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DOE OSTI2026

Legacy Analysis of Milky Way Dwarf Spheroidal Satellite Galaxies: An Update

Studies of Fermi Large Area Telescope (LAT) data coincident with dwarf spheroidal satellite galaxies (dSphs) of the Milky Way have put the most stringent constraints on models of annihilating dark matter (DM) with candidate masses in the GeV–TeV range. Recent results found the presence of small, local significance excesses from these targets, at the 2σ–3σ level. However, these excesses disagree on the predicted properties of the DM candidate, and their significance vanishes when considering correction factors for the number of trials. In this work, we apply key improvements to the analysis of dSphs. We use stricter cuts on the data, implement a method to adaptively model the background, and assume an updated framework for DM annihilation. We find that our improved background modeling leads to a better agreement between the model and the data. This produces an increase in the local and global significance of the dSph excess compared to previous studies. Finally, we find that the DM properties obtained in this work are less dependent on the sample of dSphs being considered compared to previous studies, while remaining in agreement with the predictions from the Galactic center excess observed by Fermi/LAT and the antiproton excess observed by the Alpha Magnetic Spectrometer (AMS-02). Considering our improvements, a future significant increase in the number of dwarfs may lead to a definitive confirmation or exclusion of the DM interpretation of the Galactic center excess.

cold dark matter↗

DOE OSTI2014

Chemistry of new particle growth in mixed urban and biogenic emissions – insights from CARES

Regional new particle formation and growth events (NPEs) were observed on most days over the Sacramento and western Sierra foothills area of California in June 2010 during the Carbonaceous Aerosols and Radiative Effect Study (CARES). Simultaneous particle measurements at both the T0 (Sacramento, urban site) and the T1 (Cool, rural site located ~40 km northeast of Sacramento) sites of CARES indicate that the NPEs usually occurred in the morning with the appearance of an ultrafine mode at ~15 nm (in mobility diameter, D m , measured by a mobility particle size spectrometer operating in the range10-858 nm) followed by the growth of this modal diameter to ~50 nm in the afternoon. These events were generally associated with southwesterly winds bringing urban plumes from Sacramento to the T1 site. The growth rate was on average higher at T0 (7.1±2.7 nm h -1 ) than at T1 (6.2±2.5 nm h -1 ), likely due to stronger anthropogenic influences at T0. Using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), we investigated the evolution of the size-resolved chemical composition of new particles at T1. Our results indicate that the growth of new particles was driven primarily by the condensation of oxygenated organic species and, to a lesser extent, ammonium sulfate. New particles appear to be fully neutralized during growth, consistent with high NH 3 concentration in the region. Nitrogen-containing organic ions (i.e., CHN + , CH 4 N+,C2H3N + , and C 2 H N + ) that are indicative of the presence of alkyl-amine species in submicrometer particles enhanced significantly during the NPE days, suggesting that amines might have played a role in these events. Our results also indicate that the bulk composition of the ultrafine mode organics during NPEs was very similar to that of anthropogenically influenced secondary organic aerosol (SOA) observed in transported urban plumes. In addition, the concentrations of species representative of urban emissions (e.g., black carbon,CO, NO x , and toluene) were significantly higher whereas thephoto-oxidation products of biogenic VOCs (volatile organic compounds) and the biogenically influenced SOA also increased moderately during the NPE days compared to the non-event days. These results indicate that the frequently occurring NPEs over the Sacramento and Sierra Nevada regions were mainly driven by urban plumes from Sacramento and the San Francisco Bay Area, and that the interaction of regional biogenic emissions with the urban plumes has enhanced the new particle growth. This finding has important implications for quantifying the climate impacts of NPEs on global scale.

