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Tropospheric Ozone Over the North Pacific from Ozonesdonde Observations

As part of the TRACE-P mission, ozone vertical profile measurements were made at a number of locations in the North Pacific. At most of the sites there is also a multi-year record of ozonesonde observations. From seven locations in the western Pacific (Hong Kong; Taipei; Jeju Island, Korea; and Naha, Kagoshima, Tsukuba, and Sapporo, Japan), a site in the central Pacific (Hilo, HI), and a site on the west coast of the U.S. (Trinidad Head, CA) both a seasonal and event specific picture of tropospheric ozone over the North Pacific emerges. At all of the sites there is a pronounced spring maximum through the troposphere. There are, however, differences in the timing and strength of this feature. Over Japan the northward movement of the jet during the spring and summer influences the timing of the seasonal maximum. The ozone profiles suggest that transport of ozone rich air from the stratosphere plays a strong role in the development of this maximum. During March and April at Hong Kong ozone is enhanced in a layer that extends from the lower free troposphere into the upper troposphere that likely has its origin in biomass burning in northern Southeast Asia and equatorial Africa. During the winter the Pacific subtropical sites (latitude -25N) are dominated by air with a low-latitude, marine source that gives low ozone amounts particularly in the upper troposphere. In the summer in the boundary layer at all of the sites marine air dominates and ozone amounts are generally quite low (less than 25 ppb). The exception is near large population centers (Tokyo and Taipei but not Hong Kong) where pollution events can give amounts in excess of 80 ppb. During the TRACE-P intensive campaign period (February-April 2001) tropospheric ozone amounts were rather typical of those seen in the long-term records of the stations with multi-year soundings.

Oltmans, S. J.

Insights into Tropical Tropospheric Ozone from Satellite and Sonde Data

The first climatological overview of total, stratospheric and tropospheric ozone in the southern hemisphere tropical and subtropics is based on ozone sounding data from 10 sites comprising the Southern Hemisphere Additional OZonesondes (SHADOZ) network. Observations were made over: Ascension Island; Nairobi, Kenya; Irene, South Africa; Reunion Island; Watukosek, Java; Fiji; Tahiti; American Samoa; San Cristobal, Galapagos; Natal, Brazil. The data reside at: http://code916.gsfc.nasa.gov/Data_services/shadoz. SHADOZ ozone time-series and profiles give a perspective on tropical total, stratospheric and tropospheric ozone. Prominent features are highly variable tropospheric ozone and a zonal wave-one pattern in total (and tropospheric) column ozone. Dynamical and chemical influences appear to be of comparable magnitude though model studies are needed to quantify this. In addition to leading the SHADOZ network, we have been producing near-real tropical tropospheric ozone ('TTO') data from the Total Ozone Mapping Spectrometer (TOMS) since 1997 with Prof. Hudson and students at the University of Maryland: http://metosrv2.umd.edu/~tropo. Further perspective on the complexity of tropospheric ozone variability is shown using satellite observations.

Thompson, Anne M.

Feasibility of Sensing Tropospheric Ozone with MODIS 9.6 Micron Observations

With the infrared observations made by the Moderate Resolution Imaging Spectrometer (MODIS) on board the EOS-Aqua satellite, which include the 9.73 micron channel, a method is developed to deduce horizontal patterns of tropospheric ozone in cloud free conditions on a scale of about 100 km. It is assumed that on such small scale, at a given instant, horizontal changes in stratospheric ozone are small compared to that in the troposphere. From theoretical simulations it is found that uncertainties in the land surface emissivity and the vertical thermal stratification in the troposphere can lead to significant errors in the inferred tropospheric ozone. Because of this reason in order to derive horizontal patterns of tropospheric ozone in a given geographic area a tuning of this method is necessary with the help of a few dependent cases. After tuning, this method is applied to independent cases of MODIS data taken over Los Angeles basin in cloud free conditions to derive horizontal distribution of ozone in the troposphere. Preliminary results indicate that the derived patterns of ozone resemble crudely the patterns of surface ozone reported by EPA.

Prabhakara, C.

