Development, Demonstration, and Evaluation of Routine Monitoring of Aerosol Carbon, Oxygen, and Sulfur Content.

Traditional online measurements of the chemical composition of particulate matter have relied on expensive and complex research-grade instrumentation based on mass spectrometry and/or chromatography. However, routine monitoring requires lower-cost alternatives that can be operated autonomously, and such tools are lacking. Routine monitoring of particulate matter, especially organic aerosol, relies instead on offline techniques such as filter collection that require significant operator effort. To address this gap, we present here a new online instrument, the "ChemSpot", that provides information on organic aerosol mass loading, volatility, and degree of oxygenation, along with sulfur content. The instrument grows particles with water condensation, impacts them onto a passivated surface with low heat capacity, and uses stepped thermal desorption of analytes to a combination of flame ionization detector (FID) and flame photometric detector (FPD) and then to a CO2 detector downstream of the FID/FPD setup. By relying on detectors designed for gas chromatography, calibration is achieved almost entirely through the introduction of gases without the need for regular introduction of particle-phase calibrants. Particle collection efficiency of greater than 95% was achieved consistently, and the collection cell was shown to rapidly and precisely heat to ∼800 °C at a rate as fast as 10 °C per second. Measurements of total organic carbon, volatility distribution of organic aerosol, total sulfur, and oxygen-to-carbon ratio (O:C) collected during a continuous multi-week period are presented here to demonstrate the autonomous operation of "ChemSpot". Colocated measurements with a mass spectrometer, an aerosol chemical speciation monitor (ACSM), show good correlation and relatively low bias between the instruments (mean absolute percentage error of 21% and 27% for organic carbon and equivalent sulfate measurements, respectively).

Strong temperature influence and indiscernible ventilation effect on dynamics of some semivolatile organic compounds in the indoor air of an office.

Many manmade organic air pollutants are semivolatile and primarily used and exposed indoors. It remains unclear how indoor environmental parameters affect indoor air dynamics of semivolatile organic compounds (SVOCs) in real-world indoor conditions, which directly relates to human exposure. By making time-resolved SVOC measurements over multiple weeks in an office, we characterized the indoor air dynamics of six representative SVOCs which were mainly present in the gas phase and of indoor origins, and investigated the effects of the temperature and ventilation rate. The six species include di-isobutyl phthalate and di-n-butyl phthalate, as well as two n-alkanes and two siloxanes. Airborne concentrations of all six SVOCs responded strongly and quickly to changes in the indoor temperature. The temperature dependence of individual species can be well fitted in the form of the van't Hoff equation, and explained 65-86% of the observed variation in the logarithm-transformed concentrations. In contrast, increasing the ventilation rate by a factor of 3-5 for hours at a constant temperature had no discernible influence on the SVOC concentrations. Further kinetic modeling analysis suggests that the observed fast temperature response and indiscernible ventilation effect are both associated with SVOC sorption onto indoor surfaces, which dramatically slows the response of SVOC concentration to changes in the ventilation rate and speeds up the response to changes in the temperature. These results highlight the importance of sorption reservoirs on regulating indoor SVOC dynamics and also have important implications for controlling and assessing indoor air exposure to SVOCs.

Natural and Anthropogenically Influenced Isoprene Oxidation in Southeastern United States and Central Amazon.

Anthropogenic emissions alter secondary organic aerosol (SOA) formation chemistry from naturally emitted isoprene. We use correlations of tracers and tracer ratios to provide new perspectives on sulfate, NOx, and particle acidity influencing isoprene-derived SOA in two isoprene-rich forested environments representing clean to polluted conditions-wet and dry seasons in central Amazonia and Southeastern U.S. summer. We used a semivolatile thermal desorption aerosol gas chromatograph (SV-TAG) and filter samplers to measure SOA tracers indicative of isoprene/HO2 (2-methyltetrols, C5-alkene triols, 2-methyltetrol organosulfates) and isoprene/NOx (2-methylglyceric acid, 2-methylglyceric acid organosulfate) pathways. Summed concentrations of these tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 µg m-3 reduction in sulfate corresponds with at least ∼0.5 µg m-3 reduction in isoprene-derived SOA. We also find that isoprene/NOx pathway SOA mass primarily comprises organosulfates, ∼97% in the Amazon and ∼55% in Southeastern United States. We infer under natural conditions in high isoprene emission regions that preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought of as representative of an anthropogenic influence. We further report the first field observations showing that particle acidity correlates positively with 2-methylglyceric acid partitioning to the gas phase and negatively with the ratio of 2-methyltetrols to C5-alkene triols.