Setyan, Ari↗

DOE OSTI2015

Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NO x = NO + NO 2 ) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NO x -dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NO x perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NO x can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NO x pathways, O 3 versus NO 3 -initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO–HR-ToF-CIMS are highly correlated with, and explain at least 25–50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmospheric aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O:C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ~50 % RH in the sampling inlets. Furthermore, while the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2016

Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2 O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range are complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15 H 24 (e.g., β -caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15 H 22 , abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and O x , which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive ( τ OH ~ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ~ –0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OS C ~ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. Furthermore, these results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: seasonal and diel variations and impact of anthropogenic emissions

Abstract. During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ∼ 0. 15 is consistent with the largely uniform and high O : C value (∼ 0. 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O : C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O : C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the κ value with O : C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O : C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O : C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O : C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in κorg with O : C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between κorg and O : C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

Thalman, Ryan↗

DOE OSTI2018

Urban influence on the concentration and composition of submicron particulate matter in central Amazonia

An understanding of how anthropogenic emissions affect the concentrations and composition of airborne particulate matter (PM) is fundamental to quantifying the influence of human activities on climate and air quality. The central Amazon Basin, especially around the city of Manaus, Brazil, has experienced rapid changes in the past decades due to ongoing urbanization. Herein, changes in the concentration and composition of submicron PM due to pollution downwind of the Manaus metropolitan region are reported as part of the GoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a suite of other gas- and particle-phase instruments were deployed at the T3 research site, 70 km downwind of Manaus, during the wet season. At this site, organic components represented 79±7 % of the non-refractory PM 1 mass concentration on average, which was in the same range as several upwind sites. However, the organic PM 1 was considerably more oxidized at T3 compared to upwind measurements. Positive-matrix factorization (PMF) was applied to the time series of organic mass spectra collected at the T3 site, yielding three factors representing secondary processes (73±15 % of total organic mass concentration) and three factors representing primary anthropogenic emissions (27±15 %). Fuzzy c-means clustering (FCM) was applied to the afternoon time series of concentrations of NO y , ozone, total particle number, black carbon, and sulfate. Four clusters were identified and characterized by distinct air mass origins and particle compositions. Two clusters, Bkgd-1 and Bkgd-2, were associated with background conditions. Bkgd-1 appeared to represent near-field atmospheric PM production and oxidation of a day or less. Bkgd-2 appeared to represent material transported and oxidized for two or more days, often with out-of-basin contributions. Two other clusters, Pol-1 and Pol-2, represented the Manaus influence, one apparently associated with the northern region of Manaus and the other with the southern region of the city. A composite of the PMF and FCM analyses provided insights into the anthropogenic effects on PM concentration and composition. The increase in mass concentration of submicron PM ranged from 25 % to 200 % under polluted compared with background conditions, including contributions from both primary and secondary PM. Furthermore, a comparison of PMF factor loadings for different clusters suggested a shift in the pathways of PM production under polluted conditions. Nitrogen oxides may have played a critical role in these shifts. Increased concentrations of nitrogen oxides can shift pathways of PM production from HO 2 -dominant to NO-dominant as well as increase the concentrations of oxidants in the atmosphere. Consequently, the oxidation of biogenic and anthropogenic precursor gases as well as the oxidative processing of preexisting atmospheric PM can be accelerated. This combined set of results demonstrates the susceptibility of atmospheric chemistry, air quality, and associated climate forcing to anthropogenic perturbations over tropical forests.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2018

Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol

Abstract. Secondary organic aerosol (SOA) is a complex mixture of hundreds of semi-volatile to extremely low-volatility organic compounds that are chemically processed in the atmosphere, including via heterogeneous oxidation by gas-phase radicals. Relative humidity (RH) has a substantial impact on particle phase, which can affect how SOA evolves in the atmosphere. In this study, SOA from dark α -pinene ozonolysis is heterogeneously aged by OH radicals in a flow tube at low and high RH. At high RH (RH = 89 %) there is substantial loss of particle volume (~60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH = 25 %) there is little mass loss (< 20 %) at the same OH exposure. Mass spectra of the SOA particles were measured as a function of OH exposure using a vacuum ultraviolet aerosol mass spectrometer (VUV-AMS). The mass spectra observed at low RH overall exhibit minor changes with oxidation and negligible further changes above an OH exposure = 2×10 12 molecule cm -3 s suggesting limited impact of oxidation on the particle composition. In contrast, the mass spectra observed at high RH exhibit substantial and continuous changes as a function of OH exposure. Further, at high RH clusters of peaks in the mass spectra exhibit unique decay patterns, suggesting different responses of various species to oxidation. A model of heterogeneous oxidation has been developed to understand the origin of the difference in aging between the low- and high-RH experiments. Differences in diffusivity of the SOA between the low- and high-RH experiments alone can explain the difference in compositional change but cannot explain the difference in mass loss. Instead, the difference in mass loss is attributable to RH-dependent differences in the OH uptake coefficient and/or the net probability of fragmentation, with either or both larger at high RH compared to low RH. These results illustrate the important impact of relative humidity on the fate of SOA in the atmosphere.

