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The Whole Atmosphere Community Climate Model version 6 (WACCM6) is a major update of the whole atmosphere modeling capability in the Community Earth System Model (CESM), featuring enhanced physical, chemical and aerosol parameterizations. This work describes WACCM6 and some of the important features of the model. WACCM6 can reproduce many modes of variability and trends in the middle atmosphere, including the Quasi‐Biennial Oscillation, Stratospheric Sudden Warmings and the evolution of Southern Hemisphere springtime ozone depletion over the 20th century. WACCM6 can also reproduce the climate and temperature trends of the 20th century throughout the atmospheric column. The representation of the climate has improved in WACCM6, relative to WACCM4. In addition, there are improvements in high latitude climate variability at the surface and sea ice extent in WACCM6 over the lower top version of the model (CAM6) that come from the extended vertical domain and expanded aerosol chemistry in WACCM6, highlighting the importance of the stratosphere and tropospheric chemistry for high latitude climate variability.

22 pags., 11 figs., 2 tabs. -- Open Access funded by Creative Commons Atribution Licence 4.0, Halogenated very short lived substances (VSLS) affect the ozone budget in the atmosphere. Brominated VSLS are naturally emitted from the ocean, and current oceanic emission inventories vary dramatically. We present a new global oceanic emission inventory of Br‐VSLS (bromoform and dibromomethane), considering the physical forcing in the ocean and the atmosphere, as well as the ocean biogeochemistry control. A data‐oriented machine‐learning emulator was developed to couple the air‐sea exchange with the ocean biogeochemistry. The predicted surface seawater concentrations and the surface atmospheric mixing ratios of Br‐VSLS are evaluated with long‐term, global‐scale observations; and the predicted vertical distributions of Br‐VSLS are compared to the global airborne observations in both boreal summer and winter. The global marine emissions of bromoform and dibromomethane are estimated to be 385 and 54 Gg Br per year, respectively. The new oceanic emission inventory of Br‐VSLS is more skillful than the widely used top‐down approaches for representing the seasonal/spatial variations and the annual means of atmospheric concentrations. The new approach improves the model predictability for the coupled Earth system model and can be used as a basis for investigating the past and future ocean emissions and feedbacks under climate change. This model framework can be used to calculate the bidirectional oceanic fluxes for other compounds of interest., S.‐Y. W. is supported by the NCAR Advanced Study Program (ASP) Postdoctoral Fellowship. The CESM project is supported primarily by the National Science Foundation (NSF). This material is based upon work supported by NCAR, which is a major facility sponsored by the NSF under Cooperative Agreement 1852977. The computing and data storage resources, including the Cheyenne supercomputer (doi:10.5065/D6RX99HX), were provided by the Computational and Information Systems Laboratory (CISL) at NCAR. The Atmospheric Tomography Mission (ATom) is funded by the Earth Science Project Office at NASA (NNX15AJ23G). The NOAA ground‐based measurements were supported in part by NOAA's Atmospheric Chemistry, Carbon Cycle and Climate Program of its Climate Program Office. NASA's ATom mission was funded as a NASA Earth Science Venture ‐ suborbital mission. We thank NASA ESPO, the NASA DC‐8 crew, and the ATom Science Team for their exceptional professionalism in support of this mission. Franziska Ziska (GEOMAR, Germany) and colleagues are acknowledged for compiling the HalOcAt data set. Tomás Sherwen (University of York, UK) and Britton Stephens (NCAR, USA) are acknowledged for helpful discussions. CAM‐chem is a component of the NCAR CESM which is publicly available on the project website (http://www.cesm. ucar.edu/). The HalOcAt data set used for the training of the machine‐learning emulator is available in Ziska et al. (doi: https://doi.org/10.5194/acp‐13‐8915‐ 2013). The NCAR CESM Large Ensemble data set is available from the project website (http://www.cesm.ucar. edu/projects/community‐projects/ LENS/). The NCAR TOGA, UCI WAS, and NOAA PFP measurements during the NASA ATom campaign is available from Wofsy et al. (2018).

Global multiconstituent concentration and emission fields obtained from the assimilation of the satellite retrievals of ozone, CO, NO2, HNO3, and SO2 from the Ozone Monitoring Instrument (OMI), Global Ozone Monitoring Experiment 2, Measurements of Pollution in the Troposphere, Microwave Limb Sounder, and Atmospheric Infrared Sounder (AIRS)/OMI are used to understand the processes controlling air pollution during the Korea‐United States Air Quality (KORUS‐AQ) campaign. Estimated emissions in South Korea were 0.42 Tg N for NOx and 1.1 Tg CO for CO, which were 40% and 83% higher, respectively, than the a priori bottom‐up inventories, and increased mean ozone concentration by up to 7.5 ± 1.6 ppbv. The observed boundary layer ozone exceeded 90 ppbv over Seoul under stagnant phases, whereas it was approximately 60 ppbv during dynamical conditions given equivalent emissions. Chemical reanalysis showed that mean ozone concentration was persistently higher over Seoul (75.10 ± 7.6 ppbv) than the broader KORUS‐AQ domain (70.5 ± 9.2 ppbv) at 700 hPa. Large bias reductions (>75%) in the free tropospheric OH show that multiple‐species assimilation is critical for balanced tropospheric chemistry analysis and emissions. The assimilation performance was dependent on the particular phase. While the evaluation of data assimilation fields shows an improved agreement with aircraft measurements in ozone (to less than 5 ppbv biases), CO, NO2, SO2, PAN, and OH profiles, lower tropospheric ozone analysis error was largest at stagnant conditions, whereas the model errors were mostly removed by data assimilation under dynamic weather conditions. Assimilation of new AIRS/OMI ozone profiles allowed for additional error reductions, especially under dynamic weather conditions. Our results show the important balance of dynamics and emissions both on pollution and the chemical assimilation system performance., Key Points Multiconstituent data assimilation during KORUS‐AQ showed that emissions in South Korea were 0.42 Tg N for NOx and 1.1 Tg CO for COThese emissions were 40% and 83% higher, respectively, than the a priori bottom‐up inventories and increased ozone by up to 7.5 ± 1.6 ppbvMean ozone concentration was persistently higher over Seoul (75.1 ± 7.6 ppbv) than the broader KORUS‐AQ domain (70.5 ± 9.2 ppbv) at 700 hPa

Tropospheric ozone (O 3 ) pollution is known to damage vegetation, reducing photosynthesis and stomatal conductance, resulting in modified plant transpiration to the atmosphere. We use an Earth system model to show that global transpiration response to near-present-day surface tropospheric ozone results in large-scale global perturbations to net outgoing long-wave and incoming shortwave radiation. Our results suggest that the radiative effect is dominated by a reduction in shortwave cloud forcing in polluted regions, in response to ozone-induced reduction in land-atmosphere moisture flux and atmospheric humidity. We simulate a statistically significant response of annual surface air temperature of up to ~ +1.5 K due to this ozone effect in vegetated regions subjected to ozone pollution. This mechanism is expected to further increase the net warming resulting from historic and future increases in tropospheric ozone.