Discoveries about Tropospheric Ozone Pollution from Satellite and Sounding

We have been producing near-real time tropospheric ozone satellite maps from the TOMS (Total Ozone Mapping Spectrometer) sensor since 1997. This is most readily done for the tropics, where the stratospheric and tropospheric ozone column amounts can be discriminated readily. Maps for 1996-2000 for the operational Earth-Probe instrument reside at: chttp://www.atmos.umd.edu/-trope>. Pollution in the tropics is influenced by biomass burning and by transport patterns that favor recirculation and in other cases reflect climate variability like the El-Nino-Southern Oscillation [Thompson et al., 2001]. Time permitting, examples of mid-latitude, intercontinental transport of ozone pollution sensed by TOMS will be shown. The satellite view of chemical-dynamical interactions in tropospheric ozone is not adequate to capture vertical variability. Thus, in 1998, NASA's Goddard Space Flight Center and a team of international sponsors established the SHADOZ (Southern Hemisphere ADditional OZonesondes) project to address the gap in tropical ozone soundings. SHADOZ augments launches and provides a public archive of ozonesonde data from twelve tropical stations at http://croc.gsfc.nasa.gov/shadoz. Further insights into the role of chemical and dynamical influences have emerged from the first 4-5 years of SHADOZ data (less than 2000 ozone profiles): (a) highly variable tropospheric ozone; (b) a zonal wave-one pattern in tropospheric column ozone; (c) convective variability affects tropospheric ozone over the Indian and Pacific Ocean; (d) a "tropical Atlantic Paradox" appears in December-January-February.

Thompson, Anne M.

An Improved Retrieval of Tropospheric Nitrogen Dioxide from GOME

We present a retrieval of tropospheric nitrogen dioxide (NO2) columns from the Global Ozone Monitoring Experiment (GOME) satellite instrument that improves in several ways over previous retrievals, especially in the accounting of Rayleigh and cloud scattering. Slant columns, which are directly fitted without low-pass filtering or spectral smoothing, are corrected for an artificial offset likely induced by spectral structure on the diffuser plate of the GOME instrument. The stratospheric column is determined from NO2 columns over the remote Pacific Ocean to minimize contamination from tropospheric NO2. The air mass factor (AMF) used to convert slant columns to vertical columns is calculated from the integral of the relative vertical NO2 distribution from a global 3-D model of tropospheric chemistry driven by assimilated meteorological data (Global Earth Observing System (GEOS)-CHEM), weighted by altitude dependent scattering weights computed with a radiative transfer model (Linearized Discrete Ordinate Radiative Transfer), using local surface albedos determined from GOME observations at NO2 wavelengths. The AMF calculation accounts for cloud scattering using cloud fraction, cloud top pressure, and cloud optical thickness from a cloud retrieval algorithm (GOME Cloud Retrieval Algorithm). Over continental regions with high surface emissions, clouds decrease the AMT by 20- 30% relative to clear sky. GOME is almost twice as sensitive to tropospheric NO2 columns over ocean than over land. Comparison of the retrieved tropospheric NO2 columns for July 1996 with GEOS-CHEM values tests both the retrieval and the nitrogen oxide radical (NOx) emissions inventories used in GEOS-CHEM. Retrieved tropospheric NO2 columns over the United States, where NOx emissions are particularly well known, are within 18% of GEOS-CHEM columns and are strongly spatially correlated (r = 0.78, n = 288, p less than 0.005). Retrieved columns show more NO2 than GEOS-CHEM columns over the Transvaal region of South Africa and industrial regions of the northeast United States and Europe. They are lower over Houston, India, eastern Asia, and the biomass burning region of central Africa, possibly because of biases from absorbing aerosols.

Martin, Randall V.

