Formaldehyde Distribution over North America: Implications for Satellite Retrievals of Formaldehyde Columns and Isoprene Emission

Formaldehyde (HCHO) columns measured from space provide constraints on emissions of volatile organic compounds (VOCs). Quantitative interpretation requires characterization of errors in HCHO column retrievals and relating these columns to VOC emissions. Retrieval error is mainly in the air mass factor (AMF) which relates fitted backscattered radiances to vertical columns and requires external information on HCHO, aerosols, and clouds. Here we use aircraft data collected over North America and the Atlantic to determine the local relationships between HCHO columns and VOC emissions, calculate AMFs for HCHO retrievals, assess the errors in deriving AMFs with a chemical transport model (GEOS-Chem), and draw conclusions regarding space-based mapping of VOC emissions. We show that isoprene drives observed HCHO column variability over North America; HCHO column data from space can thus be used effectively as a proxy for isoprene emission. From observed HCHO and isoprene profiles we find an HCHO molar yield from isoprene oxidation of 1.6 ± 0.5, consistent with current chemical mechanisms. Clouds are the primary error source in the AMF calculation; errors in the HCHO vertical profile and aerosols have comparatively little effect. The mean bias and 1σ uncertainty in the GEOS-Chem AMF calculation increase from <1% and 15% for clear skies to 17% and 24% for half-cloudy scenes. With fitting errors, this gives an overall 1σ error in HCHO satellite measurements of 25–31%. Retrieval errors, combined with uncertainties in the HCHO yield from isoprene oxidation, result in a 40% (1σ) error in inferring isoprene emissions from HCHO satellite measurements.Earth and Planetary SciencesEngineering and Applied Science

Concentrations and Sources of Organic Carbon Aerosol in the Free Troposphere over North America

Aircraft measurements of water-soluble organic carbon (WSOC) aerosol over NE North America during summer 2004 (ITCT-2K4) are simulated with a global chemical transport model (GEOS-Chem) to test our understanding of the sources of organic carbon (OC) aerosol in the free troposphere (FT). Elevated concentrations were observed in plumes from boreal fires in Alaska and Canada. WSOC aerosol concentrations outside of these plumes average 0.9 ± 0.9 μg C m−3 in the FT (2–6 km). The corresponding model value is 0.7 ± 0.6 μg C m−3, including 42% from biomass burning, 36% from biogenic secondary organic aerosol (SOA), and 22% from anthropogenic emissions. Previous OC aerosol observations over the NW Pacific in spring 2001 (ACE-Asia) averaged 3.3 ± 2.8 μg C m−3 in the FT, compared to a model value of 0.3 ± 0.3 μg C m−3. WSOC aerosol concentrations in the boundary layer (BL) during ITCT-2K4 are consistent with OC aerosol observed at the IMPROVE surface network. The model is low in the boundary layer by 30%, which we attribute to secondary formation at a rate comparable to primary anthropogenic emission. Observed WSOC aerosol concentrations decrease by a factor of 2 from the BL to the FT, as compared to a factor of 10 decrease for sulfate, indicating that most of the WSOC aerosol in the FT originates in situ. Despite reproducing mean observed WSOC concentrations in the FT to within 25%, the model cannot account for the variance in the observations (R = 0.21). Covariance analysis of FT WSOC aerosol with other measured chemical variables suggests an aqueous-phase mechanism for SOA generation involving biogenic precursors.Earth and Planetary SciencesEngineering and Applied Science

Ozone-CO Correlations Determined by the TES Satellite Instrument in Continental Outflow Regions

Collocated measurements of tropospheric ozone (O3) and carbon monoxide (CO) from the Tropospheric Emission Spectrometer (TES) aboard the EOS Aura satellite provide information on O3-CO correlations to test our understanding of global anthropogenic influence on O3. We examine the global distribution of TES O3-CO correlations in the middle troposphere (618 hPa) for July 2005 and compare to correlations generated with the GEOS-Chem chemical transport model and with ICARTT aircraft observations over the eastern United States (July 2004). The TES data show significant O3-CO correlations downwind of polluted continents, with dO3/dCO enhancement ratios in the range 0.4–1.0 mol mol−1 and consistent with ICARTT data. The GEOS-Chem model reproduces the O3-CO enhancement ratios observed in continental outflow, but model correlations are stronger and more extensive. We show that the discrepancy can be explained by spectral measurement errors in the TES data. These errors will decrease in future data releases, which should enable TES to provide better information on O3-CO correlations.Earth and Planetary SciencesEngineering and Applied Science

Summertime Influence of Asian Pollution in the Free Troposphere over North America