We investigate the contributions of emission changes from 10 world regions, as well as the global methane concentration change, on the global tropospheric ozone burden change from 1980 to 2010. The...

Wildland fires involve complicated processes that are challenging to represent in chemical transport models. Recent airborne measurements reveal remarkable chemical tomography in fresh wildland fire plumes, which remain yet to be fully explored using models. Here, we present a high-resolution large eddy simulation model coupled to chemistry to study the chemical evolution in fresh wildland fire plume. The model is configured for a large fire heavily sampled during the Fire Influence on Regional to Global Environments and Air Quality field campaign, and a variety of airborne measurements are used to evaluate the chemical heterogeneity revealed by the model. We show that the model captures the observed cross-transect variations of a number of compounds quite well, including ozone (O3), nitrous acid (HONO), and peroxyacetyl nitrate. The combined observational and modeling results suggest that the top and edges of fresh plume drive the photochemistry, while dark chemistry is also present but in the lower part of the plume. The model spatial resolution is shown to be very important as it may shift the chemical regime, leading to biases in O3 and NOx chemistry. Based on findings in this work, we speculate that the impact of small fires on air quality may be largely underestimated in models with coarse spatial resolutions.

International audience; Nitrous acid (HONO) is an important radical precursor that can impact secondary pollutant levels, especially in urban environments. Due to uncertainties in its heterogeneous formation mechanisms, models often under predict HONO concentrations. A number of heterogeneous sources at the ground have been proposed but there is no consensus about which play a significant role in the urban boundary layer. We present a new one-dimensional chemistry and transport model which performs surface chemistry based on molecular collisions and chemical conversion, allowing us to add detailed HONO formation chemistry at the ground. We conducted model runs for the 2010 CalNex campaign, finding good agreement with observations for key species such as O3, NOx, and HOx. With the ground sources implemented, the model captures the diurnal and vertical profile of the HONO observations. Primary HOx production from HONO photolysis is 2–3 times more important than O3 or HCHO photolysis at mid-day, below 10 m. The HONO concentration, and its contribution to HOx, decreases quickly with altitude. Heterogeneous chemistry at the ground provided a HONO source of 2.5 × 1011 molecules cm−2 s−1 during the day and 5 × 1010 molecules cm−2 s−1 at night. The night time source was dominated by NO2 hydrolysis. During the day, photolysis of surface HNO3/nitrate contributed 45%–60% and photo-enhanced conversion of NO2 contributed 20%–45%. Sensitivity studies addressing the uncertainties in both photolytic mechanisms show that, while the relative contribution of either source can vary, HNO3/nitrate is required to produce a surface HONO source that is strong enough to explain observations.

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both model simulations are compared to airborne observations from a recent global‐scale, multiseasonal campaign, the NASA Atmospheric Tomography Mission (ATom). We find that both CAM‐chem and GEOS‐Chem capture the measured acetone vertical distributions in the remote atmosphere reasonably well. The combined observational and modeling analysis suggests that (i) the ocean strongly regulates the atmospheric budget of acetone. The tropical and subtropical oceans are mostly a net source of acetone, while the high‐latitude oceans are a net sink. (ii) CMIP6 anthropogenic emission inventory may underestimate acetone and/or its precursors in the Northern Hemisphere. (iii) The MEGAN biogenic emissions model may overestimate acetone and/or its precursors, and/or the biogenic oxidation mechanisms may overestimate the acetone yields. (iv) The models consistently overestimate acetone in the upper troposphere‐lower stratosphere over the Southern Ocean in austral winter. (v) Acetone contributes up to 30–40% of hydroxyl radical production in the tropical upper troposphere/lower stratosphere.

We report airborne measurements of acetaldehyde (CH(3)CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH(3)CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH(3)CHO is estimated to be 34 Tg a(−1) (42 Tg a(−1) if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH(3)CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH(3)CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH(3)CHO production in the remote troposphere. The higher-than-expected CH(3)CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models.

Author(s): Tang, Wenfu; Emmons, Louisa K; Jr, Arellano Avelino F; Gaubert, Benjamin; Knote, Christoph; Tilmes, Simone; Buchholz, Rebecca R; Pfister, Gabriele G; Diskin, Glenn S; Blake, Donald R; Blake, Nicola J; Meinardi, Simone; DiGangi, Joshua P; Choi, Yonghoon; Woo, Jung-Hun; He, Cenlin; Schroeder, Jason R; Suh, Inseon; Lee, Hyo-Jung; Jo, Hyun-Young; Kanaya, Yugo; Jung, Jinsang; Lee, Youngjae; Kim, Danbi

Understanding changes in the burden and growth rate of atmospheric methane (CH4) has been the focus of several recent studies but still lacks scientific consensus. Here we investigate the role of decreasing anthropogenic carbon monoxide (CO) emissions since 2002 on hydroxyl radical (OH) sinks and tropospheric CH4 loss. We quantify this impact by contrasting two model simulations for 2002–2013: (1) a Measurement of the Pollution in the Troposphere (MOPITT) CO reanalysis and (2) a Control-Run without CO assimilation. These simulations are performed with the Community Atmosphere Model with Chemistry of the Community Earth System Model fully coupled chemistry climate model with prescribed CH4 surface concentrations. The assimilation of MOPITT observations constrains the global CO burden, which significantly decreased over this period by ~20%. We find that this decrease results to (a) increase in CO chemical production, (b) higher CH4 oxidation by OH, and (c) ~8% shorter CH4 lifetime. We elucidate this coupling by a surrogate mechanism for CO-OH-CH4 that is quantified from the full chemistry simulations.