Highly Speciated Measurements of Terpenoids Emitted from Laboratory and Mixed-Conifer Forest Prescribed Fires.

Wildland fires in the western United States are projected to increase in frequency, duration, and size. Characterized by widespread and diverse conifer forests, burning within this region may lead to significant terpenoid emissions. Terpenoids constitute a major class of highly reactive secondary organic aerosol (SOA) precursors, with significant structure-dependent variability in reactivity and SOA-formation potential. In this study, highly speciated measurements of terpenoids emitted from laboratory and prescribed fires were achieved using two-dimensional gas chromatography. Nearly 100 terpenoids were measured in smoke samples from 71 fires, with high variability in the dominant compounds. Terpenoid emissions were dependent on plant species and tissues. Canopy/needle-derived emissions dominated in the laboratory fires, whereas woody-tissue-derived emissions dominated in the prescribed fires. Such differences likely have implications for terpenoid emissions from high vs low intensity fires and suggest that canopy-dominant laboratory fires may not accurately represent terpenoid emissions from prescribed fires or wildland fires that burn with low intensity. Predicted SOA formation was sensitive to the diversity of emitted terpenoids when compared to assuming a single terpene surrogate. Given the demonstrated linkages between fuel type, fire terpenoid emissions, and the subsequent implications for plume chemistry, speciated measurements of terpenoids in smoke derived from diverse ecosystems and fire regimes may improve air quality predictions downwind of wildland fires.

Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States.

The chemical complexity of atmospheric organic aerosol (OA) has caused substantial uncertainties in understanding its origins and environmental impacts. Here, we provide constraints on OA origins through compositional characterization with molecular-level details. Our results suggest that secondary OA (SOA) from monoterpene oxidation accounts for approximately half of summertime fine OA in Centreville, AL, a forested area in the southeastern United States influenced by anthropogenic pollution. We find that different chemical processes involving nitrogen oxides, during days and nights, play a central role in determining the mass of monoterpene SOA produced. These findings elucidate the strong anthropogenic-biogenic interaction affecting ambient aerosol in the southeastern United States and point out the importance of reducing anthropogenic emissions, especially under a changing climate, where biogenic emissions will likely keep increasing.

Observations of sesquiterpenes and their oxidation products in central Amazonia during the wet and dry seasons.

Biogenic volatile organic compounds (BVOCs) from the Amazon forest region represent the largest source of organic carbon emissions to the atmosphere globally. These BVOC emissions dominantly consist of volatile and intermediate-volatility terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). We collected quartz filter samples with 12 h time resolution and performed hourly in situ measurements with a semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) at a rural site ("T3") located to the west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon2014/5) field campaign to measure intermediate-volatility and semi-volatile BVOCs and their oxidation products during the wet and dry seasons. We speciated and quantified 30 sesquiterpenes and 4 diterpenes with mean concentrations in the range 0.01-6.04 ngm-3 (1-670ppqv). We estimate that sesquiterpenes contribute approximately 14 and 12% to the total reactive loss of O3 via reaction with isoprene or terpenes during the wet and dry seasons, respectively. This is reduced from ~ 50-70 % for within-canopy reactive O3 loss attributed to the ozonolysis of highly reactive sesquiterpenes (e.g., ß-caryophyllene) that are reacted away before reaching our measurement site. We further identify a suite of their oxidation products in the gas and particle phases and explore their role in biogenic SOA formation in the central Amazon region. Synthesized authentic standards were also used to quantify gas- and particle-phase oxidation products derived from ß-caryophyllene. Using tracer-based scaling methods for these products, we roughly estimate that sesquiterpene oxidation contributes at least 0.4-5 % (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. By comparing our field data to laboratory-based sesquiterpene oxidation experiments we confirm that more than 40 additional observed compounds produced through sesquiterpene oxidation are present in Amazonian SOA, warranting further efforts towards more complete quantification.

