Re-Examining Chemical Conditions of Past Chamber Studies of Secondary Organic Aerosol Formation
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Goss, Matthew B.↗
Engineering topics
Heald, Colette L.
Publications and source records attributed to Heald, Colette L..
Can we achieve atmospheric chemical environments in the laboratory? An integrated model-measurement approach to chamber SOA studies
Secondary organic aerosol (SOA), atmospheric particulate matter formed from low-volatility products of volatile organic compound (VOC) oxidation, affects both air quality and climate. Current 3D models, however, cannot reproduce the observed variability in atmospheric organic aerosol. Because many SOA model descriptions are derived from environmental chamber experiments, our ability to represent atmospheric conditions in chambers directly affects our ability to assess the air quality and climate impacts of SOA. Here, we develop an approach that leverages global modeling and detailed mechanisms to design chamber experiments that mimic the atmospheric chemistry of organic peroxy radicals (RO 2 ), a key intermediate in VOC oxidation. Drawing on decades of laboratory experiments, we develop a framework for quantitatively describing RO 2 chemistry and show that no previous experimental approaches to studying SOA formation have accessed the relevant atmospheric RO 2 fate distribution. We show proof-of-concept experiments that demonstrate how SOA experiments can access a range of atmospheric chemical environments and propose several directions for future studies.
Science & Technology - Other Topics↗
Can we achieve atmospheric chemical environments in the laboratory? An integrated model-measurement approach to chamber SOA studies
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54 ENVIRONMENTAL SCIENCES↗
Constraining Remote Oxidation Capacity with ATom Observations
The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation in the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias with the exception of wintertime NOy, for which a model overestimate may indicate insufficient wet scavenging and/or missing loss on seasalt aerosol but large uncertainties remain that require further studies of NOy partitioning and removal in the troposphere. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by new estimates of ocean VOC sources and additional modeled reactivity in this region would be difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOC, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in modeled acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean VOC sources in the model increases annual surface cOHRmod by 10 % and improves model-measurement agreement for acetaldehyde particularly in winter but cannot resolve the model summertime bias. Doing so would require a 100 Tg yr−1 source of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.
Travis, Katherine R.↗
Evaluating Model Parameterizations of Submicron Aerosol Scattering and Absorption with in situ Data from ARCTAS 2008
Accurate modeling of the scattering and absorption of ultraviolet and visible radiation by aerosols is essential for accurate simulations of atmospheric chemistry and climate. Closure studies using in situ measurements of aerosol scattering and absorption can be used to evaluate and improve models of aerosol optical properties without interference from model errors in aerosol emissions, transport, chemistry, or deposition rates. Here we evaluate the ability of four externally mixed, fixed size distribution parameterizations used in global models to simulate submicron aerosol scattering and absorption at three wavelengths using in situ data gathered during the 2008 Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. The four models are the NASA Global Modeling Initiative (GMI) Combo model, GEOS-Chem v9- 02, the baseline configuration of a version of GEOS-Chem with online radiative transfer calculations (called GC-RT), and the Optical Properties of Aerosol and Clouds (OPAC v3.1) package. We also use the ARCTAS data to perform the first evaluation of the ability of the Aerosol Simulation Program (ASP v2.1) to simulate submicron aerosol scattering and absorption when in situ data on the aerosol size distribution are used, and examine the impact of different mixing rules for black carbon (BC) on the results. We find that the GMI model tends to overestimate submicron scattering and absorption at shorter wavelengths by 10-23 percent, and that GMI has smaller absolute mean biases for submicron absorption than OPAC v3.1, GEOS-Chem v9-02, or GC-RT. However, the changes to the density and refractive index of BC in GCRT improve the simulation of submicron aerosol absorption at all wavelengths relative to GEOS-Chem v9-02. Adding a variable size distribution, as in ASP v2.1, improves model performance for scattering but not for absorption, likely due to the assumption in ASP v2.1 that BC is present at a constant mass fraction throughout the aerosol size distribution. Using a core-shell mixing rule in ASP overestimates aerosol absorption, especially for the fresh biomass burning aerosol measured in ARCTAS-B, suggesting the need for modeling the time-varying mixing states of aerosols in future versions of ASP.