International audience; The hydroxyl radical (OH) is the primary daytime oxidant in the troposphere and provides the main loss mechanism for many pollutants and greenhouse gases, including methane (CH4). Global mean tropospheric OH differs by as much as 80% among various global models, for reasons that are not well understood. We use neural networks (NNs), trained using archived output from eight chemical transport models (CTMs) that participated in the Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols and Transport Model Intercomparison Project (POLMIP), to quantify the factors responsible for differences in tropospheric OH and resulting CH4 lifetime (τCH4) between these models. Annual average τCH4, for loss by OH only, ranges from 8.0 to 11.6 years for the eight POLMIP CTMs. The factors driving these differences were quantified by inputting 3-D chemical fields from one CTM into the trained NN of another CTM. Across all CTMs, the largest mean differences in τCH4 (ΔτCH4) result from variations in chemical mechanisms (ΔτCH4 = 0.46 years), the photolysis frequency (J) of O3 → O(1D) (0.31 years), local O3 (0.30 years), and CO (0.23 years). The ΔτCH4 due to CTM differences in NOx (NO + NO2) is relatively low (0.17 years), although large regional variation in OH between the CTMs is attributed to NOx. Differences in isoprene and J(NO2) have negligible overall effect on globally averaged tropospheric OH, although the extent of OH variations due to each factor depends on the model being examined. This study demonstrates that NNs can serve as a useful tool for quantifying why tropospheric OH varies between global models, provided that essential chemical fields are archived.

[1] Validation results are reported for the MOPITT (Measurements of Pollution in the Troposphere) “Version 5” (V5) product for tropospheric carbon monoxide (CO) and are compared to results for the “Version 4” product. The V5 retrieval algorithm introduces (1) a method for reducing retrieval bias drift associated with long-term instrumental degradation, (2) a more exact representation of the effects of random errors in the radiances and, for the first time, (3) the use of MOPITT's near-infrared (NIR) radiances to complement the thermal-infrared (TIR) radiances. Exploiting TIR and NIR radiances together facilitates retrievals of CO in the lowermost troposphere. V5 retrieval products based (1) solely on TIR measurements, (2) solely on NIR measurements and (3) on both TIR and NIR measurements are separately validated and analyzed. Actual retrieved CO profiles and total columns are compared with equivalent retrievals based on in situ measurements from (1) routine NOAA aircraft sampling mainly over North America and (2) the “HIAPER Pole to Pole Observations” (HIPPO) field campaign. Particular attention is focused on the long-term stability and geographical uniformity of the retrieval errors. Results for the retrieved total column clearly indicate reduced temporal bias drift in the V5 products compared to the V4 product, and do not exhibit a positive bias in the Southern Hemisphere, which is evident in the V4 product.

[1] Satellite measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) are used to examine the global, seasonal variations of several hydrocarbons, including carbon monoxide (CO), ethane (C2H6), acetylene (C2H2), and hydrogen cyanide (HCN). We focus on quantifying large-scale seasonal behavior from the middle troposphere to the stratosphere, particularly in the tropics, and furthermore make detailed comparisons with the Whole Atmosphere Community Climate Model (WACCM) chemistry climate model (incorporating tropospheric photochemistry, time-varying hydrocarbon emissions, and meteorological fields nudged from reanalysis). Comparisons with Microwave Limb Sounder (MLS) measurements of CO are also included to understand sampling limitations of the ACE-FTS data and biases among observational data sets. Results show similar overall variability for CO, C2H6, and C2H2, with a semiannual cycle in the tropical upper troposphere related to seasonallyvarying sources and deep tropical convection, plus a maximum during Northern Hemisphere summer tied to the Asian monsoon anticyclone. These species also reveal a strong annual cycle above the tropical tropopause, tied to annual variations in the upward branch of Brewer-Dobson circulation. HCN reveals substantial differences from the other species, due to a longer photochemical lifetime and a chemical sink associated with ocean surface contact, which produces a minimum in the tropical upper troposphere not observed in the other species. For HCN, transport to the stratosphere occurs primarily through the Asian summer monsoon anticyclone. Overall, the WACCM simulation is able to reproduce most of the large-scale features observed in the ACE-FTS data, suggesting a reasonable simulation of sources and large-scale transport. The model is too low in the Southern Hemisphere subtropics during Austral spring, which indicates underestimate of biomass burning emissions and/or insufficient vertical transport in the model.

[1] In this work, we map and develop for the first time an independent satellite constrained NOx emission inventory for India for 2005 using an inverse technique and iterative procedure. We used OMI tropospheric NO2 column retrievals over the Indian region, with tropospheric NO2 columns simulated by the WRF-Chem model using the INTEX-B emission inventory. We determined the local relationship between modeled emissions and tropospheric columns and iteratively apply this relationship to OMI observations to derive an optimized NOx emission inventory on a 0.5° × 0.5° grid. The optimized total NOx emissions for India amount to 1.9 TgN/y and agree within 25% with EDGARv4.1 and the INTEX-B estimate. Our top-down inventory captures many of the missing hotspots in the original inventory and suggests that the INTEX-B inventory overestimates emissions over the Western and Eastern Indo-Gangetic region and underestimates point sources. We further evaluate the effect of the top-down inventory on surface ozone, which clearly indicates significant changes in spatial distribution.

[1] We present source estimates of atmospheric carbon monoxide from nonmethane volatile organic compound (NMVOC) oxidation during a period of 8 years (1997–2004) using a Bayesian inversion analysis. The optimized global NMVOC-derived CO source strength indicates a change of a factor of 2 between the 1997–1998 strong El Nino and subsequent La Nina conditions. For comparison, the average 8 year interannual variability (IAV) is 18%. The variation of NMVOC-derived CO is closely correlated with the Oceanic Nino Index (ONI) and surface temperature. A time-lagged correlation analysis between ONI and NMVOC-derived CO inventory indicated El Nino/Southern Oscillation leads the Northern Hemisphere (NH) NMVOC-derived CO production by about 3 months earlier than the Southern Hemisphere's (SH). The SH NMVOC-derived CO was positively correlated with the lagged-ONI (r = 0.57), while the temperature change barely influenced SH NMVOC-derived CO (r = 0.01). In the NH, temperature was more robustly correlated with NMVOC-derived CO (r = 0.58) than the lagged-ONI (r = 0.35). In particular, the extra-tropical temperature showed a strong correlation (r = 0.90) with the NH NMVOC-derived CO and suggested its primary role in controlling the interannual variability of the NH NMVOC-derived CO.

