Effect of sulfate aerosol on tropospheric NOx and ozone budgets: Model simulations and TOPSE evidence

The distributions of NOx and O3 are analyzed during TOPSE (Tropospheric Ozone Production about the Spring Equinox). In this study these data are compared with the calculations of a global chemical/transport model (Model for OZone And Related chemical Tracers (MOZART)). Specifically, the effect that hydrolysis of N2O5 on sulfate aerosols has on tropospheric NOx and O3 budgets is studied. The results show that without this heterogeneous reaction, the model significantly overestimates NOx concentrations at high latitudes of the Northern Hemisphere (NH) in winter and spring in comparison to the observations during TOPSE; with this reaction, modeled NOx concentrations are close to the measured values. This comparison provides evidence that the hydrolysis of N2O5 on sulfate aerosol plays an important role in controlling the tropospheric NOx and O3 budgets. The calculated reduction of NOx attributed to this reaction is 80 to 90% in winter at high latitudes over North America. Because of the reduction of NOx, O3 concentrations are also decreased. The maximum O3reduction occurs in spring although the maximum NOx reduction occurs in winter when photochemical O3 production is relatively low. The uncertainties related to uptake coefficient and aerosol loading in the model is analyzed. The analysis indicates that the changes in NOxdue to these uncertainties are much smaller than the impact of hydrolysis of N2O5 on sulfate aerosol. The effect that hydrolysis of N2O5 on global NOx and O3 budgets are also assessed by the model. The results suggest that in the Northern Hemisphere, the average NOx budget decreases 50% due to this reaction in winter and 5% in summer. The average O3 budget is reduced by 8% in winter and 6% in summer. In the Southern Hemisphere (SH), the sulfate aerosol loading is significantly smaller than in the Northern Hemisphere. As a result, sulfate aerosol has little impact on NOx and O3 budgets of the Southern Hemisphere

Age spectra and other transport diagnostics in the North American monsoon UTLS from SEAC4^{4}RS in situ trace gas measurements

The upper troposphere and lower stratosphere (UTLS) region during the summer monsoon season over North America (NAM) is influenced by the transport of air from a variety of source regions over a wide range of timescales (hours to years). Age spectra are useful for characterizing the transport into such a region, and in this study we use and build on recently developed techniques to infer age spectra from trace gas measurements with photochemical lifetimes from days to centuries. We show that the measurements taken by the whole-air sampler instrument during the SEAC$^{4}$RS campaign can be used to derive not only age spectra, but also path-integrated lifetimes of each of the trace gases and partitioning between North American and tropical surface source origins. The method used here can also clearly identify and adjust for measurement outliers that were influenced by polluted surface source regions. The results are generally consistent with expected transport features of the NAM but also provide a range of transport diagnostics (age spectra, trace gas lifetimes and surface source regions) that have not previously been computed solely from in situ measurements. These methods may be applied to many other existing in situ datasets, and the transport diagnostics can be compared with chemistry–climate model transport in the UTLS

Modelling the Inorganic Bromine Partitioning in the Tropical Tropopause over the Pacific Ocean

The stratospheric inorganic bromine burden (Bry) arising from the degradation of brominated very short-lived organic substances (VSL org ), and its partitioning between reactive and reservoir species, is needed for a comprehensive assessment of the ozone depletion potential of brominated trace gases. Here we present modelled inorganic bromine abundances over the Pacific tropical tropopause based on aircraft observations of VSL org of two campaigns of the Airborne Tropical TRopopause EXperiment (ATTREX 2013 carried out over eastern Pacific and ATTREX 2014 carried out over the western Pacific) and chemistry-climate simulations (along ATTREX flight tracks) using the specific meteorology prevailing. Using the Community Atmosphere Model with Chemistry (CAM-Chem), we model that BrO and Br are the daytime dominant species. Integrated across all ATTREX flights BrO represents ~ 43 % and 48 % of daytime Bry abundance at 17 km over the Western and Eastern Pacific, respectively. The results also show zones where Br/BrO >1 depending on the solar zenith angle (SZA), ozone concentration and temperature. On the other hand, BrCl and BrONO 2 were found to be the dominant night-time species with ~ 61% and 56 % of abundance at 17 km over the Western and Eastern Pacific, respectively. The western-to-eastern differences in the partitioning of inorganic bromine are explained by different abundances of ozone (O3), nitrogen dioxide (NO2) , and total inorganic chlorine (Cly).Fil: Navarro, María A.. University of Miami; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Universidad Tecnologica Nacional. Facultad Regional Mendoza. Secretaría de Ciencia, Tecnología y Postgrado; ArgentinaFil: Atlas, Elliot. University of Miami; Estados UnidosFil: Rodriguez Lloeveras, Xavier. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Kinnison, Douglas E.. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Lamarque, Jean Francois. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Tilmes, Simone. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Thornberry, Troy. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados UnidosFil: Rollins, Andrew. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados UnidosFil: Elkins, James W.. Earth System Research Laboratory; Estados UnidosFil: Hintsa, Eric J.. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados UnidosFil: Moore, Fred L.. State University of Colorado at Boulder; Estados Unidos. Earth System Research Laboratory; Estados Unido

