Bulk organic aerosol analysis by PTR-MS: an improved methodology for the determination of total organic mass, O:C and H:C ele- mental ratios and the average molecular formula

International audienceWe have recently shown in this journal (Müller et al., Anal. Chem. 2017, 89, 10889-10897) how a proton-transfer-reaction mass spectrometry (PTR-MS) analyzer measured particulate organic matter in urban atmospheres using the "Chemical Analysis of Aerosol Online" (CHARON) inlet. Our initial CHARON studies did not take into account fragmentation of protonated analyte molecules, which introduced a small but significant negative bias in the determination of bulk organic aerosol parameters. Herein, we studied the ionic fragmentation of 26 oxidized organic compounds typically found in atmospheric particles. This allowed us to derive a correction algorithm for the determination of the bulk organic mass concentration, m OA , the bulk-average hydrogen to carbon ratio, (H:C) bulk, the bulk-average oxygen-to-carbon, (O:C) bulk , and the bulk-average molecular formula, MF bulk. The correction algorithm was validated against AMS data using two sets of published data. Finally, we determined MF bulk of particles generated from the reaction of -pinene and ozone and compared and discussed the results in relation to the literature

Spectral absorption of biomass burning aerosol determined from retrieved single scattering albedo during ARCTAS

Actinic flux, as well as aerosol chemical and optical properties, were measured aboard the NASA DC-8 aircraft during the ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) mission in Spring and Summer 2008. These measurements were used in a radiative transfer code to retrieve spectral (350-550 nm) aerosol single scattering albedo (SSA) for biomass burning plumes encountered on 17 April and 29 June. Retrieved SSA values were subsequently used to calculate the absorption Angstrom exponent (AAE) over the 350-500 nm range. Both plumes exhibited enhanced spectral absorption with AAE values that exceeded 1 (6.78 ± 0.38 for 17 April and 3.34 ± 0.11 for 29 June). This enhanced absorption was primarily due to organic aerosol (OA) which contributed significantly to total absorption at all wavelengths for both 17 April (57.7%) and 29 June (56.2%). OA contributions to absorption were greater at UV wavelengths than at visible wavelengths for both cases. Differences in AAE values between the two cases were attributed to differences in plume age and thus to differences in the ratio of OA and black carbon (BC) concentrations. However, notable differences between AAE values calculated for the OA (AAEOA) for 17 April (11.15 ± 0.59) and 29 June (4.94 ± 0.19) suggested differences in the plume AAE values might also be due to differences in organic aerosol composition. The 17 April OA was much more oxidized than the 29 June OA as denoted by a higher oxidation state value for 17 April (+0.16 vs. -0.32). Differences in the AAEOA, as well as the overall AAE, were thus also possibly due to oxidation of biomass burning primary organic aerosol in the 17 April plume that resulted in the formation of OA with a greater spectral-dependence of absorption. © Author(s) 2012. CC Attribution 3.0 License

Global Budget of Methanol: Constraints from Atmospheric Observations

We use a global three-dimensional model simulation of atmospheric methanol to examine the consistency between observed atmospheric concentrations and current understanding of sources and sinks. Global sources in the model include 128 Tg yr−1 from plant growth, 38 Tg yr−1 from atmospheric reactions of CH3O2 with itself and other organic peroxy radicals, 23 Tg yr−1 from plant decay, 13 Tg yr−1 from biomass burning and biofuels, and 4 Tg yr−1 from vehicles and industry. The plant growth source is a factor of 3 higher for young than from mature leaves. The atmospheric lifetime of methanol in the model is 7 days; gas-phase oxidation by OH accounts for 63% of the global sink, dry deposition to land 26%, wet deposition 6%, uptake by the ocean 5%, and aqueous-phase oxidation in clouds less than 1%. The resulting simulation of atmospheric concentrations is generally unbiased in the Northern Hemisphere and reproduces the observed correlations of methanol with acetone, HCN, and CO in Asian outflow. Accounting for decreasing emission from leaves as they age is necessary to reproduce the observed seasonal variation of methanol concentrations at northern midlatitudes. The main model discrepancy is over the South Pacific, where simulated concentrations are a factor of 2 too low. Atmospheric production from the CH3O2 self-reaction is the dominant model source in this region. A factor of 2 increase in this source (to 50–100 Tg yr−1) would largely correct the discrepancy and appears consistent with independent constraints on CH3O2 concentrations. Our resulting best estimate of the global source of methanol is 240 Tg yr−1. More observations of methanol concentrations and fluxes are needed over tropical continents. Better knowledge is needed of CH3O2 concentrations in the remote troposphere and of the underlying organic chemistry.Earth and Planetary Science