© 2016. American Geophysical Union. All Rights Reserved. We examine in detail a 1 year global reanalysis of carbon monoxide (CO) that is based on joint assimilation of conventional meteorological observations and Measurement of Pollution in The Troposphere (MOPITT) multispectral CO retrievals in the Community Earth System Model (CESM). Our focus is to assess the impact to the chemical system when CO distribution is constrained in a coupled full chemistry-climate model like CESM. To do this, we first evaluate the joint reanalysis (MOPITT Reanalysis) against four sets of independent observations and compare its performance against a reanalysis with no MOPITT assimilation (Control Run). We then investigate the CO burden and chemical response with the aid of tagged sectoral CO tracers.We estimate the total tropospheric CO burden in 2002 (from ensemble mean and spread) to be 371 ± 12%Tg for MOPITT Reanalysis and 291 ± 9%Tg for Control Run. Our multispecies analysis of this difference suggests that (a) direct emissions of CO and hydrocarbons are too low in the inventory used in this study and (b) chemical oxidation, transport, and deposition processes are not accurately and consistently represented in the model. Increases in CO led to net reduction of OH and subsequent longer lifetime of CH4 (Control Run: 8.7 years versus MOPITT Reanalysis: 9.3 years). Yet at the same time, this increase led to 5-10% enhancement of Northern Hemisphere O3 and overall photochemical activity via HOx recycling. Such nonlinear effects further complicate the attribution to uncertainties in direct emissions alone. This has implications to chemistry-climate modeling and inversion studies of longer-lived species.

Author(s): Kaser, L; Karl, T; Yuan, B; Mauldin, RL; Cantrell, CA; Guenther, AB; Patton, EG; Weinheimer, AJ; Knote, C; Orlando, J; Emmons, L; Apel, E; Hornbrook, R; Shertz, S; Ullmann, K; Hall, S; Graus, M; De Gouw, J; Zhou, X; Ye, C | Abstract: The hydroxyl radical (OH) is the most important oxidant in the atmosphere and the primary sink for isoprene, the dominant volatile organic compound emitted by vegetation. Recent research on the atmospheric oxidation capacity in isoprene-dominated environments has suggested missing radical sources leading to significant overestimation of the lifetime of isoprene. Here we report, for the first time, a comprehensive experimental budget of isoprene in the planetary boundary layer based on airborne flux measurements along with in situ OH observations in the Southeast and Central U.S. Our findings show that surface heterogeneity of isoprene emissions lead to a physical separation of isoprene and OH resulting in an effective slowdown in the chemistry. Depending on surface heterogeneity, the intensity of segregation (Is) could locally slow down isoprene chemistry up to 30%. The effect of segregated reactants in the planetary boundary layer on average has an influence on modeled OH radicals that is comparable to that of recently proposed radical recycling mechanisms.

© 2015. American Geophysical Union. All Rights Reserved. We show the results and evaluation with independent measurements from assimilating both MOPITT (Measurements Of Pollution In The Troposphere) and IASI (Infrared Atmospheric Sounding Interferometer) retrieved profiles into the Community Earth System Model (CESM). We used the Data Assimilation Research Testbed ensemble Kalman filter technique, with the full atmospheric chemistry CESM component Community Atmospheric Model with Chemistry. We first discuss the methodology and evaluation of the current data assimilation system with coupled meteorology and chemistry data assimilation. The different capabilities of MOPITT and IASI retrievals are highlighted, with particular attention to instrument vertical sensitivity and coverage and how these impact the analyses. MOPITT and IASI CO retrievals mostly constrain the CO fields close to the main anthropogenic, biogenic, and biomass burning CO sources. In the case of IASI CO assimilation, we also observe constraints on CO far from the sources. During the simulation time period (June and July 2008), CO assimilation of both instruments strongly improves the atmospheric CO state as compared to independent observations, with the higher spatial coverage of IASI providing better results on the global scale. However, the enhanced sensitivity of multispectral MOPITT observations to near surface CO over the main source regions provides synergistic effects at regional scales.

The Measurements of Pollution in the Troposphere (MOPITT) instrument on the NASA Terra platform has now acquired over thirteen years of global tropospheric carbon monoxide (CO) observations, forming the longest satellite record for an important pollutant. [...]

The global distributions of sulfate and soot particles in the atmosphere are calculated, and the effect of aerosol particles on tropospheric oxidants is studied using a global chemical/transport/aerosol model. The model is developed in the framework of the National Center for Atmospheric Research (NCAR) global three-dimensional chemical/transport model (Model for Ozone and Related Chemical Tracers (MOZART)). In addition to the gas-phase photochemistry implemented in the MOZART model, the present study also accounts for the formation of sulfate and black carbon aerosols as well as for heterogeneous reactions on particles. The simulated global sulfate aerosol distributions and seasonal variation are compared with observations. The seasonal variation of sulfate aerosols is in agreement with measurements, except in the Arctic region. The calculated vertical profiles of sulfate aerosol agree well with the observations over North America. In the case of black carbon the calculated surface distribution is in fair agreement with observations. The effects of aerosol formation and heterogeneous reactions on the surface of sulfate aerosols are studied. The model calculations show the following: (1) The concentration of H2O2 is reduced when sulfate aerosols are formed due to the reaction of SO2 + H2O2 in cloud droplets. The gas-phase reaction SO2 + OH converts OH to HO2, but the reduction of OH and enhancement of HO2 are insignificant (

The impact of lightning on tropospheric reactive nitrogen NOx (NO + NO2) and nitrogen reservoir species (HNO3, peroxyacetyl nitrate (PAN), N2O5, and HNO4) has been evaluated using a global chemical/transport model. Comparison of calculations made with and without lightning show that lightning has a significant effect on the nitrogen species on a global scale, resulting in significant enhancements of NOx, HNO3, and PAN over the no lightning case. Of the nitrogen species, HNO3 is influenced the most, comprising approximately 60 to 80% of the total increase in the nitrogen species concentration. The increase in PAN accounts for approximately 20 to 30% of the nitrogen enhancement by lightning in the middle troposphere. In the lower troposphere of the tropics, NOx is rapidly converted into HNO3 due to the high OH concentration in this region. As a result, the enhancement in NOx from direct lightning emission is limited primarily to the upper troposphere. The conversion between NOx and less reactive nitrogen species (PAN and HNO3) also plays an important role in affecting NOx, especially over the oceans where lightning activity is low. The model results suggest that recycling of NOx from the lightning-enhanced PAN and HNO3 produces 2 to 10 parts per trillion by volume (pptv) increases in NOx over the oceans in the lower troposphere of the tropics. The enhancement of NOx over the oceans can partially explain the observations of NOx (mixing ratios of typically 10–50 pptv) over the tropical oceans, which are characterized by higher concentrations than would be expected from direct transport of NOx from the continents.

