Publications

Abstract. The role of chlorine atoms (Cl) in atmospheric oxidation was traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex showed it to be an important primary (first generation) radical source. Ratios of volatile organic compounds (VOCs) have been proposed as a sensitive method to quantify Cl oxidation, but have shown little evidence for a significant role of Cl outside of the Arctic. We used a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl-sensitivity of the most commonly used VOC ratios (i-butane, n-butane, and propane) as a function of NOx and secondary radical production. Model results indicated these and faster reacting VOC tracer ratios could not detect the influence of Cl unless the sustained ratio of OH to Cl was below 200. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect can obscure the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The OH to Cl ratio was below 200 for approximately three hours in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratios to follow the values expected for OH oxidation despite the significant input of primary Cl from ClNO2 photolysis in the morning. Despite the prevalence of secondary OH as an oxidant in Los Angeles, Cl may play an important role in tropospheric chemistry. The reactivity of Cl in Los Angeles during CalNex was more than an order of magnitude larger than that of OH. In addition, because of its reactivity toward different classes of VOCs and its greater propensity to participate in chain propagation rather than sink reactions, Cl atoms have a different impact on regional atmospheric oxidation than do OH radicals.

Abstract. Fires emit a substantial amount of non-methane organic gases (NMOGs), the atmospheric oxidation of which can contribute to ozone and secondary particulate matter formation. However, the abundance and reactivity of these fire NMOGs are uncertain and historically not well constrained. In this work, we expand the representation of fire NMOGs in a global chemical transport model, GEOS-Chem. We update emission factors to Andreae (2019) and the chemical mechanism to include recent aromatic and ethene and ethyne model improvements (Bates et al., 2021; Kwon et al., 2021). We expand the representation of NMOGs by adding lumped furans to the model (including their fire emission and oxidation chemistry) and by adding fire emissions of nine species already included in the model, prioritized for their reactivity using data from the Fire Influence on Regional to Global Environments (FIREX) laboratory studies. Based on quantified emissions factors, we estimate that our improved representation captures 72 % of emitted, identified NMOG carbon mass and 49 % of OH reactivity from savanna and temperate forest fires, a substantial increase from the standard model (49 % of mass, 28 % of OH reactivity). We evaluate fire NMOGs in our model with observations from the Amazon Tall Tower Observatory (ATTO) in Brazil, Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) and DC3 in the US, and Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in boreal Canada. We show that NMOGs, including furan, are well simulated in the eastern US with some underestimates in the western US and that adding fire emissions improves our ability to simulate ethene in boreal Canada. We estimate that fires provide 15 % of annual mean simulated surface OH reactivity globally, as well as more than 75 % over fire source regions. Over continental regions about half of this simulated fire reactivity comes from NMOG species. We find that furans and ethene are important globally for reactivity, while phenol is more important at a local level in the boreal regions. This is the first global estimate of the impact of fire on atmospheric reactivity.

Abstract. Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X = Br, Cl and I) and very short-lived halogenated substances (VSLS; CHBr3, CH2Br2, CHBrCl2, C2HCl3, CHCl3 and CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere, and for their key role in aerosol formation. Insufficient characterization of the sources and emission rate of VHOCs limits our present ability to understand and assess their impact in both the troposphere and the stratosphere. Over the last two decades several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge about emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and the fluxes of several chlorinated and brominated VHOCs from different landforms and vegetated sites at the Dead Sea during different seasons. Fluxes were highly variable but were generally positive (emissive), corresponding with elevated mixing ratios for all of the VHOCs investigated in the four investigated site types – bare soil, coastal, cultivated and natural vegetated sites – except for fluxes of CH3I and C2HCl3 over the vegetated sites. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHBr3 > CHBrCl2 > CHCl3. This finding can be explained by the enrichment of soil with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the formation and emission of all the above trihalomethanes but also for CH2Br2. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the high correlations of flux with methyl halides, and particularly with CH3I, suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevate emission of VHOCs from bare soil under semi-arid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes, and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes.

