ALBERT

Description: Online and offline measurements of ambient particulate matter (PM) near the urban and industrial Houston Ship Channel in Houston, Texas, USA, during May 2015 were utilized to characterize its chemical composition and to evaluate the relative contributions of primary, secondary, biogenic, and anthropogenic sources. Aerosol mass spectrometry (AMS) on nonrefractory PM1 (PM ≤ 1 µm) indicated major contributions from sulfate (averaging 50 % by mass), organic aerosol (OA, 40 %), and ammonium (14 %). Positive matrix factorization (PMF) of AMS data categorized OA on average as 22 % hydrocarbon-like organic aerosol (HOA), 29 % cooking-influenced less-oxidized oxygenated organic aerosol (CI-LO-OOA), and 48 % more-oxidized oxygenated organic aerosol (MO-OOA), with the latter two sources indicative of secondary organic aerosol (SOA). Chemical analysis of PM2.5 (PM ≤ 2.5 µm) filter samples agreed that organic matter (35 %) and sulfate (21 %) were the most abundant components. Organic speciation of PM2.5 organic carbon (OC) focused on molecular markers of primary sources and SOA tracers derived from biogenic and anthropogenic volatile organic compounds (VOCs). The sources of PM2.5 OC were estimated using molecular marker-based positive matric factorization (MM-PMF) and chemical mass balance (CMB) models. MM-PMF resolved nine factors that were identified as diesel engines (11.5 %), gasoline engines (24.3 %), nontailpipe vehicle emissions (11.1 %), ship emissions (2.2 %), cooking (1.0 %), biomass burning (BB, 10.6 %), isoprene SOA (11.0 %), high-NOx anthropogenic SOA (6.6 %), and low-NOx anthropogenic SOA (21.7 %). Using available source profiles, CMB apportioned 41 % of OC to primary fossil sources (gasoline engines, diesel engines, and ship emissions), 5 % to BB, 15 % to SOA (including 7.4 % biogenic and 7.6 % anthropogenic), and 39 % to other sources that were not included in the model and are expected to be secondary. This study presents the first application of in situ AMS-PMF, MM-PMF, and CMB for OC source apportionment and the integration of these methods to evaluate the relative roles of biogenic, anthropogenic, and BB-SOA. The three source apportionment models agreed that ∼ 50 % of OC is associated with primary emissions from fossil fuel use, particularly motor vehicles. Differences among the models reflect their ability to resolve sources based upon the input chemical measurements, with molecular marker-based methods providing greater source specificity and resolution for minor sources. By combining results from MM-PMF and CMB, BB was estimated to contribute 11 % of OC, with 5 % primary emissions and 6 % BB-SOA. SOA was dominantly anthropogenic (28 %) rather than biogenic (11 %) or BB-derived. The three-model approach demonstrates significant contributions of anthropogenic SOA to fine PM. More broadly, the findings and methodologies presented herein can be used to advance local and regional understanding of anthropogenic contributions to SOA.

Description: Organosulfates are secondary organic aerosol (SOA) products that form from reactions of volatile organic compounds (VOC), such as isoprene, in the presence of sulfate that is primarily emitted by fossil fuel combustion. This study examines the anthropogenic influence on biogenic organosulfate formation at an urban site in Atlanta, Georgia (GA) in the southeastern United States (US). Organosulfates were analyzed in fine particulate matter (PM2.5) collected during August 2015 in Atlanta using hydrophilic interaction liquid chromatography (HILIC), tandem mass spectrometry (MS/MS), and high-resolution time-of-flight (ToF) mass spectrometry. By their MS/MS response, 32 major organosulfate species were identified, selected species were quantified, and other species were semi-quantified using surrogate standards. Organosulfates accounted for 16.5 % of PM2.5 organic carbon (OC). Isoprene-derived organosulfates were the most abundant, dominated by methyltetrol sulfate which accounted for 12.6 % of PM2.5 OC. Together, the isoprene-derived organosulfates accounted for the majority of the isoprene-derived SOA that had been previously observed in Atlanta, but had not been identified at the molecular level. Other major species included seven monoterpene-derived organosulfates, five diesel and/or biodiesel-derived organosulfates, and three new organosulfates that are also expected to derive from isoprene. Organosulfate species and concentrations in Atlanta were compared to those in a rural forested site in Centreville, Alabama (AL) during summer 2013, which were also dominated by isoprene-derived organosulfates. In Atlanta, isoprene-derived organosulfate concentrations were 2–6 times higher and accounted for twice as much OC. The greatest enhancement in concentration was observed for 2-methylglyceric acid sulfate whose formation is enhanced in the presence of nitrogen oxides (NO and NO2; NOx) and is a tracer for isoprene high-NOx SOA. The isoprene-derived organosulfates indicated a stronger influence of NOx in Atlanta compared to Centreville. Overall, these results suggest that SOA in the southeastern US can be reduced by controlling NOx and SO2 emissions from fossil fuel combustion. This study gives insights into the major organosulfate species that should be targets for future measurements in urban environments and standard development.