In this second of two companion papers, we present results from a new global three-dimensional chemical transport model, called MOZART (model for ozone and related chemical tracers). MOZART is developed in the framework of the National Center for Atmospheric Research (NCAR) Community Climate Model (CCM) and includes a detailed representation of tropospheric chemistry. The model provides the distribution of 56 chemical species at a spatial resolution of 2.8° in both latitude and longitude, with 25 levels in the vertical (from the surface to level of 3 mbar) and a time step of 20 min. The meteorological information is supplied from a 2-year run of the NCAR Community Climate Model. The simulated distributions of ozone (O 3 ) and its precursors are evaluated by comparison with observational data. The distribution of methane, nonmethane hydrocarbons (NMHCs), and CO are generally well simulated by the model. The model evaluation in the tropics stresses the need for a better representation of biomass burning emissions in order to evaluate the budget of carbon monoxide, nitrogen species, and ozone with more accuracy in these regions. MOZART reproduces the NO observations in most parts of the troposphere. Nitric acid, however, is overestimated over the Pacific by up to a factor of 10 and over continental regions by a factor of 2-3. Discrepancies are also found in the simulation of PAN in the upper troposphere and in biomass burning regions. These results highlight shortcomings in our understanding of the nitrogen budget in the troposphere. The seasonal cycle of ozone in the troposphere is generally well reproduced by the model in comparison with ozone soundings. MOZART tends, however, to underestimate O 3 at higher latitudes, and specifically above 300 mbar. The global photochemical production and destruction of ozone in the troposphere are 3018 Tg/yr and 2511 Tg/yr, respectively (net ozone production of 507 Tg/yr). The stratospheric influx of O 3 is estimated to be 391 Tg/yr and the surface dry deposition 898 Tg/yr. The calculated global lifetime of methane is 9.9 years in the annual average.

Products from the Measurements Of Pollution In The Troposphere (MOPITT) instrument are regularly validated using in situ airborne measurements. However, few of these measurements reach into the upper troposphere, thus hindering MOPITT validation in that region. Here we evaluate upper tropospheric (~500 hPa to the tropopause) MOPITT CO profiles by comparing them to satellite Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) retrievals and to measurements from the High-performance Instrumented Airborne Platform for Environmental Research Pole to Pole Observations (HIPPO) Quantum Cascade Laser Spectrometer (QCLS). Direct comparison of colocated v5 MOPITT thermal infrared-only retrievals, v3.0 ACE-FTS retrievals, and HIPPO-QCLS measurements shows a slight positive MOPITT CO bias within its 10% accuracy requirement with respect to the other two data sets. Direct comparison of colocated ACE-FTS and HIPPO-QCLS measurements results in a small number of samples due to the large disparity in sampling pattern and density of these data sets. Thus, two additional indirect techniques for comparison of noncoincident data sets have been applied: tracer-tracer (CO-O3) correlation analysis and analysis of profiles in tropopause coordinates. These techniques suggest a negative bias of ACE-FTS with respect to HIPPO-QCLS; this could be caused by differences in resolution (horizontal, vertical) or by deficiencies in the ACE-FTS CO retrievals below ~20 km of altitude, among others. We also investigate the temporal stability of MOPITT and ACE-FTS data, which provide unique global CO records and are thus important in climate analysis. Our results indicate that the relative bias between the two data sets has remained generally stable during the 2004–2010 period.

This study uses a global chemical transport model to estimate the distribution of isocyanic acid (HNCO). HNCO is toxic, and concentrations exceeding 1 ppbv have been suggested to have negative health effects. Based on fire studies, HNCO emissions were scaled to those of hydrogen cyanide (30%), resulting in yearly total emissions of 1.5 Tg for 2008, from both anthropogenic and biomass burning sources. Loss processes included heterogeneous uptake (pH dependent), dry deposition (like formic acid), and reaction with the OH radical (k = 1 × 10−15 molecule−1 cm3 s−1). Annual mean surface HNCO concentrations were highest over parts of China (maximum of 470 pptv), but episodic fire emissions gave much higher levels, exceeding 4 ppbv in tropical Africa and the Amazon, and exceeding 10 ppbv in Southeast Asia and Siberia. This suggests that large biomass burning events could result in deleterious health effects for populations in these regions. For the tropospheric budget, using the model-calculated pH the HNCO lifetime was 37 days, with the split between dry deposition and heterogeneous loss being 95%:5%. Fixing the heterogeneous loss rate at pH = 7 meant that this process dominated, accounting for ∼70% of the total loss, giving a lifetime of 6 days, and resulting in upper tropospheric concentrations that were essentially zero. However, changing the pH does not notably impact the high concentrations found in biomass burning regions. More observational data is needed to evaluate the model, as well as a better representation of the likely underestimated biofuel emissions, which could mean more populations exposed to elevated HNCO concentrations.

We have recovered vertical profiles of stratospheric N2O from spectra observed using a ground-based mm-wave spectrometer during the Arctic spring. The measurements were made from Thule, Greenland (76.3 deg N, 68.4 deg W) on nine occasions from late February to late March, 1992 as part of the Upper Atmosphere Research Satellite (UARS) Correlative Measurements Program and the European Arctic Stratospheric Ozone Experiment (EASOE). During late February Thule was under inside edge of the Arctic vortex and mixing ratio profiles measured in that period are substantially reduced from typical high-latitude summer values. By late March the polar vortex had moved well away from Thule and N2O mixing ratios were greatly increased, coinciding with a basic change in circulation that brought in air from the Aleutian high. The motion of the vortex is also illustrated in the change in potential vorticity above Thule. A correlation with ozone balloonsonde data from Thule is made and compared to similar analyses of the Airborne Arctic Stratospheric Expedition (AASE) measurements. Within the sensitivity of our analysis, the correlation of N2O and O3 shows no evidence of ozone depletion within the vortex during this period; however, there is a distinct difference in the correlation inside and outside the vortex.

Measurements of chlorine monoxide in the stratosphere over Thule, Greenland (73.6 N, 68.4 W) were made quasi-continuously during the period February 8 to March 24, 1992, using a high-sensitivity ground based mm-wave spectrometer. These observations give diurnal, short term, and long term changes in the mixing ratio and vertical distribution of ClO. At an equivalent time after the Antarctic winter solstice, very large concentrations (up to approximately 1.5 ppbv) occur in lower stratospheric ClO, resulting in massive ozone destruction. We saw no evidence for large (approximately 1 top 1.5 ppbv) amounts of ClO in the 16-25 km range over Thule in February or March, in agreement with UARS (satellite) observations by the MLS mm-wave spectrometer for this period, and in marked contrast to UARS/MLS and ER-2 aircraft measurements over northern Europe and eastern Canada, respectively, during January, 1992. We have evidence for smaller enhancements (approximately 0.2 to 0.5 ppbv) in the 18-30 km range during late February-early March, which could result from transport of residual low NO2 air following earlier polar stratospheric cloud (PSC) processing (the last of which occurred at least one month earlier, however) or the result of chemical processing by Pinatubo aerosols. Direct influence of Pinatubo aerosols on Arctic ozone during the spring of 1992 has been difficult to assess, and this enhancement of low-altitude ClO might be a significant indicator of aerosol effects.