Abstract. Methyl chloroform (MCF) is a man-made chlorinated solvent contributing to the destruction of stratospheric ozone and is controlled under the Montreal Protocol on Substances that Deplete the Ozone Layer. Long-term, high-frequency observations of MCF carried out at three European sites show a constant decline of the background mixing ratios of MCF. However, we observe persistent non-negligible mixing ratio enhancements of MCF in pollution episodes suggesting unexpectedly high ongoing emissions in Europe. In order to identify the source regions and to give an estimate of the magnitude of such emissions, we have used a Bayesian inversion method and a point source analysis, based on high-frequency long-term observations at the three European sites. The inversion identified south-eastern France (SEF) as a region with enhanced MCF emissions. This estimate was confirmed by the point source analysis. We performed this analysis using an eleven-year data set, from January 2002 to December 2012. Overall emissions estimated for the European study domain decreased nearly exponentially from 1.1 Gg yr−1 in 2002 to 0.32 Gg yr−1 in 2012, of which the estimated emissions from the SEF region accounted for 0.49 Gg yr−1 in 2002 and 0.20 Gg yr−1 in 2012. The European estimates are a significant fraction of the total semi-hemisphere (30–90° N) emissions, contributing a minimum of 9.8% in 2004 and a maximum of 33.7% in 2011, of which on average 50% are from the SEF region. On the global scale, the SEF region is thus responsible from a minimum of 2.6% (in 2003) to a maximum of 10.3% (in 2009) of the global MCF emissions.

High mixing ratios of ozone (O3) in the northern Front Range (NFR) of Colorado are not limited to the urban Denver area but were also observed in rural areas where oil and gas activity is the primary source of O3 precursors. On individual days, oil and gas O3 precursors can contribute in excess of 30 ppb to O3 growth and can lead to exceedances of the EPA O3 National Ambient Air Quality Standard. Data used in this study were gathered from continuous surface O3 monitors for June–August 2013–2015 as well as additional flask measurements and mobile laboratories that were part of the FRAPPE/DISCOVER-AQ field campaign of July–August 2014. Overall observed O3 levels during the summer of 2014 were lower than in 2013, likely due to cooler and damper weather than an average summer. This study determined the median hourly surface O3 mixing ratio in the NFR on summer days with limited photochemical production to be approximately 45–55 ppb. Mobile laboratory and flask data collected on three days provide representative case studies of different O3 formation environments in and around Greeley, Colorado. Observations of several gases (including methane, ethane, CO, nitrous oxide) along with O3 are used to identify sources of O3 precursor emissions. A July 23 survey demonstrated low O3 (45–60 ppb) while August 3 and August 13 surveys recorded O3 levels of 75–80 ppb or more. August 3 exemplifies influence of moderate urban and high oil and gas O3 precursor emissions. August 13 demonstrates high oil and gas emissions, low agricultural emissions, and CO measurements that were well correlated with ethane from oil and gas, suggesting an oil and gas related activity as a NOx and O3 precursor source. Low isoprene levels indicated that they were not a significant contributor to O3 precursors measured during the case studies.

Halogen‐driven ozone and hydrocarbon losses in springtime Arctic boundary layer are investigated using a regional chemical transport model. Surface observations of ozone at Alert and Barrow and aircraft observations of ozone and hydrocarbons during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment from February to May in 2000 are analyzed. We prescribe halogen radical distributions on the basis of GOME BrO observations. Tropospheric GOME BrO column shows an apparent anticorrelation with surface temperature over high‐BrO regions. The enhancements of tropospheric BrO columns coincide with movements of cold polar air masses. While GOME BrO measurements reach the maximum in March, simulated near‐surface ozone loss peaks in April because of the increasing daylight hours and hence the time for chemical processing. At its peak, the area of simulated near‐surface ozone depletions (O 3 < 20 ppbv) covers >50% of the northern high latitudes. Analysis of surface measurements at Alert and Barrow points to the importance of long‐range transport of ozone‐poor air from high‐BrO regions. We find that specifying a BrO layer thickness of 300 m results in the best overall agreement between observed and simulated ozone. The apparent halogen‐driven ozone loss up to 1 km was reproduced in the model because of vertical transport of ozone‐poor air from low altitudes. When the empirical Cl/Br ratios derived from previous observations are used, the model can reproduce the observed halogen loss of light alkanes and acetylene. The Cl/Br ratios from a recent box model study using an accepted chemical mechanism are, however, much higher than the empirical results. We show that the hydrocarbon loss is not as sensitive to the prescribed thickness of the halogen layer as the ozone loss, therefore representing a more robust measure for evaluating satellite BrO column measurements.

