Publications

Abstract. Gas-phase elemental mercury (Hg°) was measured aboard the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in spring 2006. Flights were conducted around Mexico City and on two subsequent deployments over the North Pacific based out of Honolulu, Hawaii and Anchorage, Alaska. Data obtained from 0.15–12 km altitude showed that Hg° exhibited a relatively constant vertical profile centered around 100 ppqv. Highly concentrated pollution plumes emanating from the Mexico City urban agglomeration revealed that mixing ratios of Hg° as large as 500 ppqv were related to combustion tracers such as CO, but not SO2 which is presumably released locally from coal burning, refineries, and volcanoes. Our analysis of Mexico City plumes indicated that widespread multi-source urban/industrial emissions may have a more important influence on Hg° than specific point sources. Over the Pacific, correlations with CO, CO2, CH4, and C2Cl4 were diffuse overall, but recognizable on flights out of Anchorage and Honolulu. In distinct plumes originating from the Asian continent the Hg°- CO relationship yielded an average value of ~0.56 ppqv/ppbv, in good agreement with previous findings. A prominent feature of the INTEX-B dataset was frequent total depletion of Hg° in the upper troposphere when stratospherically influenced air was encountered. Ozone data obtained with the differential absorption lidar (DIAL) showed that the stratospheric impact on the tropospheric column was a common and pervasive feature on all flights out of Honolulu and Anchorage. We propose that this is likely a major factor driving large-scale seasonality in Hg° mixing ratios, especially at mid-latitudes, and an important process that should be incorporated into global chemical transport models.

Abstract Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC 4 RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM 1 ) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM 1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM 1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM 1 emission estimate (1530 ± 570 Gg yr −1 ) is over 3 times that of the NEI PM 2.5 estimate and is also higher than the PM 2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

Aircraft observations of ozone and its precursors (NO, NOy, CO, and nonmethane hydrocarbons) were made near Japan (26°-44°N) between 21 and 24 April 1998 to investigate the effect of transport and chemistry on the tropospheric ozone over east Asia in spring. The average mixing ratios of ozone and its precursors in the upper troposphere were higher than those observed during February-March 1994. Significantly higher values of CO indicate that the influence of surface sources mediated by convection was large throughout the troposphere during the period. Highly polluted air masses were observed in the upper troposphere at 8-11 km over the Japan Sea on 24 April. These air masses were influenced by cumulus convection associated with a cold front over northeast China about 1 day prior to the observation. However, the majority of observed air masses in the upper troposphere were not directly affected by the recent emissions of the ozone precursors from east Asia. Instead, convection over other regions in the northern midlatitude, followed by long-range transport, affected the abundances of ozone precursors in the upper troposphere. In these air masses, ozone was positively correlated with NOx and C3H8, indicating the effect of photochemical ozone production. The diurnal-average column-integrated rate of ozone production, estimated by a photochemical box model, was larger than the NH average and local stratospheric flux at NH midlatitudes in spring by a factor of 3-20. The net production rates in the majority of the air masses were estimated to be 0.5-4.4 ppbv d-1 in the upper troposphere. These results indicate the important role photochemistry plays in controlling the upper tropospheric ozone abundance in spring.

Analysis of chemical transport on Flight 10 of the 1999 Pacific Exploratory Mission (PEM) Tropics B mission clarifies the role of the South Pacific Convergence Zone (SPCZ) in establishing ozone and other trace gas distributions in the southwestern tropical Pacific. The SPCZ is found to be a barrier to mixing in the lower troposphere but a mechanism for convective mixing of tropical boundary layer air from northeast of the SPCZ with upper tropospheric air arriving from the west. A two‐dimensional cloud‐resolving model is used to quantify three critical processes in global and regional transport: convective mixing, lightning NO x production, and wet scavenging of soluble species. Very low NO and O 3 tropical boundary layer air from the northeastern side of the SPCZ entered the convective updrafts and was transported to the upper troposphere where it mixed with subtropical upper tropospheric air containing much larger NO and O 3 mixing ratios that had arrived from Australia. Aircraft observations show that very little NO appears to have been produced by electrical discharges within the SPCZ convection. We estimate that at least 90% of the HNO 3 and H 2 O 2 that would have been in upper tropospheric cloud outflow had been removed during transport through the cloud. Lesser percentages are estimated for less soluble species (e.g., <50% for CH 3 OOH). Net ozone production rates were decreased in the upper troposphere by ∼60% due to the upward transport and outflow of low‐NO boundary layer air. However, this outflow mixed with much higher NO air parcels on the southwest edge of the cloud, and the mixture ultimately possessed a net ozone production potential intermediate between those of the air masses on either side of the SPCZ.