Li, Ziyue (ORCID:0000000191017737)↗

DOE OSTI2018

Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US

Abstract. Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2 × sulfate, R N/2S ≈ 0.8 to 0.9) with approximately 70 % of total ammonia and ammonium (NH x ) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H + ] air (H + in µg m -3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid–liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic–organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C ≥ 0.6) compounds including several isoprene-derived tracers as well as levoglucosan but decrease particle-phase partitioning for low O : C, monoterpene-derived species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Ubiquitous influence of wildfire emissions and secondary organic aerosol on summertime atmospheric aerosol in the forested Great Lakes region

Long-range aerosol transport affects locations hundreds of kilometers from the point of emission, leading to distant particle sources influencing rural environments that have few major local sources. Source apportionment was conducted using real-time aerosol chemistry measurements made in July 2014 at the forested University of Michigan Biological Station near Pellston, Michigan, a site representative of the remote forested Great Lakes region. Size-resolved chemical composition of individual 0.5–2.0 µm particles was measured using an aerosol time-of-flight mass spectrometer (ATOFMS), and non-refractory aerosol mass less than 1 µm (PM 1 ) was measured with a high-resolution aerosol mass spectrometer (HR-AMS). The field site was influenced by air masses transporting Canadian wildfire emissions and urban pollution from Milwaukee and Chicago. During wildfire-influenced periods, 0.5–2.0 µm particles were primarily aged biomass burning particles (88 % by number). These particles were heavily coated with secondary organic aerosol (SOA) formed during transport, with organics (average O∕C ratio of 0.8) contributing 89 % of the PM 1 mass. During urban-influenced periods, organic carbon, elemental carbon–organic carbon, and aged biomass burning particles were identified, with inorganic secondary species (ammonium, sulfate, and nitrate) contributing 41 % of the PM 1 mass, indicative of atmospheric processing. With current models underpredicting organic carbon in this region and biomass burning being the largest combustion contributor to SOA by mass, these results highlight the importance for regional chemical transport models to accurately predict the impact of long-range transported particles on air quality in the upper Midwest, United States, particularly considering increasing intensity and frequency of Canadian wildfires.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Free tropospheric aerosols at the Mt. Bachelor Observatory: more oxidized and higher sulfate content compared to boundary layer aerosols

Abstract. Understanding the properties and life cycle processes of aerosol particles in regional air masses is crucial for constraining the climate impacts of aerosols on a global scale. In this study, characteristics of aerosols in the boundary layer (BL) and free troposphere (FT) of a remote continental region in the western US were studied using a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) deployed at the Mount Bachelor Observatory (MBO; 2763 m a.s.l.) in central Oregon in summer 2013. In the absence of wildfire influence, the average ( ± 1 σ ) concentration of non-refractory submicrometer particulate matter (NR- PM 1 ) at MBO was 2.8 ( ± 2.8) µ g m -3 and 84 % of the mass was organic. The other NR- PM 1 components were sulfate (11 %), ammonium (2.8 %), and nitrate (0.9 %). The organic aerosol (OA) at MBO from these clean periods showed clear diurnal variations driven by the boundary layer dynamics with significantly higher concentrations occurring during daytime, upslope conditions. NR- PM 1 contained a higher mass fraction of sulfate and was frequently acidic when MBO resided in the FT. In addition, OA in the FT was found to be highly oxidized (average O/C of 1.17) with low volatility while OA in BL-influenced air masses was moderately oxidized (average O/C of 0.67) and semivolatile. There are indications that the BL-influenced OA observed at MBO was more enriched in organonitrates and organosulfur compounds (e.g., MSA) and appeared to be representative of biogenic secondary organic aerosol (SOA) originated in the BL. A summary of the chemical compositions of NR- PM 1 measured at a number of other high-altitude locations in the world is presented and similar contrasts between FT and BL aerosols were observed. The significant compositional and physical differences observed between FT and BL aerosols may have important implications for understanding the climate effects of regional background aerosols.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