Interpretation of TOMS Observations of Tropical Tropospheric Ozone with a Global Model and In Situ Observations

We interpret the distribution of tropical tropospheric ozone columns (TTOCs) from the Total Ozone Mapping Spectrometer (TOMS) by using a global three-dimensional model of tropospheric chemistry (GEOS-CHEM) and additional information from in situ observations. The GEOS-CHEM TTOCs capture 44% of the variance of monthly mean TOMS TTOCs from the convective cloud differential method (CCD) with no global bias. Major discrepancies are found over northern Africa and south Asia where the TOMS TTOCs do not capture the seasonal enhancements from biomass burning found in the model and in aircraft observations. A characteristic feature of these northern topical enhancements, in contrast to southern tropical enhancements, is that they are driven by the lower troposphere where the sensitivity of TOMS is poor due to Rayleigh scattering. We develop an efficiency correction to the TOMS retrieval algorithm that accounts for the variability of ozone in the lower troposphere. This efficiency correction increases TTOC's over biomass burning regions by 3-5 Dobson units (DU) and decreases them by 2-5 DU over oceanic regions, improving the agreement between CCD TTOCs and in situ observations. Applying the correction to CCD TTOCs reduces by approximately DU the magnitude of the "tropical Atlantic paradox" [Thompson et al, 2000], i.e. the presence of a TTOC enhancement over the southern tropical Atlantic during the northern African biomass burning season in December-February. We reproduce the remainder of the paradox in the model and explain it by the combination of upper tropospheric ozone production from lightning NOx, peristent subsidence over the southern tropical Atlantic as part of the Walker circulation, and cross-equatorial transport of upper tropospheric ozone from northern midlatitudes in the African "westerly duct." These processes in the model can also account for the observed 13-17 DU persistent wave-1 pattern in TTOCs with a maximum above the tropical Atlantic and a minimum over the tropical Pacific during all seasons. The photochemical effects of mineral dust have only a minor role on the modeled distribution of TTOCs, including over northern Africa, due to multiple competing effects. The photochemical effects of mineral dust globally decease annual mean OH concentrations by 9%. A global lightning NOx source of 6 Tg N yr(sup -1) in the model produces a simulation that is most consistent with TOMS and in situ observations.

Martin, Randall V.

Tropospheric and stratospheric ozone from assimilation of Aura data

Ozone is an atmospheric trace gas with multiple impacts on the environment. Global ozone fields are needed for air quality predictions, estimation of the ultraviolet radiation reaching the surface, climate-radiation studies, and may also have an impact on longer-term weather predictions. We estimate global ozone fields in the stratosphere and troposphere by combining the data from EOS Aura satellite with an ozone model using data assimilation. Ozone exhibits a large temporal variability in the lower stratosphere. Our previous work showed that assimilation of satellite data from limb-sounding geometry helps constrain ozone profiles in that region. We assimilated ozone data from the Aura Microwave Limb Sounder (MLS) and the Ozone Monitoring Instrument (OMI) into the ozone system at NASA's Global Modeling and Assimilation Office (GMAO). Ozone is transported within a general circulation model (GCM) which includes parameterizations for stratospheric photochemistry, tropospheric chemistry, and a simple scheme for heterogeneous ozone loss. The focus of this study is on the representation of ozone in the lower stratosphere and tropospheric ozone columns. We plan to extend studies of tropospheric ozone distribution through assimilation of ozone data from the Tropospheric Emission Spectrometer (TES). Comparisons with ozone sondes and occultation data show that assimilation of Aura data reproduces ozone gradients and variability in the lower stratosphere well. We proceed by separating the contributions to temporal changes in the ozone field into those that are due to the model and those that are due to the assimilation of Aura data. The impacts of Aura data are illustrated and their role in the representation of ozone variability in the lower stratosphere and troposphere is shown.

Stajner, I.

Effects of the 2004 El Nino on Tropospheric Ozone and Water Vapor

The global effects of the 2004 El Nino on tropospheric ozone and H2O based on Aura OM1 and MLS measurements are analyzed. Although it was a weak El Nino from a historical perspective, it produced significant changes in these parameters in tropical latitudes. Tropospheric ozone increased by 10-20% over most of the western Pacific region and decreased by about the same amount over the eastern Pacific region. H2O in the upper troposphere showed similar changes but with opposite sign. These zonal changes in tropospheric ozone and H2O are caused by the eastward shift in the Walker circulation in the tropical pacific region during El Nino. For the 2004 El Nino, biomass burning did not have a significant effect on the ozone budget in the troposphere unlike the 1997 El Nino. Zonally averaged tropospheric column ozone did not change significantly either globally or over the tropical and subtropical latitudes.

Chandra, S.