Alvarado, Matthew J.↗
Asian Outflow and Trans-Pacific Transport of Carbon Monoxide and Ozone Pollution: An Integrated Satellite, Aircraft, and Model Perspective
Satellite observations of carbon monoxide (CO) from the Measurements of Pollution in the Troposphere (MOPITT) instrument are combined with measurements from the Transport and Chemical Evolution Over the Pacific (TRACE-P) aircraft mission over the northwest Pacific and with a global three-dimensional chemical transport model (GEOS-CHEM) to quantify Asian pollution outflow and its trans-Pacific transport during spring 2001. Global CO column distributions in MOPITT and GEOS-CHEM are highly correlated (R(exp 2) = 0.87), with no significant model bias. The largest regional bias is over Southeast Asia, where the model is 18% too high. A 60% decrease of regional biomass burning emissions in the model (to 39 Tg/yr) would correct the discrepancy; this result is consistent with TRACE-P observations. MOPITT and TRACE-P also give consistent constraints on the Chinese source of CO from fuel combustion (181 Tg CO/yr). Four major events of trans-Pacific transport of Asian pollution in spring 2001 were seen by MOPITT, in situ platforms, and GEOS-CHEM. One of them was sampled by TRACE-P (26-27 February) as a succession of pollution layers over the northeast Pacific. These layers all originated from one single event of Asian outflow that split into northern and southern plumes over the central Pacific. The northern plume (sampled at 6-8 km off California) had no ozone enhancement. The southern subsiding plume (sampled at 2-4 km west of Hawaii) contained a 8 - 17 ppbv ozone enhancement, driven by decomposition of peroxyacetylnitrate (PAN) to nitrogen oxides (NOx). This result suggests that PAN decomposition in trans-Pacific pollution plumes subsiding over the United States could lead to significant enhancements of surface ozone.
Heald, Colette L.↗
Transport and Chemical Evolution over the Pacific (TRACE-P)Aircraft Mission: Design, Execution, and First Results
The NASA Transport and Chemical Evolution over the Pacific (TRACE-P) aircraft mission was conducted in February-April 2001 over the NW Pacific (1) to characterize the Asian chemical outflow and relate it quantitatively to its sources and (2) to determine its chemical evolution. It used two aircraft, a DC-8 and a P-3B, operating out of Hong Kong and Yokota Air Force Base (near Tokyo), with secondary sites in Hawaii, Wake Island, Guam, Okinawa, and Midway. The aircraft carried instrumentation for measurements of long-lived greenhouse gases, ozone and its precursors, aerosols and their precursors, related species, and chemical tracers. Five chemical transport models (CTMs) were used for chemical forecasting. Customized bottom-up emission inventories for East Asia were generated prior to the mission to support chemical forecasting and to serve as a priori for evaluation with the aircraft data. Validation flights were conducted for the Measurements Of Pollution In The Troposphere (MOPITT) satellite instrument and revealed little bias (6 plus or minus 2%) in the MOPITT measurements of CO columns. A major event of transpacific Asian pollution was characterized through combined analysis of TRACE-P and MOPITT data. The TRACE-P observations showed that cold fronts sweeping across East Asia and the associated warm conveyor belts (WCBs) are the dominant pathway for Asian outflow to the Pacific in spring. The WCBs lift both anthropogenic and biomass burning (SE Asia) effluents to the free troposphere, resulting in complex chemical signatures. The TRACE-P data are in general consistent with a priori emission inventories, lending confidence in our ability to quantify Asian emissions from socioeconomic data and emission factors. However, the residential combustion source in rural China was found to be much larger than the a priori, and there were also unexplained chemical enhancements (HCN, CH3Cl, OCS, alkylnitrates) in Chinese urban plumes. The Asian source of CCl4 was found to be much higher than government estimates. Measurements of HCN and CH3CN indicated a dominant biomass burning source and ocean sink for both gases. Large fractions of sulfate and nitrate were found to be present in dust aerosols. Photochemical activity in the Asian outflow was strongly reduced by aerosol attenuation of UV radiation, with major implications for the concentrations of HOx, radicals. New particle formation, apparently from ternary nucleation involving NH3, was observed in Chinese urban plumes.
Jacob, Daniel J.↗