The potential role of methanesulfonic acid (MSA) in aerosol formation and growth and the associated radiative forcings

Atmospheric marine aerosol particles impact Earth's albedo and climate. These particles can be primary or secondary and come from a variety of sources, including sea salt, dissolved organic matter, volatile organic compounds, and sulfur-containing compounds. Dimethylsulfide (DMS) marine emissions contribute greatly to the global biogenic sulfur budget, and its oxidation products can contribute to aerosol mass, specifically as sulfuric acid and methanesulfonic acid (MSA). Further, sulfuric acid is a known nucleating compound, and MSA may be able to participate in nucleation when bases are available. As DMS emissions, and thus MSA and sulfuric acid from DMS oxidation, may have changed since pre-industrial times and may change in a warming climate, it is important to characterize and constrain the climate impacts of both species. Currently, global models that simulate aerosol size distributions include contributions of sulfate and sulfuric acid from DMS oxidation, but to our knowledge, global models typically neglect the impact of MSA on size distributions. In this study, we use the GEOS-Chem-TOMAS (GC-TOMAS) global aerosol microphysics model to determine the impact on aerosol size distributions and subsequent aerosol radiative effects from including MSA in the size-resolved portion of the model. The effective equilibrium vapor pressure of MSA is currently uncertain, and we use the Extended Aerosol Inorganics Model (E-AIM) to build a parameterization for GC-TOMAS of MSA's effective volatility as a function of temperature, relative humidity, and available gas-phase bases, allowing MSA to condense as an ideally nonvolatile or semivolatile species or too volatile to condense. We also present two limiting cases for MSA's volatility, assuming that MSA is always ideally nonvolatile (irreversible condensation) or that MSA is always ideally semivolatile (quasi-equilibrium condensation but still irreversible condensation). We further present simulations in which MSA participates in binary and ternary nucleation with the same efficacy as sulfuric acid whenever MSA is treated as ideally nonvolatile. When using the volatility parameterization described above (both with and without nucleation), including MSA in the model changes the global annual averages at 900 hPa of submicron aerosol mass by 1.2 %, N3 (number concentration of particles greater than 3 nm in diameter) by -3.9 % (non-nucleating) or 112.5 % (nucleating), N80 by 0.8 % (non-nucleating) or 2.1 % (nucleating), the cloud-albedo aerosol indirect effect (AIE) by -8.6 mW m -2 (non-nucleating) or -26 mW m -2 (nucleating), and the direct radiative effect (DRE) by -15 mW m -2 (non-nucleating) or -14  mW m -2 (nucleating). The sulfate and sulfuric acid from DMS oxidation produces 4–6 times more submicron mass than MSA does, leading to an ~10 times stronger cooling effect in the DRE. But the changes in N80 are comparable between the contributions from MSA and from DMS-derived sulfate/sulfuric acid, leading to comparable changes in the cloud-albedo AIE. Model–measurement comparisons with the Heintzenberg et al. (2000) dataset over the Southern Ocean indicate that the default model has a missing source or sources of ultrafine particles: the cases in which MSA participates in nucleation (thus increasing ultrafine number) most closely match the Heintzenberg distributions, but we cannot conclude nucleation from MSA is the correct reason for improvement. Model–measurement comparisons with particle-phase MSA observed with a customized Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) from the ATom campaign show that cases with the MSA volatility parameterizations (both with and without nucleation) tend to fit the measurements the best (as this is the first use of MSA measurements from ATom, we provide a detailed description of these measurements and their calibration). However, no one model sensitivity case shows the best model–measurement agreement for both Heintzenberg and the ATom campaigns. As there are uncertainties in both MSA's behavior (nucleation and condensation) and the DMS emissions inventory, further studies on both fronts are needed to better constrain MSA's past, current, and future impacts upon the global aerosol size distribution and radiative forcing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Contributions of biomass-burning, urban, and biogenic emissions to the concentrations and light-absorbing properties of particulate matter in central Amazonia during the dry season