Higher measured than modeled ozone production at increased NOx levels in the Colorado Front Range

Abstract. Chemical models must correctly calculate the ozone formation rate, P(O3), to accurately predict ozone levels and to test mitigation strategies. However, air quality models can have large uncertainties in P(O3) calculations, which can create uncertainties in ozone forecasts, especially during the summertime when P(O3) is high. One way to test mechanisms is to compare modeled P(O3) to direct measurements. During summer 2014, the Measurement of Ozone Production Sensor (MOPS) directly measured net P(O3) in Golden, CO, approximately 25 km west of Denver along the Colorado Front Range. Net P(O3) was compared to rates calculated by a photochemical box model that was constrained by measurements of other chemical species and that used a lumped chemical mechanism and a more explicit one. Median observed P(O3) was up to a factor of 2 higher than that modeled during early morning hours when nitric oxide (NO) levels were high and was similar to modeled P(O3) for the rest of the day. While all interferences and offsets in this new method are not fully understood, simulations of these possible uncertainties cannot explain the observed P(O3) behavior. Modeled and measured P(O3) and peroxy radical (HO2 and RO2) discrepancies observed here are similar to those presented in prior studies. While a missing atmospheric organic peroxy radical source from volatile organic compounds co-emitted with NO could be one plausible solution to the P(O3) discrepancy, such a source has not been identified and does not fully explain the peroxy radical model–data mismatch. If the MOPS accurately depicts atmospheric P(O3), then these results would imply that P(O3) in Golden, CO, would be NOx-sensitive for more of the day than what is calculated by models, extending the NOx-sensitive P(O3) regime from the afternoon further into the morning. These results could affect ozone reduction strategies for the region surrounding Golden and possibly other areas that do not comply with national ozone regulations. Thus, it is important to continue the development of this direct ozone measurement technique to understand P(O3), especially under high-NOx regimes

Evaluation of simulated O-3 production efficiency during the KORUS-AQ campaign: Implications for anthropogenic NOx emissions in Korea

We examine O3 production and its sensitivity to precursor gases and boundary layer mixing in Korea by using a 3-D global chemistry transport model and extensive observations during the KORea-US cooperative Air Quality field study in Korea, which occurred in May–June 2016. During the campaign, observed aromatic species onboard the NASA DC-8 aircraft, especially toluene, showed high mixing ratios of up to 10 ppbv, emphasizing the importance of aromatic chemistry in O3 production. To examine the role of VOCs and NOx in O3 chemistry, we first implement a detailed aromatic chemistry scheme in the model, which reduces the normalized mean bias of simulated O3 mixing ratios from –26% to –13%. Aromatic chemistry also increases the average net O3 production in Korea by 37%. Corrections of daytime PBL heights, which are overestimated in the model compared to lidar observations, increase the net O3 production rate by ~10%. In addition, increasing NOx emissions by 50% in the model shows best performance in reproducing O3 production characteristics, which implies that NOx emissions are underestimated in the current emissions inventory. Sensitivity tests show that a 30% decrease in anthropogenic NOx emissions in Korea increases the O3 production efficiency throughout the country, making rural regions ~2 times more efficient in producing O3 per NOx consumed. Simulated O3 levels overall decrease in the peninsula except for urban and other industrial areas, with the largest increase (~6 ppbv) in the Seoul Metropolitan Area (SMA). However, with simultaneous reductions in both NOx and VOCs emissions by 30%, O3 decreases in most of the country, including the SMA. This implies the importance of concurrent emission reductions for both NOx and VOCs in order to effectively reduce O3 levels in Korea

Ambient Observations of Sub-1.0 Hygroscopic Growth Factor and F(RH) Values: Case Studies from Surface and Airborne Measurements