Ambient Gas-Particle Partitioning of Tracers for Biogenic Oxidation.

Exchange of atmospheric organic compounds between gas and particle phases is important in the production and chemistry of particle-phase mass but is poorly understood due to a lack of simultaneous measurements in both phases of individual compounds. Measurements of particle- and gas-phase organic compounds are reported here for the southeastern United States and central Amazonia. Polyols formed from isoprene oxidation contribute 8% and 15% on average to particle-phase organic mass at these sites but are also observed to have substantial gas-phase concentrations contrary to many models that treat these compounds as nonvolatile. The results of the present study show that the gas-particle partitioning of approximately 100 known and newly observed oxidation products is not well explained by environmental factors (e.g., temperature). Compounds having high vapor pressures have higher particle fractions than expected from absorptive equilibrium partitioning models. These observations support the conclusion that many commonly measured biogenic oxidation products may be bound in low-volatility mass (e.g., accretion products, inorganic-organic adducts) that decomposes to individual compounds on analysis. However, the nature and extent of any such bonding remains uncertain. Similar conclusions are reach for both study locations, and average particle fractions for a given compound are consistent within ∼25% across measurement sites.

Effects of Particle Filters and Selective Catalytic Reduction on Heavy-Duty Diesel Drayage Truck Emissions at the Port of Oakland.

Effects of fleet modernization and use of diesel particle filters (DPF) and selective catalytic reduction (SCR) on heavy-duty diesel truck emissions were studied at the Port of Oakland in California. Nitrogen oxides (NOx), black carbon (BC), particle number (PN), and size distributions were measured in the exhaust plumes of ∼1400 drayage trucks. Average NOx, BC, and PN emission factors for newer engines (2010-2013 model years) equipped with both DPF and SCR were 69 ± 15%, 92 ± 32%, and 66 ± 35% lower, respectively, than 2004-2006 engines without these technologies. Intentional oxidation of NO to NO2 for DPF regeneration increased tailpipe NO2 emissions, especially from older (1994-2006) engines with retrofit DPFs. Increased deployment of advanced controls has further skewed emission factor distributions; a small number of trucks emit a disproportionately large fraction of total BC and NOx. The fraction of DPF-equipped drayage trucks increased from 2 to 99% and the median engine age decreased from 11 to 6 years between 2009 and 2013. Over this period, fleet-average BC and NOx emission factors decreased by 76 ± 22% and 53 ± 8%, respectively. Emission changes occurred rapidly compared to what would have been observed due to natural (i.e., unforced) turnover of the Port truck fleet. These results provide a preview of more widespread emission changes expected statewide and nationally in the coming years.

Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States.

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations.

Insights into secondary organic aerosol formation mechanisms from measured gas/particle partitioning of specific organic tracer compounds.

In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.

Development of a new consumable-free thermal modulator for comprehensive two-dimensional gas chromatography.

A simple and cost-effective GC×GC modulator requiring no moving parts or consumables, hence suitable for field analysis and monitoring, was developed. The modulator was constructed from a specially designed Silcosteel® trapping capillary, installed outside the GC oven, and coated inside with polydimethylsiloxane (PDMS) stationary phase. Dual-stage modulation was accomplished by resistively heating alternate segments of the trap with a custom-designed capacitive discharge power supply. The performance of the proposed modulator was comparable to many GC×GC systems currently in use, with the injection band widths as low as 60 ms at half height. With proper selection of the stationary phase in the trap, the modulator can be used for the analysis of complex mixtures with volatility range spanning from n-C5 to n-C40.