Urbanization and deforestation have important impacts on atmospheric particulate matter (PM) over Amazonia. This study presents observations and analysis of PM1 concentration, composition, and optical properties in central Amazonia during the dry season, focusing on the anthropogenic impacts. The primary study site was located 70 km downwind of Manaus, a city of over 2 million people in Brazil, as part of the GoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol mass spectrometer (AMS) provided data on PM1 composition, and aethalometer measurements were used to derive the absorption coefficient babs,BrC of brown carbon (BrC) at 370 nm. Non-refractory PM1 mass concentrations averaged 12.2 µg m -3 at the primary study site, dominated by organics (83 %), followed by sulfate (11 %). A decrease in babs,BrC was observed as the mass concentration of nitrogen-containing organic compounds decreased and the organic PM1 O:C ratio increased, suggesting atmospheric bleaching of the BrC components. The organic PM1 was separated into six different classes by positive-matrix factorization (PMF), and the mass absorption efficiency Eabs associated with each factor was estimated through multivariate linear regression of babs,BrC on the factor loadings. The largest Eabs values were associated with urban (2.04±0.14 m2 g -1 ) and biomass-burning (0.82±0.04 to 1.50±0.07 m2 g -1 ) sources. Together, these sources contributed at least 80 % of babs,BrC while accounting for 30 % to 40 % of the organic PM1 mass concentration. In addition, a comparison of organic PM1 composition between wet and dry seasons revealed that only part of the 9-fold increase in mass concentration between the seasons can be attributed to biomass burning. Biomass-burning factor loadings increased by 30-fold, elevating its relative contribution to organic PM1 from about 10 % in the wet season to 30 % in the dry season. However, most of the PM1 mass (>60 %) in both seasons was accounted for by biogenic secondary organic sources, which in turn showed an 8-fold seasonal increase in factor loadings. A combination of decreased wet deposition and increased emissions and oxidant concentrations, as well as a positive feedback on larger mass concentrations are thought to play a role in the observed increases. Furthermore, fuzzy c-means clustering identified three clusters, namely “baseline”, “event”, and “urban” to represent different pollution influences during the dry season. The baseline cluster, representing the dry season background, was associated with a mean mass concentration of 9±3 µg m -3 . This concentration increased on average by 3 µg m -3 for both the urban and the event clusters. The event cluster, representing an increased influence of biomass burning and long-range transport of African volcanic emissions, was characterized by remarkably high sulfate concentrations. The urban cluster, representing the influence of Manaus emissions on top of the baseline, was characterized by an organic PM1 composition that differed from the other two clusters. The differences discussed suggest a shift in oxidation pathways as well as an accelerated oxidation cycle due to urban emissions, in agreement with findings for the wet season.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Predictions of the glass transition temperature and viscosity of organic aerosols from volatility distributions