Future Climate Impacts of Direct Radiative Forcing Anthropogenic Aerosols, Tropospheric Ozone, and Long-lived Greenhouse Gases

Long-lived greenhouse gases (GHGs) are the most important driver of climate change over the next century. Aerosols and tropospheric ozone (O3) are expected to induce significant perturbations to the GHG-forced climate. To distinguish the equilibrium climate responses to changes in direct radiative forcing of anthropogenic aerosols, tropospheric ozone, and GHG between present day and year 2100, four 80-year equilibrium climates are simulated using a unified tropospheric chemistry-aerosol model within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) 110. Concentrations of sulfate, nitrate, primary organic (POA) carbon, secondary organic (SOA) carbon, black carbon (BC) aerosols, and tropospheric ozone for present day and year 2100 are obtained a priori by coupled chemistry-aerosol GCM simulations, with emissions of aerosols, ozone, and precursors based on the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenario (SRES) A2. Changing anthropogenic aerosols, tropospheric ozone, and GHG from present day to year 2100 is predicted to perturb the global annual mean radiative forcing by +0.18 (considering aerosol direct effects only), +0.65, and +6.54 W m(sup -2) at the tropopause, and to induce an equilibrium global annual mean surface temperature change of +0.14, +0.32, and +5.31 K, respectively, with the largest temperature response occurring at northern high latitudes. Anthropogenic aerosols, through their direct effect, are predicted to alter the Hadley circulation owing to an increasing interhemispheric temperature gradient, leading to changes in tropical precipitation. When changes in both aerosols and tropospheric ozone are considered, the predicted patterns of change in global circulation and the hydrological cycle are similar to those induced by aerosols alone. GHG-induced climate changes, such as amplified warming over high latitudes, weakened Hadley circulation, and increasing precipitation over the Tropics and high latitudes, are consistent with predictions of a number of previous GCM studies. Finally, direct radiative forcing of anthropogenic aerosols is predicted to induce strong regional cooling over East and South Asia. Wintertime rainfall over southeastern China and the Indian subcontinent is predicted to decrease because of the increased atmospheric stability and decreased surface evaporation, while the geographic distribution of precipitation is also predicted to be altered as a result of aerosol-induced changes in wind flow.

Chen, Wei-Ting

Laser Sounder for Global Measurement of CO2 Concentrations in the Troposphere from Space

Measurements of tropospheric CO2 abundance with global-coverage, a few hundred km spatial and monthly temporal resolution are needed to quantify processes that regulate CO2 storage by the land and oceans. The Orbiting Carbon Observatory (OCO) is the first space mission focused on atmospheric CO2 for measuring total column CO, and O2 by detecting the spectral absorption in reflected sunlight. The OCO mission is an essential step, and will yield important new information about atmospheric CO2 distributions. However there are unavoidable limitations imposed by its measurement approach. These include best accuracy only during daytime at moderate to high sun angles, interference by cloud and aerosol scattering, and limited signal from CO2 variability in the lower tropospheric CO2 column. We have been developing a new laser-based technique for the remote measurement of the tropospheric CO2 concentrations from orbit. Our initial goal is to demonstrate a lidar technique and instrument technology that will permit measurements of the CO2 column abundance in the lower troposphere from aircraft. Our final goal is to develop a space instrument and mission approach for active measurements of the CO2 mixing ratio at the 1-2 ppmv level. Our technique is much less sensitive to cloud and atmospheric scattering conditions and would allow continuous measurements of CO2 mixing ratio in the lower troposphere from orbit over land and ocean surfaces during day and night. Our approach is to use the 1570nm CO2 band and a 3-channel laser absorption spectrometer (i.e. lidar used an altimeter mode), which continuously measures at nadir from a near polar circular orbit. The approach directs the narrow co-aligned laser beams from the instrument's lasers toward nadir, and measures the energy of the laser echoes reflected from land and water surfaces. It uses several tunable fiber laser transmitters which allowing measurement of the extinction from a single selected CO2 absorption line in the 1570 nm band. This band is free from interference from other gases and has temperature insensitive absorption lines. During the measurement the lasers are tuned on- and off- a selected CO2 line near 1572 nm and a selected O2 line near 768 nm in the Oxygen A band at kHz rates. The lasers use tunable diode seed lasers followed by fiber amplifiers, and have spectral widths much narrower than the gas absorption lines. The receiver uses a 1-m diameter telescope and photon counting detectors and measures the background light and energies of the laser echoes from the surface. The extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on and offline surface echo via the differential optical absorption technique. Our technique rapidly alternates between several on-line wavelengths set to the sides of the selected gas absorption lines. It exploits the atmospheric pressure broadening of the lines to weight the measurement sensitivity to the atmospheric column below 5 km. This maximizes sensitivity to CO2 in the boundary layer, where variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column will use an identical approach with an O2 line. Thee laser frequencies are tunable and have narrow (MHz) line widths. In combination with sensitive photon counting detectors these enables much higher spectral resolution and precision than is possible with passive spectrometer. 1aser backscatter profiles are also measured, which permits identifying measurements made to cloud tops and through aerosol layers. The measurement approach using lasers in common-nadir-zenith path allows retrieving CO2 column mixing ratios in the lower troposphere irrespective of sun angle. Pulsed laser signals, time gated receiver and a narrow receiver field-of-view are used to isolate the surface laser echo signals and to exclude photons scattered from clouds and aerosols. Nonetheless, the optical absorption change due to a change of a few ppO2 is small, <1 % which makes achieving the needed measurement sensitivities and stabilities quite challenging. Measurement SNRs and stabilities of >600:1 are needed to estimate CO2 mixing ratio at the 1-2 ppm level. We have calculated characteristics of the technique and have demonstrated aspects of the laser, detector and receiver approaches in th e laboratory We have also measured O2 in an absorption cell, and made C02 measurements over a 400 m long (one way) horizontal path using a sensor breadboard. We will describe these and more details of our approach in the paper.