Observations of ozone-poor air in the tropical tropopause layer

Ozonesondes reaching the tropical tropopause layer (TTL) over the west Pacific have occasionally measured layers of very low ozone concentrations - less than 15 ppbv - raising the question of how prevalent such layers are and how they are formed. In this paper, we examine aircraft measurements from the Airborne Tropical Tropopause Experiment (ATTREX), the Coordinated Airborne Studies in the Tropics (CAST) and the Convective Transport of Active Species in the Tropics (CONTRAST) experiment campaigns based in Guam in January-March 2014 for evidence of very low ozone concentrations and their relation to deep convection. The study builds on results from the ozonesonde campaign conducted from Manus Island, Papua New Guinea, as part of CAST, where ozone concentrations as low as 12 ppbv were observed between 100 and 150 hPa downwind of a deep convective complex. TTL measurements from the Global Hawk unmanned aircraft show a marked contrast between the hemispheres, with mean ozone concentrations in profiles in the Southern Hemisphere between 100 and 150 hPa of between 10.7 and 15.2 ppbv. By contrast, the mean ozone concentrations in profiles in the Northern Hemisphere were always above 15.4 ppbv and normally above 20 ppbv at these altitudes. The CAST and CONTRAST aircraft sampled the atmosphere between the surface and 120 hPa, finding very low ozone concentrations only between the surface and 700 hPa; mixing ratios as low as 7 ppbv were regularly measured in the boundary layer, whereas in the free troposphere above 200 hPa concentrations were generally well in excess of 15 ppbv. These results are consistent with uplift of almost-unmixed boundary-layer air to the TTL in deep convection. An interhemispheric difference was found in the TTL ozone concentrations, with values < 15 ppbv measured extensively in the Southern Hemisphere but seldom in the Northern Hemisphere. This is consistent with a similar contrast in the low-level ozone between the two hemispheres found by previous measurement campaigns. Further evidence of a boundary-layer origin for the uplifted air is provided by the anticorrelation between ozone and halogenated hydrocarbons of marine origin observed by the three aircraft

Reactive nitrogen budget during the NASA SONEX Mission

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of reactive nitrogen in the upper troposphere (8–12 km altitude). The median measured total reactive nitrogen (NOy) mixing ratio was 425 parts per trillion by volume (pptv). A data set merged to the HNO3 measurement time resolution was used to calculate NOy (NOy sum) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing it to measured NOy (NOy meas.). Comparisons were done for tropospheric air (O3 \u3c100 parts per billion by volume (ppbv)) and stratospherically influenced air (O3 \u3e 100 ppbv) with both showing good agreement between NOy sum and NOy meas. (slope \u3e0.9 and r² ≈ 0.9). The total reactive nitrogen budget in the upper troposphere over the North Atlantic appears to be dominated by a mixture of NOx (NO + NO2), HNO3, and PAN. In tropospheric air median values of NOx/NOywere ≈ 0.25, HNO3/NOy ≈ 0.35 and PAN/NOy ≈ 0.17. Particulate NO3− and alkyl nitrates together composed \u3c10% of NOy, while model estimated HNO4 averaged 12%. For the air parcels sampled during SONEX, there does not appear to be a large reservoir of unidentified NOy compounds

Inverse modelling of carbonyl sulfide: implementation, evaluation and implications for the global budget