Description: Products of secondary organic aerosol (SOA) from aromatic volatile organic compounds (VOCs) – 2,3-dihydroxy-4-oxopentanoic acid, dicarboxylic acids, nitromonoaromatics, and furandiones – were evaluated for their potential to serve as anthropogenic SOA tracers with respect to their (1) ambient concentrations and detectability in PM2.5 in Iowa City, IA, USA; (2) gas–particle partitioning behaviour; and (3) source specificity by way of correlations with primary and secondary source tracers and literature review. A widely used tracer for toluene-derived SOA, 2,3-dihydroxy-4-oxopentanoic acid was only detected in the particle phase (Fp = 1) at low but consistently measurable ambient concentrations (averaging 0.3 ng m−3). Four aromatic dicarboxylic acids were detected at relatively higher concentrations (9.1–34.5 ng m−3), of which phthalic acid was the most abundant. Phthalic acid had a low particle-phase fraction (Fp =  0.26) likely due to quantitation interferences from phthalic anhydride, while 4-methylphthalic acid was predominantly in the particle phase (Fp = 0.82). Phthalic acid and 4-methylphthalic acid were both highly correlated with 2,3-dihydroxy-4-oxopentanoic acid (rs = 0.73, p = 0.003; rs = 0.80, p 

Description: Products of secondary organic aerosol (SOA) from aromatic volatile organic compounds (VOC) – 2,3-dihydroxy-4-oxopentanoic acid, dicarboxylic acids, nitromonoaromatics, and furandiones – were evaluated for their potential to serve as anthropogenic SOA tracers with respect to their 1) ambient concentrations and detectability in PM2.5 in Iowa City, IA, USA, 2) gas-particle partitioning behaviour, and 3) source specificity by way of correlations with primary and secondary source tracers and literature review. A widely used tracer for toluene-derived SOA, 2,3-dihydroxy-4-oxopentanoic acid was only detected in the particle phase (Fp = 1) at low, but consistently measureable ambient concentrations (averaging 0.3 ng m−3). Four aromatic dicarboxylic acids were detected at relatively higher concentrations (9.1–34.5 ng m−3), of which phthalic acid was the most abundant. Phthalic acid had a low particle-phase fraction (Fp = 0.26) likely due to quantitation interferences from phthalic anhydride, while 4-methylphthalic acid was predominantly in the particle phase (Fp = 0.82). Phthalic acid and 4-methyl phthalic acid were both highly correlated with 2,3-dihydroxy-4-oxopentanoic acid (rs = 0.73, p = 0.003; rs = 0.80, p 〈 0.001, respectively), suggesting that they were derived from aromatic VOC. Isophthalic and terephthalic acids, however, were detected only in the particle phase (Fp = 1) and correlations suggested association with primary emission sources. Nitromonoaromatics were dominated by particle-phase concentrations of 4-nitrocatechol (1.6 ng m−3) and 4-methyl-5-nitrocatechol (1.6 ng m−3) that were associated with biomass burning. Meanwhile, 4-hydroxy-3-nitrobenzyl alcohol was detected in a lower concentration (0.06 ng m−3) in the particle phase only (Fp = 1), and is known as a product of toluene photooxidation. Furandiones in the atmosphere have only been attributed to the photooxidation of aromatic hydrocarbons, however the substantial partitioning toward the gas phase (Fp ≤ 0.16) and their water sensitivity limit their application as tracers. The outcome of this study is the demonstration that 2,3-dihydroxy-4-oxopentanoic acid, phthalic acid, 4-methylphthalic acid, and 4-hydroxy-3-nitrobenzyl alcohol are good candidates for tracing SOA from aromatic VOC.