South Korea has recently achieved developed country status with the second largest megacity in the world, the Seoul Metropolitan Area (SMA). This study provides insights into future changes in air quality for rapidly emerging megacities in the East Asian region. We present total OH reactivity observations in the SMA conducted at an urban Seoul site (May-June, 2015) and a suburban forest site (Sep, 2015). The total OH reactivity in an urban site during the daytime was observed at similar levels (∼15 s(-1)) to those previously reported from other East Asian megacity studies. Trace gas observations indicate that OH reactivity is largely accounted for by NOX (∼50%) followed by volatile organic compounds (VOCs) (∼35%). Isoprene accounts for a substantial fraction of OH reactivity among the comprehensive VOC observational dataset (25-47%). In general, observed total OH reactivity can be accounted for by the observed trace gas dataset. However, observed total OH reactivity in the suburban forest area cannot be largely accounted for (∼70%) by the trace gas measurements. The importance of biogenic VOC (BVOCs) emissions and oxidations used to evaluate the impacts of East Asian megacity outflows for the regional air quality and climate contexts are highlighted in this study.

Abstract. The National Aeronautics and Space Administration (NASA) conducted the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission during 2008 as a part of the International Polar Year (IPY). The purpose of ARCTAS was to study the factors responsible for changes in the Arctic's atmospheric composition and climate. A major emphasis was to investigate Arctic haze, which is most pronounced during winter and early spring. This study focuses on the spring phase of ARCTAS (ARCTAS-A) that was based in Alaska during April 2008. Although anthropogenic emissions historically have been associated with Arctic haze, biomass burning emissions dominated the ARCTAS-A period and have been the focus of many ARCTAS related studies. This study determines mean transport characteristics of anthropogenic emissions during ARCTAS-A. Trajectories are initiated each day from three significant regions of anthropogenic emissions (Asia, North America, and Europe). The fifteen day forward trajectories are calculated using data from the Weather Research and Forecasting (WRF) model at 45 km horizontal resolution. The trajectory calculations indicate: origins of emissions that reach the Arctic (defined as north of 70° N) within fifteen days, pathways of these emissions, Arctic entry locations, and altitudes at which the trajectories enter the Arctic. Three cases during the ARCTAS-A period (one for each of the regions above) are examined using backward trajectories and chemical fingerprinting based on in situ data sampled from the NASA DC-8. The fingerprinting utilizes volatile organic compounds that represent pure anthropogenic tracers, Asian anthropogenic pollution, incomplete combustion, and natural gas emissions. We determine flight legs containing anthropogenic emissions and the pathways travelled by these emissions. Results show that the DC-8 sampled anthropogenic emissions from Asia, North America, and Europe during the spring phase of ARCTAS. The pathways travelled by these emissions agree with our derived transport characteristics and previous studies of Arctic transport. Meteorological analysis and trajectory calculations indicate that middle latitude cyclones and their associated warm conveyor belts play an important role in lofting the surface based emissions to their sampling altitude in all three cases.

Abstract. Emissions of airborne particles from biomass burning are a significant source of black carbon (BC) and brown carbon (BrC) in rural areas of developing countries where biomass is the predominant energy source for cooking and heating. This study explores the molecular composition of organic aerosols from household cooking emissions with a focus on identifying fuel-specific compounds and BrC chromophores. Traditional meals were prepared by a local cook with dung and brushwood-fueled cookstoves in a village in Palwal district, Haryana, India. Cooking was done in a village kitchen while controlling for variables including stove type, fuel moisture, and meal. Fine particulate matter (PM2.5) emissions were collected on filters, and then analyzed via nanospray desorption electrospray ionization–high-resolution mass spectrometry (nano-DESI-HRMS) and high-performance liquid chromatography–photodiode array–high-resolution mass spectrometry (HPLC-PDA-HRMS) techniques. The nano-DESI-HRMS analysis provided an inventory of numerous compounds present in the particle phase. Although several compounds observed in this study have been previously characterized using gas chromatography methods a majority of the species in the nano-DESI spectra were newly observed biomass burning compounds. Both the stove (chulha or angithi) and the fuel (brushwood or dung) affected the composition of organic aerosols. The geometric mean of the PM2.5 emission factor and the observed molecular complexity increased in the following order: brushwood–chulha (7.3 ± 1.8 g kg−1 dry fuel, 93 compounds), dung–chulha (21.1 ± 4.2 g kg−1 dry fuel, 212 compounds), and dung–angithi (29.8 ± 11.5 g kg−1 dry fuel, 262 compounds). The mass-normalized absorption coefficient (MACbulk) for the organic-solvent extractable material for brushwood PM2.5 was 3.7 ± 1.5 and 1.9 ± 0.8 m2 g−1 at 360 and 405 nm, respectively, which was approximately a factor of two higher than that for dung PM2.5. The HPLC-PDA-HRMS analysis showed that, regardless of fuel type, the main chromophores were CxHyOz lignin fragments. The main chromophores accounting for the higher MACbulk values of brushwood PM2.5 were C8H10O3 (tentatively assigned to syringol), nitrophenols C8H9NO4, and C10H10O3 (tentatively assigned to methoxycinnamic acid).

