Los Angeles Summer Midday Particulate Carbon: Primary and Secondary Aerosol

Aerosol sampling during photochemically active times across the Los Angeles Basin has provided evidence of secondary formation of organic aerosol from gas-phase precursors at midday. Ambient organic carbon/elemental carbon ratios exceeded the estimated ratio of organic carbon/elemental carbon in primary source emissions on most sampling days at all sites. The concentration of secondary organic aerosol was calculated by using ambient data and estimates of the organic carbon/elemental carbon ratio in primary source emissions. Nonparametric sign correlations comparing calculated secondary organic carbon concentrations with tracers of both primary and secondary aerosols supported the method used to quantify secondary organic carbon. Secondary organic aerosol appears to have contributed roughly half of the organic aerosol in Pasadena during midday summer conditions

Photochemical Organonitrate Formation in Wet Aerosols

Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal and OH &ndash; containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 hour irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen-sulfates (CHNOS). These were also the dominant products formed in the dark chamber indicating non-radical formation. In the humid chamber (> 70 % RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m/z&minus; 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.</html

Los Angeles Summer Midday Particulate Carbon: Primary and Secondary Aerosol

Aerosol sampling during photochemically active times across the Los Angeles Basin has provided evidence of secondary formation of organic aerosol from gas-phase precursors at midday. Ambient organic carbon/elemental carbon ratios exceeded the estimated ratio of organic carbon/elemental carbon in primary source emissions on most sampling days at all sites. The concentration of secondary organic aerosol was calculated by using ambient data and estimates of the organic carbon/elemental carbon ratio in primary source emissions. Nonparametric sign correlations comparing calculated secondary organic carbon concentrations with tracers of both primary and secondary aerosols supported the method used to quantify secondary organic carbon. Secondary organic aerosol appears to have contributed roughly half of the organic aerosol in Pasadena during midday summer conditions

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOA$_{AQ}$). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOA$_{AQ}$. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of watersoluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH ·) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 μM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra highresolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS– MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOA$_{AQ}$

Size-resolved aerosol composition at an urban and a rural site in the Po Valley in summertime: implications for secondary aerosol formation

The aerosol size-segregated chemical composition was analyzed at an urban (Bologna) and a rural (San Pietro Capofiume) site in the Po Valley, Italy, during June and July 2012, by ion-chromatography (major water-soluble ions and organic acids) and evolved gas analysis (total and water-soluble carbon), to investigate sources and mechanisms of secondary aerosol formation during the summer. A significant enhancement of secondary organic and inorganic aerosol mass was observed under anticyclonic conditions with recirculation of planetary boundary layer air but with substantial differences between the urban and the rural site. The data analysis, including a principal component analysis (PCA) on the size-resolved dataset of chemical concentrations, indicated that the photochemical oxidation of inorganic and organic gaseous precursors was an important mechanism of secondary aerosol formation at both sites. In addition, at the rural site a second formation process, explaining the largest fraction (22 %) of the total variance, was active at nighttime, especially under stagnant conditions. Nocturnal chemistry in the rural Po Valley was associated with the formation of ammonium nitrate in large accumulation-mode (0.42–1.2 µm) aerosols favored by local thermodynamic conditions (higher relative humidity and lower temperature compared to the urban site). Nocturnal concentrations of fine nitrate were, in fact, on average 5 times higher at the rural site than in Bologna. The water uptake by this highly hygroscopic compound under high RH conditions provided the medium for increased nocturnal aerosol uptake of water-soluble organic gases and possibly also for aqueous chemistry, as revealed by the shifting of peak concentrations of secondary compounds (water-soluble organic carbon (WSOC) and sulfate) toward the large accumulation mode (0.42–1.2 µm). Contrarily, the diurnal production of WSOC (proxy for secondary organic aerosol) by photochemistry was similar at the two sites but mostly affected the small accumulation mode of particles (0.14–0.42 µm) in Bologna, while a shift to larger accumulation mode was observed at the rural site. A significant increment in carbonaceous aerosol concentration (for both WSOC and water-insoluble carbon) at the urban site was recorded mainly in the quasi-ultrafine fraction (size range 0.05–0.14 µm), indicating a direct influence of traffic emissions on the mass concentrations of this range of particles

Composition and major sources of organic compounds of aerosol particulate matter sampled during the ACE-Asia campaign

The organic compound tracers of atmospheric particulate matter, as well as organic carbon (OC) and elemental carbon (EC), have been characterized for samples acquired during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) from Gosan, Jeju Island, Korea, from Sapporo, Japan, and from Chichi-jima Island in the western North Pacific, as well as on the National Oceanic and Atmospheric Administration R/V Ronald H. Brown. Total extracts were analyzed by gas chromatography–mass spectrometry to determine both polar and aliphatic compounds. Total particles, organic matter, and lipid and saccharide compounds were high during the Asian dust episode (early April 2001) compared to levels at other times. The organic matter can be apportioned to seven emission sources and to significant oxidationproducing secondary products during long-range transport. Terrestrial natural background compounds are vascular plant wax lipids derived from direct emission and as part of desert sand dust. Fossil fuel utilization is obvious and derives from petroleum product and coal combustion emissions. Saccharides are a major polar (water-soluble) carbonaceous fraction derived from soil resuspension (agricultural activities). Biomass-burning smoke is evident in all samples and seasons. It contributes up to 13% of the total compound mass as water-soluble constituents. Burning of refuse is another source of organic particles. Varying levels of marine-derived lipids are superimposed during aerosol transport over the ocean. Secondary oxidation products increase with increasing transport distance and time. The ACE-Asia aerosols are composed not only of desert dust but also of soil dust, smoke from biomass and refuse burning, and emissions from fossil fuel use in urban areas

Spatial distributions of oxygenated organic compounds (dicarboxylic acids, fatty acids, and levoglucosan) in marine aerosols over the western Pacific and off the coast of East Asia: Continental outflow of organic aerosols during the ACE-Asia campaign

Aerosol sampling for major oxygenated organic compounds (dicarboxylic acids, fatty acids, and levoglucosan) was conducted from 15 March to 19 April 2001 on board the National Oceanic and Atmospheric Administration R/V Ronald H. Brown over the western North Pacific, the East China Sea, and the Sea of Japan, as part of the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) campaign. During the cruise, aerosol particles were collected on quartz fiber filters using a high-volume air sampler. Diacids were also collected using an annular denuder sampling system to assess their gas-particle partitioning. Concentrations of total diacids, total fatty acids, and levoglucosan were found to be higher off the coasts of East Asia than in the remote Pacific. Contributions of these organic compounds to total organic carbon and total organic matter (OM) were calculated to be 9.8 ± 2.3% and 19.0 ± 4.8%, respectively, assuming OM to be organic carbon x 1.6. Diacid concentrations were highly correlated with nss-SO2-/4 and NO-3, which originate from anthropogenic sources over East Asia. The temporal variations and chain-length distributions of fatty acids suggest that atmospheric transport of terrestrial organic materials is important off the coast of the continent. C2 – C5 diacids were present predominantly in the particulate phase. The relative abundances of C2 – C5 diacids stayed almost unchanged throughout the cruise, suggesting that deposition is more important than chemical decomposition as a sink of diacids and that they are relatively stable end products in the atmosphere