Abshire, James B.

Evidence of Convective Redistribution of Carbon Monoxide in Aura Tropospheric Emission Sounder (TES) and Microwave Limb Sounder (MLS) Observations

Vertical convective transport is a key element of the tropospheric circulation. Convection lofts air from the boundary layer into the free troposphere, allowing surface emissions to travel much further, and altering the rate of chemical processes such as ozone production. This study uses satellite observations to focus on the convective transport of CO from the boundary layer to the mid and upper troposphere. Our hypothesis is that strong convection associated with high rain rate regions leads to a correlation between mid level and upper level CO amounts. We first test this hypothesis using the Global Modeling Initiative (GMI) chemistry and transport model. We find the correlation is robust and increases as the precipitation rate (the strength of convection) increases. We next examine three years of CO profiles from the Tropospheric Emission Sounder (TES) and Microwave Limb Sounder (MLS) instruments aboard EOS Aura. Rain rates are taken from the Tropical Rainfall Measuring Mission (TRMM) 3B-42 multi-satellite product. Again we find a correlation between mid-level and upper tropospheric CO, which increases with rain rate. Our result shows the critical importance of tropical convection in coupling vertical levels of the troposphere in the transport of trace gases. The effect is seen most clearly in strong convective regions such as the Inter-tropical Convergence Zone.

Manyin, Michael

Modeling and Observations of the Response of Tropical Tropospheric Ozone to ENSO

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere, Recent results have revealed an ENSO induced wave-1 anomaly in observed tropical tropospheric column ozone, This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this result using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years, An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region, We will show targeted comparisons with SHADOZ ozonesondes over these regions to provide insight into the vertical structure. Also, comparisons with NASA's Aura satellite Microwave Limb Sounder (MLS) and Tropospheric Emissions Spectrometer (TES) instruments and other appropriate data sets will be shown. In addition, the water vapor response to ENSO will be compared to help illuminate its role relative to dynamics in impacting ozone concentrations. These results indicate that the tropospheric ozone response to ENSO is potentially a very useful chemistry-climate diagnostic and should be considered in future modeling assessments.

Oman, L. D.