In situ measurements of gas/particle-phase transitions for atmospheric semivolatile organic compounds.

An understanding of the gas/particle-phase partitioning of semivolatile compounds is critical in determining atmospheric aerosol formation processes and growth rates, which in turn affect global climate and human health. The Study of Organic Aerosol at Riverside 2005 campaign was performed to gain a better understanding of the factors responsible for aerosol formation and growth in Riverside, CA, a region with high concentrations of secondary organic aerosol formed through the phase transfer of low-volatility reaction products from the oxidation of precursor gases. We explore the ability of the thermal desorption aerosol gas chromatograph (TAG) to measure gas-to-particle-phase transitioning for several organic compound classes (polar and nonpolar) found in the ambient Riverside atmosphere by using in situ observations of several hundred semivolatile organic compounds. Here we compare TAG measurements to modeled partitioning of select semivolatile organic compounds. Although TAG was not designed to quantify the vapor phase of semivolatile organics, TAG measurements do distinguish when specific compounds are dominantly in the vapor phase, are dominantly in the particle phase, or have both phases present. Because the TAG data are both speciated and time-resolved, this distinction is sufficient to see the transition from vapor to particle phase as a function of carbon number and compound class. Laboratory studies typically measure the phase partitioning of semivolatile organic compounds by using pure compounds or simple mixtures, whereas hourly TAG phase partitioning measurements can be made in the complex mixture of thousands of polar/nonpolar and organic/inorganic compounds found in the atmosphere.

Thermal desorption comprehensive two-dimensional gas chromatography for in-situ measurements of organic aerosols.

The complexity of organic composition and temporal variability of atmospheric aerosols presents an extreme analytical challenge. Comprehensive two-dimensional gas chromatography (GC x GC) has been used on time integrated filter samples to reveal the presence of thousands of individual organic compounds in aerosols, but without defining the temporal variability in composition ideal for providing information on source resolution and human exposure to specific pollutants. We hereby introduce a new instrument, 2D-TAG, which combines our in-situ thermal desorption aerosol GC (TAG) instrument with GC x GC allowing for dramatically improved separation of organics with automated measurements at hourly timescales.

Variations of nanoparticle concentrations at the Fresno Supersite.

Particle size distributions from 3 nm to 2 mum were measured at the Fresno, CA, Supersite from August 25, 2002 through July 31, 2003. Nanoparticle (3-10 nm) concentrations and the ratio of nanoparticle to total particle concentration were inversely related to particle surface areas from 50 to 1000 mum(2) cm(-3). Elevated nanoparticle concentrations were associated with motor vehicle emissions and with photochemical particle production. In contrast with Atlanta, GA, where concentrations of photochemically derived nanoparticles exceeded 10(5) cm(-3), 5-min average nanoparticle concentrations in Fresno never exceeded 24,400 cm(-3). While photochemical particle production occurs in Fresno, evidence of new particle production (i.e., an increase in number concentration with decreasing size below 10 nm) was not observed. This suggests that photochemical particle production may have occurred at a higher altitude followed by mixing to the surface, or that the fresh particle production rate was smaller with respect to the loss rate by coagulation than it was in Atlanta. Lower production rates in Fresno are more consistent with lower concentrations of sulfur precurors and low relative humidity in Fresno than they are in Atlanta.

Particle size relationships at the Fresno Supersite.

Aerosol size distributions are presented for a winter intensive study at the Fresno Supersite. The size distributions were consistent with and predictive for continuous PM2.5 measured by beta attenuation. They varied temporally with respect to source type and intensity, with the smallest mean diameters associated with high NOx concentrations during weekday morning rush hours. Conversely, small and large particle and black carbon (BC) concentrations were higher during Sunday and weekday evenings in response to traffic and residential wood combustion emissions. Ambient PM2.5 light scattering (Bsp) was precisely but systematically underestimated during winter, probably because of heating in the sample shelter.