We analyze aircraft observations obtained during INTEX-A (1 July 14 - August 2004) to examine the summertime influence of Asian pollution in the free troposphere over North America. By applying correlation analysis and Principal Component Analysis (PCA) to the observations between 6-12 km, we find dominant influences from recent convection and lightning (13 percent of observations), Asia (7 percent), the lower stratosphere (7 percent), and boreal forest fires (2 percent), with the remaining 71 percent assigned to background. Asian airmasses are marked by high levels of CO, O3, HCN, PAN, acetylene, benzene, methanol, and SO4(2-). The partitioning of reactive nitrogen species in the Asian plumes is dominated by peroxyacetyl nitrate (PAN) (approximately 600 pptv), with varying NO(x)/HNO3 ratios in individual plumes consistent with different plumes ages ranging from 3 to 9 days. Export of Asian pollution in warm conveyor belts of mid-latitude cyclones, deep convection, and lifting in typhoons all contributed to the five major Asian pollution plumes. Compared to past measurement campaigns of Asian outflow during spring, INTEX-A observations display unique characteristics: lower levels of anthropogenic pollutants (CO, propane, ethane, benzene) due to their shorter summer lifetimes; higher levels of biogenic tracers (methanol and acetone) because of a more active biosphere; as well as higher levels of PAN, NO(x), HNO3, and O3 (more active photochemistry possibly enhanced by injection of lightning NO(x)). The high delta O3/delta CO ratio (0.76 mol mol(exp -1)) of Asian plumes during INTEX-A is due to a combination of strong photochemical production and mixing with stratospheric air along isentropic surfaces. The GEOS-Chem global chemical transport model captures the timing and location of the Asian plumes remarkably well. However, it significantly underestimates the magnitude of the enhancements

Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution, and export of NOx. The boundary layer NOx data provide top-down verification of a 50% decrease in power plant and industry NOx emissions over the eastern United States between 1999 and 2004. Observed NOx concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NOx and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NOx observations with GEOS-Chem requires a factor of 4 increase in modeled NOx yield per flash (to 500 mol/flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NOy-CO correlation analysis of the fraction f of North American NOx emissions vented to the free troposphere as NOy (sum of NOx and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NOy export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export.Earth and Planetary SciencesEngineering and Applied Science

Convective outflow of South Asian pollution: A global CTM simulation compared with EOS MLS observations

A global 3-D chemical transport model is used to analyze observations of carbon monoxide (CO) and upper tropospheric clouds from the EOS Microwave Limb Sounder (MLS). MLS observations during 25 August–6 September 2004 reveal elevated CO and dense high clouds in the upper troposphere over the Tibetan plateau and southwest China, collocating with the upper level Tibetan anticyclone. Model simulations indicate the transport of boundary layer pollution by Asian summer monsoon (ASM) convection and orographic lifting to the upper troposphere over South Asia, where simulated distributions of CO resemble MLS observations. Model results also show elevated aerosols in the anticyclone region. Analysis of model simulated CO and aerosols indicate that the Tibetan anticyclone could ‘trap’ anthropogenic emissions lifted from northeast India and southwest China. These aerosols may be responsible for the formation of some of the dense high clouds.Engineering and Applied Science

An Observationally Constrained Evaluation of the Oxidative Capacity in the Tropical Western Pacific Troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January–February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO + NO2) by a factor of two, resulting in OHCOL ~30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January–February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP

Evaluating the Atmospheric Impact of Wildfires

International audienceThe availability of more and more valuable surface and atmospheric observations, especially from satellites, and the advance of vegetation, general circulation and chemistry-transport modelling, allow quantitative evaluations and prediction of the impact of fires on both air quality and climate. These will represent both the transport of the emissions and the chemical and physical processes involved in the evolution of fire plumes. This chapter provides an overview of the methodology generally adopted for the construction of emission inventories necessary for impact evaluation, and gives a few examples of recent research and the future directions. It discusses the strong influence of meteorological and climatic conditions on the development and strength of fire events. These fires in turn impact meteorological conditions, mainly through the energy released and via their emissions of particulate matter into the atmosphere. These two effects are briefly summarized

Atmospheric Acetylene and its Relationship with CO as an Indicator of Air Mass Age

Acetylene (C2H2) and CO originating from combustion are strongly correlated in atmospheric observations, offering constraints on atmospheric dilution and chemical aging. We examine here the C2H2-CO relationships in aircraft observations worldwide, and interpret them with simple models as well as with a global chemical transport model (GEOS-Chem). A C2H2 global source of 6.6 Tg yr−1 in GEOS-Chem simulates the ensemble of global C2H2 observations without systematic bias, and captures most seasonal and regional features. C2H2/CO concentration ratios decrease from continental source regions to the remote atmosphere in a manner consistent between the observations and the model. However, the dC2H2/dCO slope from the linear regression does not show such a systematic decrease, either in the model or in the observations, reflecting variability in background air. The slope β = dlog[C2H2]/dlog[CO] of the linear regression of concentrations in log space offers information for separating the influences of dilution and chemical aging. We find that a linear mixing model with constant dilution rate and background is successful in fresh continental outflow but not in remote air. A diffusion model provides a better conceptual framework for interpreting the observations, where the value of β relative to the square root of the ratio of C2H2 and CO chemical lifetimes (1.7–1.9) measures the relative importance of dilution and chemistry. We thus find that dilution dominates in fresh outflow but chemical loss dominates in remote air. This result is supported by GEOS-Chem sensitivity simulations with modified OH concentrations, and suggests that the model overestimates OH in the southern tropics.Earth and Planetary SciencesEngineering and Applied Science