[1] Using 3 years worth of IASI (the Infrared Atmospheric Sounder Interferometer aboard METOP-A) measurements, we have identified 24 major events of uplift and transport of anthropogenic sulfur dioxide. These were all first observed over East Asia, and could be traced for over 60 hours. On 7 November 2010 a sulfur dioxide plume was observed over Northeast China and tracked for five days to North America. We discuss this event in detail with respect to build up; uplift and in-plume chemistry. We found a host of trace gas enhancements in the plume (SO2, CO, PAN, CH3OH, HCOOH and C2H2). A reasonable to very good agreement was found with MOZART-4 modeled ambient columns for all species except methanol, which was underestimated by the model by an order of magnitude. We calculate correlations of the different species and give observational evidence of secondary in-plume formation of methanol and PAN.

Due to a lack of industrialization in Western China, surface air there was, until recently, believed to be relatively unpolluted. However, recent measurements and modeling studies have found high levels of ozone (O3) there. Based on the state-of-the-science global chemical transport model MOZART-4, we identify the origin, pathway, and mechanism of trans-Eurasian transport of air pollutants to Western China in 2000. MOZART-4 generally simulates well the observed surface O3 over inland areas of China. Simulations find surface ozone concentrations over Western China on average to be about 10 ppbv higher than Eastern China. Using sensitivity studies, we find that anthropogenic emissions from all Eurasian regions except China contribute 10–15 ppbv surface O3 over Western China, superimposed upon a 35–40 ppbv natural background. Transport from European anthropogenic sources to Northwestern China results in 2–6 ppbv O3 enhancements in spring and summer. Indian anthropogenic sources strongly influence O3 over the Tibetan Plateau during the summer monsoon. Transport of O3 originating from emissions in the Middle East occasionally reach Western China and increase surface ozone there by about 1–4 ppbv. These influences are of similar magnitude as trans-Pacific and transatlantic transport of O3 and its precursors, indicating the significance of trans-Eurasian ozone transport in hemispheric transport of air pollution. Our study further indicates that mitigation of anthropogenic emissions from Europe, the Indian subcontinent, and the Middle East could benefit public health and agricultural productivity in Western China.

[1] Vertical profiles of carbon monoxide (CO) concentration and corresponding total column values derived from measurements made by the Measurements of Pollution in the Troposphere (MOPITT) satellite instrument are now being processed operationally with the “version 4” (V4) retrieval algorithm. This algorithm exploits the results of analyses of in situ data, chemical transport modeling, and radiative transfer modeling in the MOPITT postlaunch era. Improvements in the V4 product are evident in both clean and polluted conditions. The new products are validated using CO in situ measurements acquired from aircraft from 2000 to 2007. As determined by both retrieval simulations and observations, retrieval bias drift is typically about 1 ppbv/yr for levels in the middle troposphere and about 2 ppbv/yr in the upper troposphere. Retrieval simulations indicate that observed bias drift may be the result of gradual on-orbit changes in the instrument's modulation cell parameters.

[1] Measurements of atmospheric CH4 from air samples collected weekly at 46 remote surface sites show that, after a decade of near-zero growth, globally averaged atmospheric methane increased during 2007 and 2008. During 2007, CH4 increased by 8.3 ± 0.6 ppb. CH4 mole fractions averaged over polar northern latitudes and the Southern Hemisphere increased more than other zonally averaged regions. In 2008, globally averaged CH4 increased by 4.4 ± 0.6 ppb; the largest increase was in the tropics, while polar northern latitudes did not increase. Satellite and in situ CO observations suggest only a minor contribution to increased CH4 from biomass burning. The most likely drivers of the CH4 anomalies observed during 2007 and 2008 are anomalously high temperatures in the Arctic and greater than average precipitation in the tropics. Near-zero CH4 growth in the Arctic during 2008 suggests we have not yet activated strong climate feedbacks from permafrost and CH4 hydrates.

[1] Satellite observations of tropospheric chemical constituents (such as carbon monoxide, CO) reveal a persistent maximum in the upper troposphere―lower stratosphere (UTLS) associated with the Asian summer monsoon anticyclone. Diagnostic studies suggest that the strong anticyclonic circulation acts to confine air masses, but the sources of pollution and transport pathways to altitudes near the tropopause are the subject of debate. Here we use the Model for Ozone and Related Tracers 4 (MOZART-4) global chemistry transport model, driven by analyzed meteorological fields, to study the source and transport of CO in the Asian monsoon circulation. A MOZART-4 simulation for one summer is performed, and results are compared with satellite observations of CO from the Aura Microwave Limb Sounder and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer. Overall, good agreement is found between the modeled and observed CO in the UTLS, promoting confidence in the model simulation. The model results are then analyzed to understand the sources and transport pathways of CO in the Asian monsoon region, and within the anticyclone in particular. The results show that CO is transported upward by monsoon deep convection, with the main surface sources from India and Southeast Asia. The uppermost altitude of the convective transport is ∼12 km, near the level of main deep convective outflow, and much of the CO is then advected in the upper troposphere northeastward across the Pacific Ocean and southwestward with the cross-equatorial Hadley flow. However, some of the CO is also advected vertically to altitudes near the tropopause (∼16 km) by the large-scale upward circulation on the eastern side of the anticyclone, and this air then becomes trapped within the anticyclone (to the west of the convection, extending to the Middle East). Within the anticyclone, the modeled CO shows a relative maximum near 15 km, in good agreement with observations.

[1] The origin of ozone over the summertime contiguous United States during summer 2004 was examined using the Intercontinental Transport Experiment (INTEX-A) Ozonesonde Network Study (IONS-04) over North America. We estimate the budget using the global chemistry transport Model of Ozone and Related Tracers version 4 (MOZART-4) with synthetic tracers that keep track of the ozone produced from selected NOx sources (stratosphere, lightning, anthropogenic, and biomass burning sources in Eurasia and the contiguous United States, and North American boreal fires). This “model budget” is analyzed in conjunction with results from a “laminar identification method” (LID), a more empirical approach to extracting information about contributions from ozone transported down from the stratosphere, advection, and convection. Both methods give comparable results for the contribution from stratospheric ozone, an average over all sites of 20 ± 7% for the LID budget and of 26 ± 6% for the model budget (the standard deviation gives the variability over the IONS sites). These results point toward the important contribution of downward transport of ozone from the stratosphere in assessing tropospheric ozone. The contributions for the other tracers are 25 ± 9% for U.S. sources, 13 ± 5% for Eurasian sources, 3 ± 2% for boreal fires and 10 ± 2% from lightning. In the boundary layer the dominant contribution generally comes from local (U.S.) sources. Eurasian sources can add up to 8% on average for some sites, lightning up to 4%, and North American boreal fires up to 10%. Variations in the tracer contributions across the different sites can be large, but the budget estimated by the model for the entire United States is similar to the budget averaged over the IONS-04 sites which lets us conclude that the sample of locations and launch days conveys a proper representation of the large-scale picture.