The Response of Tropospheric Ozone to ENSO in Observations and a Chemistry-Climate Simulation

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere. Recent results have revealed an ENSO induced wave-l anomaly in observed tropical tropospheric column ozone. This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this result using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years. An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region. We will show targeted comparisons with observations from NASA's Aura satellite Microwave Limb Sounder (MLS), and the Tropospheric Emissions Spectrometer (TES) to provide insight into the vertical structure of ozone changes. The tropospheric ozone response to ENSO could be a useful chemistry-climate model evaluation tool and should be considered in future modeling assessments.

Oman, L. D.

Global Assimilation of EOS-Aura Data as a Means of Mapping Ozone Distribution in the Lower Stratosphere and Troposphere

Ozone in the lower stratosphere and the troposphere plays an important role in forcing the climate. However, the global ozone distribution in this region is not well known because of the sparse distribution of in-situ data and the poor sensitivity of satellite based observations to the lowermost of the atmosphere. The Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) instruments on EOS-Aura provide information on the total ozone column and the stratospheric ozone profile. This data has been assimilated into NASA s Global Earth Observing System, Version 5 (GEOS-5) data assimilation system (DAS). We will discuss the results of assimilating three years of OMI and MLS data into GEOS-5. This data was assimilated alongside meteorological observations from both conventional sources and satellite instruments. Previous studies have shown that combining observations from these instruments through the Trajectory Tropospheric Ozone Residual methodology (TTOR) or using data assimilation can yield useful, yet low biased, estimates of the tropospheric ozone budget. We show that the assimilated ozone fields in this updated version of GEOS-5 exhibit an excellent agreement with ozone sonde and High Resolution Dynamics Limb Sounder (HIRDLS) data in the lower stratosphere in terms of spatial and temporal variability as well as integrated ozone abundances. Good representation of small-scale vertical features follows from combining the MLS data with the assimilated meteorological fields. We then demonstrate how this information can be used to calculate the Stratosphere - Troposphere Exchange of ozone and its contribution to the tropospheric ozone column in GEOS-5. Evaluations of tropospheric ozone distributions from the assimilation will be made by comparisons with sonde and other in-situ observations.

Wargan, Krzysztof

Stratosphere-to-Troposphere Transport Revealed by Ground-based Lidar and Ozonesonde at a Midlatitude Site

This paper presents ozone structures measured by a ground-based ozone lidar and ozonesonde at Huntsville, Alabama, on 27-29 April 2010 originating from a stratosphere-to-troposphere transport event associated with a cutoff cyclone and tropopause fold. In this case, the tropopause reached 6 km and the stratospheric intrusion resulted in a 2-km thick elevated ozone layer with values between 70 and 85 ppbv descending from the 306-K to 298-K isentropic surface at a rate of 5 km day1. The potential temperature was provided by a collocated microwave profiling radiometer. We examine the corresponding meteorological fields and potential vorticity (PV) structures derived from the analysis data from the North American Mesoscale model. The 2-PVU (PV unit) surface, defined as the dynamic tropopause, is able to capture the variations of the ozone tropopause estimated from the ozonesonde and lidar measurements. The estimated ozone/PV ratio, from the measured ozone and model derived PV, for the mixing layer between the troposphere and stratosphere is approximately 41 ppbv/PVU with an uncertainty of approximately 33%. Within two days, the estimated mass of ozone irreversibly transported from the stratospheric into the troposphere is between 0.07 Tg (0.9 10(exp33) molecules) and 0.11 Tg (1.3 10(exp33) molecules) with an estimated uncertainty of 59%. Tropospheric ozone exhibited enormous variability due to the complicated mixing processes. Low ozone and large variability were observed in the mid-troposphere after the stratospheric intrusion due to the westerly advection including the transition from a cyclonic system to an anticyclonic system. This study using high temporal and vertical-resolution measurements suggests that, in this case, stratospheric air quickly lost its stratospheric characteristics once it is irreversibly mixed down into the troposphere.

Kuang, Shi

Tropospheric Bromine Chemistry: Implications for Present and Pre-industrial Ozone and Mercury

We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by <1-8 nmol/mol (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4 %. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

bromine

Active and Widespread Halogen Chemistry in the Tropical and Subtropical Free Troposphere

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10degN to 40degS), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (approx.3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

Wang, Siyuan

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 2, resulting in OHCOL approx.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.

Hydroxyl radical