Aromatic organosulfates in atmospheric aerosols: synthesis, characterization, and abundance.

Aromatic organosulfates are identified and quantified in fine particulate matter (PM2.5) from Lahore, Pakistan, Godavari, Nepal, and Pasadena, California. To support detection and quantification, authentic standards of phenyl sulfate, benzyl sulfate, 3-and 4-methylphenyl sulfate and 2-, 3-, and 4-methylbenzyl sulfate were synthesized. Authentic standards and aerosol samples were analyzed by ultra-performance liquid chromatography (UPLC) coupled to negative electrospray ionization (ESI) quadrupole time-of-flight (ToF) mass spectrometry. Benzyl sulfate was present in all three locations at concentrations ranging from 4 - 90 pg m-3. Phenyl sulfate, methylphenyl sulfates and methylbenzyl sulfates were observed intermittently with abundances of 4 pg m-3, 2-31 pg m-3, 109 pg m-3, respectively. Characteristic fragment ions of aromatic organosulfates include the sulfite radical (•SO3-, m/z 80) and the sulfate radical (•SO4-,m/z 96). Instrumental response factors of phenyl and benzyl sulfates varied by a factor of 4.3, indicating that structurally-similar organosulfates may have significantly different instrumental responses and highlighting the need to develop authentic standards for absolute quantitation organosulfates. In an effort to better understand the sources of aromatic organosulfates to the atmosphere, chamber experiments with the precursor toluene were conducted under conditions that form biogenic organosulfates. Aromatic organosulfates were not detected in the chamber samples, suggesting that they form through different pathways, have different precursors (e.g. naphthalene or methylnaphthalene), or are emitted from primary sources.

Composition and sources of fine particulate matter across urban and rural sites in the Midwestern United States.

The composition and sources of fine particulate matter (PM2.5) were investigated in rural and urban locations in Iowa, located in the agricultural and industrial Midwestern United States, from April 2009 to December 2012. Major chemical contributors to PM2.5 mass were sulfate, nitrate, ammonium, and organic carbon. Non-parametric statistical analyses demonstrated that the two rural sites had significantly enhanced levels of crustal materials (Si, Al) driven by agricultural activities and unpaved roads. Meanwhile, the three urban areas had enhanced levels of secondary aerosols (nitrate, sulfate, and ammonium) and combustion products (elemental carbon). The Davenport site had significantly higher levels of PM2.5 and trace metals (Fe, Pb, Zn), demonstrating the important local impact of industrial point sources on air quality. Sources of PM2.5 were evaluated by using the multi-variant positive matrix factorization (PMF) source apportionment model. For each individual site, seven to nine factors were identified: secondary sulfate (accounting for 29-30% of PM2.5), secondary nitrate (17-24%), biomass burning (9-21%), gasoline combustion (6-16%), diesel combustion (3-9%), dust (6-11%), industry (0.4-5%) and winter salt (2-6%). Source contributions demonstrated a clear urban enhancement in PM2.5 from gasoline engines (by a factor of 1.14) and diesel engines (by a factor of 2.3), which is significant due to the well-documented negative health impacts of vehicular emissions. This study presents the first source apportionment results from the state of Iowa and is broadly applicable to understanding the differences in anthropogenic and natural sources in the urban-rural continuum of particle air pollution.