[1] This study quantifies the impact of the fires in California in fall 2007 on regional air quality and especially on surface ozone by analyzing surface observations of ozone concentrations together with global chemistry transport model simulations. The latter include a synthetic tracer providing information about the amount of ozone produced from the fires. It is shown that the global model is well suited for simulating the overall fire impact and a valuable tool for extracting information about the fire influence from the observations. A clear increase in observed ozone is found when the model predicts a strong impact of pollution from the fires, where measured afternoon 8-hour concentrations increased, on average, by about 10 ppb. The findings demonstrate that intense wildfire periods can significantly increase the frequency of ozone concentrations exceeding current U.S. health standards, and might cause violations also during photochemically less active seasons. The study also demonstrates the far-reaching impact of ozone production from the fires.

[1] We present a study of the sensitivity of isoprene emission calculations in a global chemistry transport model (CTM) to input land cover characteristics and analyze the impacts of changes in isoprene on the tropospheric budgets of atmospheric key species. The CTM Model for Ozone and Related Chemical Species, version 4 (MOZART-4) includes the online calculation of isoprene emissions based on the Model of Emissions of Gases and Aerosols from Nature (MEGAN), which is driven by three different land parameter inputs. We also included a tagging scheme in the CTM, which keeps track of the production of carbon containing species from isoprene oxidation. It is found that the amount of tropospheric carbon monoxide (CO), formaldehyde (HCHO) and peroxyacetylnitrate (PAN) explained by isoprene oxidation ranges from 9–16%, 15–27%, and 22–32%, depending on the isoprene emissions scenario. Changes in the global tropospheric burden with different land cover inputs can reach up to 10% for CO, 15% for HCHO, and 20% for PAN. Changes for ozone are small on a global scale, but regionally differences are as large as 3DU in the tropospheric column and as large as 5 ppbv in the surface concentrations. Our results demonstrate that a careful integration of isoprene emissions and chemistry in CTMs is very important for simulating the budgets of a number of atmospheric trace gases. We further demonstrate that the model tagging scheme has the capability of improving conventional methods of constraining isoprene emissions from space-borne HCHO column observations, especially in regions where a considerable part of the variability in the HCHO column is not related to isoprene.

[1] In this study we estimate the radiative impact of wildfires in Alaska during the record wildfire season of 2004 by integrating model simulations and satellite observations of the top of the atmosphere (TOA) radiative fluxes and aerosol optical depth. We compare results for the summer of 2004 to results for the summer of 2000 when fire activity in the boreal zone was low. Both observations and model show a decrease in TOA clear-sky fluxes over the Alaska fire region during summer 2004 of -7 ± 6 W m -2 and -10 ± 4 W m -2 , respectively. About two thirds of the change occurs in the longwave, and one third in the shortwave, spectral range. On the bases of detailed model analysis we estimate that the changes in the longwave flux are predominantly explained by a higher surface temperature in summer 2004 compared to 2000. The change in the shortwave flux is largely caused by scattering of solar radiation on organic carbon aerosols emitted from the 2004 fires. This cooling is somewhat mitigated by the warming effect due to absorbing black carbon aerosols emitted from the fires and to a lesser extent by ozone and other greenhouse gases produced and released from the fires. Sensitivity studies with varying aerosol emission scenarios indicate that the ratio of black to organic carbon aerosol emissions of the boreal fires used in this study needs to be increased considerably to match both observations of aerosol optical depth and TOA radiation fluxes, or the biomass burning aerosols must be considerably more absorbing than parameterized in the model. While this study cannot resolve the cause of this discrepancy, it presents a powerful methodology to constrain aerosol emissions. This methodology will benefit from future improvements in measurements and modeling techniques.

[1] Carbon monoxide (CO) is a key species for tracking pollution plumes. The Measurement Of Pollution in The Troposphere (MOPITT) mission onboard the Terra satellite has already provided 7.5 years of CO atmospheric concentration measurements around the globe. Limited sensitivity to the boundary layer is well known to be a weakness of nadir looking thermal infrared sounders. This paper investigates the possibility of using the MOPITT surface measurements to detect CO emitted by cities and urban centers. By selecting the data and averaging them over long time periods, we demonstrate that the CO pollution arising from the large cities and urban areas can be distinguished from the background transported pollution. The more favorable observations are obtained during daytime and at locations where the thermal contrast (temperature gradient) between the surface and lower atmosphere is significant.

We evaluate the Meteo-France global chemistry transport 3D model MOCAGE (MOdele de Chimie Atmospherique a Grande Echelle) using the important set of aircraft measurements collected during the ICARRT/ITOP experiment. This experiment took place between US and Europe during summer 2004 (July 15-August 15). Four aircraft were involved in this experiment providing a wealth of chemical data in a large area including the North East of US and western Europe. The model outputs are compared to the following species of which concentration is measured by the aircraft: OH, H2O2, CO, NO, NO2, PAN, HNO3, isoprene, ethane, HCHO and O3. Moreover, to complete this evaluation at larger scale, we used also satellite data such as SCIAMACHY NO2 and MOPITT CO. Interestingly, the comprehensive dataset allowed us to evaluate separately the model representation of emissions, transport and chemical processes. Using a daily emission source of biomass burning, we obtain a very good agreement for CO while the evaluation of NO2 points out incertainties resulting from inaccurate ratio of emission factors of NOx/CO. Moreover, the chemical behavior of O3 is satisfactory as discussed in the paper.

