No abstract

In this study a sensitive macrophage-based in vitro reactive oxygen species (ROS) assay was coupled with chemical fractionation tools and a year-long sampling program to further our understanding of the role of water-soluble metals in aerosol toxicity. The location is the polluted urban environment of Lahore, Pakistan, where we collected 24 h PM10 and PM2.5 samples every 6(th) day from January 2007 through January 2008. The intrinsic (i.e. particulate matter (PM) mass-normalized) toxicity of the Lahore aerosol, representative of highly polluted developing nations, is compared with toxicity of aerosols from several urban environments in the USA. The monthly patterns of PM2.5 and PM10 water-soluble aerosol ROS-activity were similar with maxima in fall and mid-late winter, and minima over the period April through August and in early winter. Coarse PM ROS-activity was a consistent and significant component (42 +/- 13%) of total activity. The intrinsic activity of the PM2.5 and coarse PM was remarkably similar in a given month. Chelex treatment of the Lahore PM extracts removed a very large and consistent fraction of the water-soluble ROS-activity (96.5 +/- 2.8% for the PM10). Desferrioxamine (DFO) treatment of these extracts also removed a large and relatively consistent fraction of the water-soluble ROS-activity (87.8 +/- 5.3%). Taken together, the DFO and Chelex data imply that transition metals, particularly iron, are major factors mediating ROS-activity of water extracts of the Lahore PM. Statistical modeling (step-wise linear regression and cluster analysis) identified a small subset of metals (Mn, Co, Fe, Ni) as the potential ROS-active species. Several water-soluble "trace" metals present at very high concentrations in the PM extracts (Zn, Pb, Cd), that were effectively removed on Chelex, but are not redox-active, exhibited relatively poor correlations with ROS. The median intrinsic water-soluble ROS-activity measured in the Lahore PM was more than an order-of-magnitude greater than that measured in aerosols from the Long Beach/Los Angeles region and approximately 4-fold greater than the activity of Denver area PM.

Abstract. Organosulfates are important components of atmospheric organic aerosols, yet their structures, abundances, sources and formation processes are not adequately understood. This study presents the identification and quantitation of benzyl sulfate in atmospheric aerosols, which is the first confirmed atmospheric organosulfate with aromatic carbon backbone. Benzyl sulfate was identified and quantified in fine particulate matter (PM2.5) collected in Lahore, Pakistan, during 2007–2008. An authentic standard of benzyl sulfate was synthesized, standardized, and identified in atmospheric aerosols with quadrupole time-of-flight (Q-ToF) mass spectrometry (MS). Benzyl sulfate was quantified in aerosol samples using ultra performance liquid chromatography (UPLC) coupled to negative electrospray ionization triple quadrupole (TQ) MS. The highest benzyl sulfate concentrations were recorded in November and January 2007 (0.50 ± 0.11 ng m−3) whereas the lowest concentration was observed in July (0.05 ± 0.02 ng m−3). To evaluate matrix effects, benzyl sulfate concentrations were determined using external calibration and the method of standard addition; comparable concentrations were detected by the two methods, which ruled out significant matrix effects in benzyl sulfate quantitation. Three additional organosulfates with m/z 187, 201 and 215 were qualitatively identified as aromatic organosulfates with additional methyl substituents by high-resolution mass measurements and tandem MS. The observed aromatic organosulfates form a homologous series analogous to toluene, xylene, and trimethylbenzene, which are abundant anthropogenic volatile organic compounds (VOC), suggesting that aromatic organosulfates may be formed by secondary reactions. However, stronger statistical correlations of benzyl sulfate with combustion tracers (EC and levoglucosan) than with secondary tracers (SO42− and α-pinene-derived nitrooxy organosulfates) suggest that aromatic organosulfates may be emitted from the combustion sources or their subsequent atmospheric processing. Further studies are needed to elucidate the sources and formation pathways of aromatic organosulfates in the atmosphere.

No abstract

No abstract