrenes increased by 28.7 (95%CI: 12.3 to 47.6) %/yr in Los Angeles and 18.6 (95%CI: 7.9 to 30.3) %/yr in Beijing, likely resulted from both cities' efforts to reduce pyrogenic emissions (e.g. vehicle exhaust). These results provided indirect evidence supporting the use of 2-PHECA to hydroxy-phenanthrene ratio as an index to reflect the relative exposure contributions from petrogenic and pyrogenic sources. While our study suggested that urinary PAHCAs may be novel biomarkers of exposure to alkyl-PAHs, future studies with external exposure characterization are warranted to further validate these biomarkers.