This study reports on the first set of ambient observations of sub-1.0 hygroscopicity values (i.e., growth factor, ratio of humidified-to-dry diameter, GF=Dp,wet/Dp,dry and f(RH), ratio of humidified-to-dry scattering coefficients, less than 1) with consistency across different instruments, regions, and platforms. We utilized data from a shipboard humidified tandem differential mobility analyzer (HTDMA) during Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) in 2011, multiple instruments on the DC-8 aircraft during Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) in 2013, as well as the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe (DASH-SP) during measurement intensives during Summer 2014 and Winter 2015 in Tucson, Arizona. Sub-1.0 GFs were observed across the range of relative humidity (RH) investigated (75-95%), and did not show a RH-dependent trend in value below 1.0 or frequency of occurrence. A commonality between suppressed hygroscopicity in these experiments, including sub-1.0 GF, was the presence of smoke. Evidence of externally mixed aerosol, and thus multiple GFs, was observed during smoke periods resulting in at least one mode with GF < 1. Time periods during which the DASH-SP detected externally mixed aerosol coincide with sub-1.0 f(RH) observations. Mechanisms responsible for sub-1.0 hygroscopicity are discussed and include refractive index (RI) modifications due to aqueous processing, particle restructuring, and volatilization effects. To further investigate ambient observations of sub-1.0 GFs, f(RH), and particle restructuring, modifying hygroscopicity instruments with pre-humidification modules is recommended

Is there an aerosol signature of chemical cloud processing?

The formation of sulfate and secondary organic aerosol mass in the aqueous phase (aqSOA) of cloud and fog droplets can significantly contribute to ambient aerosol mass. While tracer compounds give evidence that aqueous-phase processing occurred, they do not reveal the extent to which particle properties have been modified in terms of mass, chemical composition, hygroscopicity, and oxidation state. We analyze data from several field experiments and model studies for six air mass types (urban, biogenic, marine, wild fire biomass burning, agricultural biomass burning, and background air) using aerosol size and composition measurements for particles 13&ndash;850&thinsp;nm in diameter. We focus on the trends of changes in mass, hygroscopicity parameter &kappa;, and oxygen-to-carbon (O&thinsp;∕&thinsp;C) ratio due to chemical cloud processing. We find that the modification of these parameters upon cloud processing is most evident in urban, marine, and biogenic air masses, i.e., air masses that are more polluted than very clean air (background air) but cleaner than heavily polluted plumes as encountered during biomass burning. Based on these trends, we suggest that the mass ratio (Rtot) of the potential aerosol sulfate and aqSOA mass to the initial aerosol mass can be used to predict whether chemical cloud processing will be detectable. Scenarios in which this ratio exceeds Rtot&sim;0.5 are the most likely ones in which clouds can significantly change aerosol parameters. It should be noted that the absolute value of Rtot depends on the considered size range of particles. Rtot is dominated by the addition of sulfate (Rsulf) in all scenarios due to the more efficient conversion of SO2 to sulfate compared to aqSOA formation from organic gases. As the formation processes of aqSOA are still poorly understood, the estimate of RaqSOA is likely associated with large uncertainties. Comparison to Rtot values as calculated for ambient data at different locations validates the applicability of the concept to predict a chemical cloud-processing signature in selected air masses.</p

Atmospheric Benzene Observations from an Oil and Gas Field in the Denver Julesburg Basin in July and August 2014

High time resolution measurements of volatile organic compounds (VOCs) were collectedusing a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the PlattevilleAtmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (ONG) developmentimpacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurementswere carried out in July and August 2014 as part of NASAs Deriving Information on Surface Conditions fromColumn and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign. ThePTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontalsurveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (meanbenzene 0.53 ppbv, maximum benzene 29.3 ppbv), primarily at night (mean nighttime benzene 0.73ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurementsindicate that benzene originated from within the WGF, and typical source signatures detected in the canistersamples implicate emissions from ONG activities rather than urban vehicular emissions as primary benzenesource. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerlyflow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that trafficemissions were not responsible for the observed high benzene levels. Previous measurements at the BoulderAtmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzeneenhancements between the two atmospheric observatories. Fugitive emissions of benzene from ONGoperations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO) or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2). We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5°) to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 %) than at coarser resolution (59 %). The cumulative probability distribution functions (CDFs) of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes) are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy) changing little across model resolutions. Model concentrations in the lower free troposphere are also insensitive to grid resolution. The overall low sensitivity of modeled concentrations to grid resolution implies that coarse resolution is adequate when modeling continental boundary layer chemistry for global applications