Abstract. Volatility and viscosity are important properties of organic aerosols (OA), affecting aerosol processes such as formation, evolution, and partitioning of OA. Volatility distributions of ambient OA particles have often been measured, while viscosity measurements are scarce. We have previously developed a method to estimate the glass transition temperature (Tg) of an organic compound containing carbon, hydrogen, and oxygen. Based on analysis of over 2400 organic compounds including oxygenated organic compounds, as well as nitrogen- and sulfur-containing organic compounds, we extend this method to include nitrogen- and sulfur-containing compounds based on elemental composition. In addition, parameterizations are developed to predict Tg as a function of volatility and the atomic oxygen-to-carbon ratio based on a negative correlation between Tg and volatility. This prediction method of Tg is applied to ambient observations of volatility distributions at 11 field sites. The predicted Tg values of OA under dry conditions vary mainly from 290 to 339 K and the predicted viscosities are consistent with the results of ambient particle-phase-state measurements in the southeastern US and the Amazonian rain forest. Reducing the uncertainties in measured volatility distributions would improve predictions of viscosity, especially at low relative humidity. We also predict the Tg of OA components identified via positive matrix factorization of aerosol mass spectrometer (AMS) data. The predicted viscosity of oxidized OA is consistent with previously reported viscosity of secondary organic aerosols (SOA) derived from α-pinene, toluene, isoprene epoxydiol (IEPOX), and diesel fuel. Comparison of the predicted viscosity based on the observed volatility distributions with the viscosity simulated by a chemical transport model implies that missing low volatility compounds in a global model can lead to underestimation of OA viscosity at some sites. The relation between volatility and viscosity can be applied in the molecular corridor or volatility basis set approaches to improve OA simulations in chemical transport models by consideration of effects of particle viscosity in OA formation and evolution.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: Seasonal and diel variations and impact of anthropogenic emissions

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60km downwind of the city of Manaus, Brazil, in central Amazonia for one year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. Also, during both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ~0.15 is consistent with the largely uniform and high O:C value (~0.8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O:C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O:C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF analysis of AMS spectra, were estimated through multi-variable linear regression. For the SOA factors, the variation of the κ value with O:C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O:C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O:C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O:C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase of κorg with O:C, as observed during this and earlier field studies. Our finding helps better understand and reconcile the differences in the relationships between κorg and O:C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Simulating organic aerosol in Delhi with WRF-Chem using the volatility-basis-set approach: exploring model uncertainty with a Gaussian process emulator

The nature and origin of organic aerosol in the atmosphere remain unclear. The gas–particle partitioning of semi-volatile organic compounds (SVOCs) that constitute primary organic aerosols (POAs) and the multigenerational chemical aging of SVOCs are particularly poorly understood. The volatility basis set (VBS) approach, implemented in air quality models such as WRF-Chem (Weather Research and Forecasting model with Chemistry), can be a useful tool to describe emissions of POA and its chemical evolution. However, the evaluation of model uncertainty and the optimal model parameterization may be expensive to probe using only WRF-Chem simulations. Gaussian process emulators, trained on simulations from relatively few WRF-Chem simulations, are capable of reproducing model results and estimating the sources of model uncertainty within a defined range of model parameters. In this study, a WRF-Chem VBS parameterization is proposed; we then generate a perturbed parameter ensemble of 111 model runs, perturbing 10 parameters of the WRF-Chem model relating to organic aerosol emissions and the VBS oxidation reactions. This allowed us to cover the model's uncertainty space and to compare outputs from each run to aerosol mass spectrometer observations of organic aerosol concentrations and O:C ratios measured in New Delhi, India. The simulations spanned the organic aerosol concentrations measured with the aerosol mass spectrometer (AMS). However, they also highlighted potential structural errors in the model that may be related to unsuitable diurnal cycles in the emissions and/or failure to adequately represent the dynamics of the planetary boundary layer. While the structural errors prevented us from clearly identifying an optimized VBS approach in WRF-Chem, we were able to apply the emulator in the following two periods: the full period (1–29 May) and a subperiod period of 14:00–16:00 h LT (local time) on 1–29 May. The combination of emulator analysis and model evaluation metrics allowed us to identify plausible parameter combinations for the analyzed periods. We demonstrate that the methodology presented in this study can be used to determine the model uncertainty and to identify the appropriate parameter combination for the VBS approach and hence to provide valuable information to improve our understanding of OA production.

54 ENVIRONMENTAL SCIENCES↗