Atmospheric O 3 , CO, SO 2 , and NO y * (NO y * ≈ NO + NO 2 + PAN + organic nitrates + HNO 3 + N 2 O 5 + ⋯) were measured in 1999–2000 at a rural/agricultural site in the Yangtze Delta of China. In this paper we analyze the measurement results to show the emission characteristics of the measured gases and to infer relevant emission ratios. Positive correlations were found between CO and NO y * with a slope (Δ[CO]/Δ[NO y *]) of 36 (ppbv/ppbv) for the winter and nighttime measurements. The ratio is considerably larger than that (≈10 ppbv/ppbv) observed in the industrialized countries. The highest CO/NO y * ratio (30–40 ppbv/ppbv) occurred in September–December 1999 and June 2000. The good correlation between CO and the biomass burning tracer CH 3 Cl and the lack of correlation with the industrial tracer C 2 Cl 4 suggests that the burning of biofuels and crop residues is a major source for the elevated CO and possibly for other trace gases as well. The average SO 2 to NO y * ratio was 1.37 ppbv/ppbv, resulting from the use of relatively high‐sulfur coals in China. The measured SO 2 /NO y * and ΔCO/ΔNO y * were compared with the respective ratios from the current emission inventories for the study region, which indicated a comparable SO 2 /NO x emission ratio but a large discrepancy for CO/NO x . The observed CO to NO y * ratio was more than 3 times the emission ratio derived from the inventories, indicating the need for further improvement of emission estimates for the rural/agricultural regions in China. Additional research will be needed to study the implications of rural emissions to atmospheric chemistry and climate on both regional and global scales.

Environmental context The production and consumption of chlorofluorocarbons (CFCs) is regulated under the Montreal Protocol and its amendments, due to their role in stratospheric ozone depletion. Global atmospheric levels of CFC-11 did not decline as rapidly as expected during 2012–2018, in large part due to emissions from eastern China. In order to further clarify global CFC-11 emissions, this work provides a rare set CFC-11 measurements from understudied countries and sources throughout Asia (1998–2018). Abstract Trichlorofluoromethane (CFC-11) is an ozone-depleting substance whose production and consumption are regulated under the Montreal Protocol. Global atmospheric CFC-11 levels declined less quickly than expected during 2012–2018, largely because of ongoing emissions from eastern Asia. Satellite measurements suggest additional CFC-11 hotspots in the Arabian Peninsula and north India/Nepal. Here we present CFC-11 levels measured in dozens of Asian cities during 1998–2018, including China and Pakistan before the 2010 phaseout of CFC-11, and China, Nepal, Pakistan, Saudi Arabia and South Korea after the phaseout. Surface measurements of CFCs in Nepal, Pakistan and Saudi Arabia are very rare, and these surveys provide important observational constraints from understudied regions. During pre-phaseout campaigns, higher CFC-11 levels were measured in Beijing than Karachi, despite much higher overall volatile organic compound (VOC) levels in Karachi. During post-phaseout campaigns, average CFC-11 levels were higher in inland Shandong Province and Seoul (1.11–1.23× background) than in western Saudi Arabia, Lahore and Kathmandu (1.02–1.11× background), despite higher levels of other VOCs in the latter regions. While China is known to emit excess CFC-11, elevated CFC-11 levels in Seoul, especially during stagnant meteorological conditions, suggest local emissions in 2015–2016. Rough emission estimates suggest that South Korea is likely a relatively minor global source of excess CFC-11. Hotspot CFC-11 levels were measured from a landfill fire in Mecca (average of 1.8× background) and from garbage burning in Nepal (1.5× background). Because garbage burning and open burning in dumps are common practices, further investigation of CFC-11 emissions at dumps and landfills worldwide is encouraged to determine their global impact.

Abstract. We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere.This depletion contributes approximately −0.10 W m−2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m−2 contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (CO(2)) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH(4)), isoprene (C(5)H(8)), methyl bromide (CH(3)Br), dimethyl sulfide, and oxygen (O(2)), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH(3)I), and CO(2) observed during the Southern Ocean Iron Enrichment Experiments.