Description: This study examines the anthropogenic influence on biogenic organosulfate formation at an urban site in Atlanta, GA in the Southeastern United States. Organosulfates were analyzed in fine particulate matter (PM2.5) collected during August 2015 in Atlanta using hydrophilic interaction liquid chromatography (HILIC), tandem mass spectrometry (MS/MS), and high-resolution time-of-flight (ToF) mass spectrometry. By their MS/MS response, 32 major organosulfate species were identified, selected species were quantified, and other species were semi-quantified using surrogate standards. Organosulfates accounted for 16.5% of PM2.5 organic carbon (OC). Isoprene-derived organosulfates were the most abundant, dominated by methyltetrol sulfate which accounted for 12.6% of PM2.5 OC. Together, the isoprene-derived organosulfates accounted for the majority of the isoprene-derived secondary organic aerosols (SOA) that had been previously observed in Atlanta, but had not been identified at the molecular level. Other major species included seven monoterpene-derived organosulfates, five diesel and/or biodiesel-derived organosulfates, and three new organosulfates that are also expected to derive from isoprene. Organosulfate species and concentrations in Atlanta were compared to those in a rural forested site in Centreville, AL during summer 2013, which were also dominated by isoprene-derived organosulfates. In Atlanta, isoprene-derived organosulfate concentrations were two to six times higher and accounted for twice as much OC. The greatest enhancement in concentration was observed for 2-methylglyceric acid sulfate, a tracer for isoprene high-NOx SOA. The isoprene-derived organosulfates indicated a stronger influence of NOx in Atlanta compared to Centreville. Overall, these results suggest that SOA in the Southeastern US can be reduced by controlling NOx and SO2 emissions from fossil fuel combustion. This study gives insights into the major organosulfate species that should be targets for future measurements in urban environments and standard development.

Description: Online and offline measurements of fine particulate matter (PM) near the urban and industrial Houston Ship Channel in Houston, Texas, USA during May 2015 were utilized to characterize its chemical composition and to evaluate the relative contributions of primary, secondary, biogenic, and anthropogenic sources. Aerosol mass spectrometry (AMS) on non-refractory PM1 (PM≤1µm) indicated major contributions from sulfate (averaging 50%), organic aerosol (OA, 40%), and ammonium (14%). Positive matrix factorization (PMF) of AMS data categorized OA on average as 22% hydrocarbon-like organic aerosol (HOA), 29% cooking influenced semi-volatile oxygenated organic aerosol (CI-SV-OOA), and 48% low-volatility oxygenated organic aerosol (LV-OOA), with the latter two sources indicative of secondary organic aerosol (SOA). Chemical analysis of PM2.5 (PM≤2.5µm) filter samples agreed that organic matter (35%) and sulfate (21%) were the most abundant components. Organic speciation of PM2.5 organic carbon (OC) focused on molecular markers of primary sources and SOA tracers derived from biogenic and anthropogenic volatile organic compounds (VOC). The sources of PM2.5 OC were estimated using molecular marker-based positive matric factorization (MM-PMF) and chemical mass balance (CMB) models. MM-PMF resolved 9 factors that were identified as diesel engines (11.5%), gasoline engines (24.3%), non-tailpipe vehicle emissions (11.1%), ship emissions (2.2%), cooking (1.0%), biomass burning (BB, 10.6%), isoprene SOA (11.0%), high-NOx anthropogenic SOA (6.6%), and low-NOx anthropogenic SOA (21.7%). Using available source profiles, CMB apportioned 41% of OC to primary fossil sources (gasoline engines, diesel engines, and ship emissions), 5% to BB, 15% to SOA (including 7.4% biogenic and 7.6% anthropogenic), and 39% to other sources that were not included in the model and are expected to be secondary. This study presents the first application of in situ AMS-PMF, MM-PMF, and CMB for OC source apportionment and the integration of these methods to evaluate the relative roles of biogenic, anthopogenic, and BB-SOA. The three source apportionment models agreed that ~50% of OC is associated with primary emissions from fossil fuel use, particularly motor vehicles. Differences among the models reflect their ability to resolve sources based upon the input chemical measurements, with molecular marker-based methods providing greater source specificity and resolution for minor sources. By combining results from MM-PMF and CMB, BB was estimated to contribute 11% of OC, with 5% of primary emissions and 6% BB-SOA. SOA was dominantly anthropogenic (28%) compared to biogenic (11%) or BB-derived. The three-model approach demonstrates significant contributions of anthropogenic SOA to fine PM. More broadly, the findings and methodologies presented herein can be used to advance local and regional understanding of anthropogenic contributions to SOA.