Using a regional chemical transport model, STEM 2K1, and the emission inventory for the Transport and Chemical Evolution Over the Pacific (TRACE‐P) period [ Woo et al. , Streets et al. , this issue ], we successfully simulated important features of the biomass burning (BB) CO outflow. Simulated results agree well with the TRACE‐P aircraft measurements and Thailand surface observations. On the basis of sensitivity studies with and without biomass emissions, we identified nine flight segments that are affected by biomass plumes during the TRACE‐P period and compared the characteristics of the BB air masses with the other air masses. The BB air masses emitted from Southeast Asia contain relatively high HCN (ΔHCN/ΔCO ∼ 0.0015) and potassium (ΔK + /ΔCO ∼ 0.0038) but very low NO y (ΔNO y /ΔCO ∼ 0.005) mixing ratios, which may be associated with the special burning condition in this region. The biomass burning air masses have high ozone production efficiency. The observed ΔO 3 /ΔNO z values were ∼17 in biomass events and 1.7 in other events. The BB influence on the trace gas distributions can be divided into two categories: the influence through direct reactions and the influence caused by BB aerosols changing J values. These two influences are discussed for the BB‐affected TRACE‐P flights and for east Asia. The BB influences on chemical species are not only determined by the BB plume intensity but also by the ambient environment caused by other emissions. In Southeast Asia, where the biogenic emissions are very strong, the OH background concentration is low, and the BB gas‐phase compounds mainly contribute to OH production. Arranged in the sensitivity to the J value change caused by BB aerosols, we have OH > HO 2 > HCHO > O 3 when evaluated on a regional average. Averaged over March, the biomass burning net influence is as high as 50% for OH, 40% for HO 2 , 60% for HCHO, and 10 ppbv for O 3 for the layers below 1 km.

In situ and laser remote measurements of gases and aerosols were made with airborne instrumentation to establish a baseline chemical signature of the atmosphere above the South Pacific Ocean during the NASA Global Tropospheric Experiment (GTE)/Pacific Exploratory Mission‐Tropics A (PEM‐Tropics A) conducted in August‐October 1996. This paper discusses general characteristics of the air masses encountered during this experiment using an airborne lidar system for measurements of the large‐scale variations in ozone (O 3 ) and aerosol distributions across the troposphere, calculated potential vorticity (PV) from the European Centre for Medium‐Range Weather Forecasting (ECMWF), and in situ measurements for comprehensive air mass composition. Between 8°S and 52°S, biomass burning plumes containing elevated levels of O 3 , over 100 ppbv, were frequently encountered by the aircraft at altitudes ranging from 2 to 9 km. Air with elevated O 3 was also observed remotely up to the tropopause, and these air masses were observed to have no enhanced aerosol loading. Frequently, these air masses had some enhanced PV associated with them, but not enough to explain the observed O 3 levels. A relationship between PV and O 3 was developed from cases of clearly defined O 3 from stratospheric origin, and this relationship was used to estimate the stratospheric contribution to the air masses containing elevated O 3 in the troposphere. The frequency of observation of the different air mass types and their average chemical composition is discussed in this paper.

Nonmethane volatile organic compounds (NMVOCs) result in ozone and aerosol production that adversely affects the environment and human health. For modeling purposes, anthropogenic NMVOC emissions have been typically compiled using the “bottom-up” approach. To minimize uncertainties of the bottom-up emission inventory, “top-down” NMVOC emissions can be estimated using formaldehyde (HCHO) observations. In this study, HCHO vertical column densities (VCDs) obtained from the Geostationary Trace gas and Aerosol Sensor Optimization spectrometer during the Korea–United States Air Quality campaign were used to constrain anthropogenic volatile organic compound (AVOC) emissions in South Korea. Estimated top-down AVOC emissions differed from those of the up-to-date bottom-up inventory over major anthropogenic source regions by factors of 1.0 ± 0.4 to 6.9 ± 3.9. Our evaluation using a 3D chemical transport model indicates that simulated HCHO mixing ratios using the top-down estimates were in better agreement with observations onboard the DC-8 aircraft during the campaign relative to those with the bottom-up emission, showing a decrease in model bias from –25% to –13%. The top-down analysis used in this study, however, has some limitations related to the use of HCHO yields, background HCHO columns, and AVOC speciation in the bottom-up inventory, resulting in uncertainties in the AVOC emission estimates. Our attempt to constrain diurnal variations of the AVOC emissions using the aircraft HCHO VCDs was compromised by infrequent aircraft observations over the same source regions. These limitations can be overcome with geostationary satellite observations by providing hourly HCHO VCDs.