A comprehensive group of reactive nitrogen species (NO, NO2, HNO3, HO2NO2, PANs, alkyl nitrates, and aerosol-NO3) were measured in the troposphere and lowermost stratosphere over North America and the Atlantic during July/August 2004 (INTEX-A) from the NASA DC-8 platform (0.1-12 km). Less reactive nitrogen species (HCN and CH3CN), that are also unique tracers of biomass combustion, were also measured along with a host of other gaseous (CO, VOC, OVOC, halocarbon) and aerosol tracers. Clean background air as well as air with influences from biogenic emissions, anthropogenic pollution, biomass combustion, and stratosphere was sampled both over continental U. S., Atlantic and Pacific. The North American upper troposphere was found to be greatly influenced by both lightning NO(x) and surface pollution lofted via convection and contained elevated concentrations of PAN, ozone, hydrocarbons, and NO(x). Under polluted conditions PAN was a dominant carrier of reactive nitrogen in the upper troposphere while nitric acid dominated in the lower troposphere. Peroxynitric acid (HO2NO2) was present in sizable concentrations always peaking at around 8 km. Aerosol nitrate appeared to be mostly contained in large soil based particles in the lower troposphere. Plumes from Alaskan fires contained large amounts of PAN and very little enhancement in ozone. Observational data suggest that lightning was a far greater contributor to NO(x) in the upper troposphere than previously believed. NO(x) and NO(y) reservoir appeared to be in steady state only in the middle troposphere where NO(x)/NO(y) was independent of air mass age. A first comparison of observed data with simulations from four 3-D models shows significant differences between observations and models as well as among models. These uncertainties likely propagate themselves in satellites derived NOx data. Observed data are interpreted to suggest that soil sinks of HCN/CH3CN are at best very small. We investigate the partitioning and interplay of the reactive nitrogen species within characteristic air masses and further examine their role in ozone formation.

The summer of 2004 was one of the largest fire seasons on record for Alaska and western Canada. We construct a daily bottom-up fire emission inventory for that season, including consideration of peat burning and high-altitude (buoyant) injection, and evaluate it in a global chemical transport model (the GEOS-Chem CTM) simulation of CO through comparison with MOPITT satellite and ICARTT aircraft observations. The inventory is constructed by combining daily area burned reports and MODIS fire hot spots with estimates of fuel consumption and emission factors based on ecosystem type. We estimate the contribution from peat burning using drainage and peat distribution maps for Alaska and Canada; 17% of the reported 5.1 × 106 ha burned were located in peatlands in 2004. Our total estimate of North American fire emissions during the summer of 2004 is 30 Tg CO, including 11 Tg from peat. Including peat burning in the GEOS-Chem simulation improves agreement with MOPITT observations. The long-range transport of fire plumes observed by MOPITT suggests that the largest fires injected a significant fraction of their emissions in the upper troposphere.

[1] During the operational phase of the ICARTT field experiment in 2004, the regional air quality model STEM showed a strong positive surface bias and a negative upper troposphere bias (compared to observed DC-8 and WP-3 observations) with respect to ozone. After updating emissions from NEI 1999 to NEI 2001 (with a 2004 large point sources inventory update), and modifying boundary conditions, low-level model bias decreases from 11.21 to 1.45 ppbv for the NASA DC-8 observations and from 8.26 to 0.34 for the NOAA WP-3. Improvements in boundary conditions provided by global models decrease the upper troposphere negative ozone bias, while accounting for biomass burning emissions improved model performance for CO. The covariances of ozone bias were highly correlated to NOz ,N Oy, and HNO3 biases. Interpolation of bias information through kriging showed that decreasing emissions in SE United States would reduce regional ozone model bias and improve model correlation coefficients. The spatial distribution of forecast errors was analyzed using kriging, which identified distinct features, which when compared to errors in postanalysis simulations, helped document improvements. Changes in dry deposition to crops were shown to reduce substantially high bias in the forecasts in the Midwest, while updated emissions were shown to account for decreases in bias in the eastern United States. Observed and modeled ozone production efficiencies for the DC-8 were calculated and shown to be very similar (7.8) suggesting that recurring ozone bias is due to overestimation of NOx emissions. Sensitivity studies showed that ozone formation in the United States is most sensitive to NOx emissions, followed by VOCs and CO. PAN as a reservoir of NOx can contribute to a significant amount of surface ozone through thermal decomposition. Citation: Mena-Carrasco, M., et al. (2007), Improving regional ozone modeling through systematic evaluation of errors using the aircraft observations during the International Consortium for Atmospheric Research on Transport and Transformation, J. Geophys. Res., 112, D12S19, doi:10.1029/2006JD007762.

The Model for Ozone and Related Chemical Tracers, version 3 (MOZART-3), which represents the chemical and physical processes from the troposphere through the lower mesosphere, was used to evaluate the representation of long- lived tracers and ozone using three different meteorological fields. The meteorological fields are based on (1) the Whole Atmosphere Community Climate Model, version 1b (WACCM1b), (2) the European Centre for Medium- Range Weather Forecasts (ECMWF) operational analysis, and (3) a new reanalysis for year 2000 from ECMWF called EXP471. Model-derived tracers (methane, water vapor, and total inorganic nitrogen) and ozone are compared to data climatologies from satellites. Model mean age of air was also derived and compared to in situ CO2 and SF6 data. A detailed analysis of the chemical fields simulated by MOZART-3 shows that even though the general features characterizing the three dynamical sets are rather similar, slight differences in winds and temperature can produce substantial differences in the calculated distributions of chemical tracers. The MOZART-3 simulations that use meteorological fields from WACCM1b and ECMWF EXP471 represented best the distribution of long-lived tracers and mean age of air in the stratosphere. There was a significant improvement using the ECMWF EXP471 reanalysis data product over the ECMWF operational data product. The effect of the quasi- biennial oscillation circulation on long- lived tracers and ozone is examined.

International audience; Measurements of carbon monoxide (CO) made as part of three aircraft experiments during the summer of 2004 over North America have been used for the continued validation of the CO retrievals from the Measurements of Pollution in the Troposphere (MOPITT) instrument on board the Terra satellite. Vertical profiles measured during the NASA INTEX-A campaign, designed to be coincident with MOPITT overpasses, as well as measurements made during the COBRA-2004 and MOZAIC experiments, provided valuable validation comparisons. On average, the MOPITT CO retrievals are biased slightly high for these North America locations. While the mean bias differs between the different aircraft experiments (e.g., 7.0 ppbv for MOZAIC to 18.4 ppbv for COBRA at 700 hPa), the standard deviations are quite large, so the results for the three data sets can be considered consistent. On average, it is estimated that MOPITT is 7–14% high at 700 hPa and ~3% high at 350 hPa. These results are consistent with the validation results for the Carr, Colorado, Harvard Forest, Massachusetts, and Poker Flats, Alaska, aircraft profiles for “phase 2” presented by Emmons et al. (2004) and are generally within the design criteria of 10% accuracy.