Exposures to particulate matter (PM) of both 10-2.5 μm (PM 10-2.5 ) and below 2.5 μm (PM 2.5 ) were measured for a cohort of taxi drivers in Shenyang, China, during August of 2007. PM samples were collected inside and outside the taxi during the drivers' workshifts, and also inside the drivers' homes when they were off-shift. Ambient PM samples were also collected at a stationary location in Shenyang. Elemental carbon (EC) and organic carbon (OC) were also measured in PM collected on quartz filters inside the taxis as well as at the stationary site. Concentrations of three nitro-polycyclic aromatic hydrocarbons (NPAHs): 1-nitropyrene (1NP), 2-nitropyrene (2NP), and 2-nitrofluoranthene (2NFl) were determined in extracts of the PM samples by using a 2D-HPLC-MS/ MS method. The 2NP and 2NFl concentrations did not change substantially with sampling location, but the 1NP concentrations were much higher in samples collected inside and outside the taxis as compared with sampling locations that were more removed from traffic. Concentration ratios of specific NPAHs were used to assess the atmospheric conditions in Shenyang during the sampling period. The relatively high ratios of 2NFl/1NP (~8-50) indicate an important contribution from secondary NPAH formation to ambient NPAH levels, especially for the non-taxi samples. The ratios of 2NFl/2NP (2.5-4.3) indicate that 2NFl is primarily formed via the hydroxyl-initiated reaction.
Diesel exhaust (DE) is a significant contributor to the toxicity associated with particulate matter (PM). 1-Nitropyrene (1-NP) has been used as a molecular marker for DE, and the urinary metabolites of 1-NP have been proposed as biomarkers for exposure to DE. In this study, several urinary 1-NP metabolites were evaluated for their utility as markers of short-term exposures to DE. The study population was a cohort of 24 taxi drivers from Shenyang, China, who submitted urine samples collected before, after, and the next morning following their workshifts. The urinary metabolites studied were isomers of hydroxy-1-nitropyrene (3-, 6-, 8- OHNPs) and hydroxy-N-acetyl-1-aminopyrene (3-,6-, 8-OHNAAPs). Exposure to DE was estimated based on exposure to 1-NP in air samples collected during and after the driver's workshift; 6- and 8-OHNP, and 8-OHNAAP were consistently detected in the drivers' urine. Concentrations of the metabolites in the taxi drivers' urine were greater than metabolite levels previously reported in non-occupationally exposed subjects; however no associations were observed between subject-specific exposures to 1-NP and urinary metabolites measured at the end of the workshift or in the next morning void. Significant autocorrelation was observed in metabolite levels in successive urine samples, from which half-lives for urinary elimination of ~10-12 h were estimated. These observations suggest that, in an occupational setting, urinary 1-NP metabolites may be more suitable as markers of ongoing exposure (timescales of several days) rather than indicators of acute exposure associated with single workshifts.
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