Carbonyl sulfide (COS) has the potential to be used as a climate diagnostic due to its close coupling to the biospheric uptake of CO2 and its role in the formation of stratospheric aerosol. The current understanding of the COS budget, however, lacks COS sources, which have previously been allocated to the tropical ocean. This paper presents a first attempt at global inverse modelling of COS within the 4-dimensional variational data-assimilation system of the TM5 chemistry transport model (TM5-4DVAR) and a comparison of the results with various COS observations. We focus on the global COS budget, including COS production from its precursors carbon disulfide (CS2) and dimethyl sulfide (DMS). To this end, we implemented COS uptake by soil and vegetation from an updated biosphere model (Simple Biosphere Model-SiB4). In the calculation of these fluxes, a fixed atmospheric mole fraction of 500 pmol mol-1 was assumed. We also used new inventories for anthropogenic and biomass burning emissions. The model framework is capable of closing the COS budget by optimizing for missing emissions using NOAA observations in the period 2000-2012. The addition of 432 Gg a-1 (as S equivalents) of COS is required to obtain a good fit with NOAA observations. This missing source shows few year-to-year variations but considerable seasonal variations. We found that the missing sources are likely located in the tropical regions, and an overestimated biospheric sink in the tropics cannot be ruled out due to missing observations in the tropical continental boundary layer. Moreover, high latitudes in the Northern Hemisphere require extra COS uptake or reduced emissions. HIPPO (HIAPER Pole-to-Pole Observations) aircraft observations, NOAA airborne profiles from an ongoing monitoring programme and several satellite data sources are used to evaluate the optimized model results. This evaluation indicates that COS mole fractions in the free troposphere remain underestimated after optimization. Assimilation of HIPPO observations slightly improves this model bias, which implies that additional observations are urgently required to constrain sources and sinks of COS. We finally find that the biosphere flux dependency on the surface COS mole fraction (which was not accounted for in this study) may substantially lower the fluxes of the SiB4 biosphere model over strong-uptake regions. Using COS mole fractions from our inversion, the prior biosphere flux reduces from 1053 to 851 Gg a-1, which is closer to 738 Gg a-1 as was found by Berry et al. (2013). In planned further studies we will implement this biosphere dependency and additionally assimilate satellite data with the aim of better separating the role of the oceans and the biosphere in the global COS budget..</p

Transport of short-lived halocarbons to the stratosphere over the Pacific Ocean

The effectiveness of transport of short-lived halocarbons to the upper troposphere and lower stratosphere remains an important uncertainty in quantifying the supply of ozone-depleting substances to the stratosphere. In early 2014, a major field campaign in Guam in the western Pacific, involving UK and US research aircraft, sampled the tropical troposphere and lower stratosphere. The resulting measurements of CH3I, CHBr3 and CH2Br2 are compared here with calculations from a Lagrangian model. This methodology benefits from an updated convection scheme that improves simulation of the effect of deep convective motions on particle distribution within the tropical troposphere. We find that the observed CH3I, CHBr3 and CH2Br2 mixing ratios in the tropical tropopause layer (TTL) are consistent with those in the boundary layer when the new convection scheme is used to account for convective transport. More specifically, comparisons between modelled estimates and observations of short-lived CH3I indicate that the updated convection scheme is realistic up to the lower TTL but is less good at reproducing the small number of extreme convective events in the upper TTL. This study consolidates our understanding of the transport of short-lived halocarbons to the upper troposphere and lower stratosphere by using improved model calculations to confirm consistency between observations in the boundary layer, observations in the TTL and atmospheric transport processes. Our results support recent estimates of the contribution of short-lived bromocarbons to the stratospheric bromine budget

Isotopic ordering in atmospheric O2 as a tracer of ozone photochemistry and the tropical atmosphere

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as Δ36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher Δ36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower Δ36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-Δ36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where Δ36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in Δ36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a ±10% range since 1978

Methyl, ethyl, and propyl nitrates: global distribution and impacts on reactive nitrogen in remote marine environments

Alkyl nitrates (RONO2) are important components of tropospheric reactive nitrogen that serve as reservoirs for nitrogen oxides (NOx ≡ NO + NO2). Here we implement a new simulation of atmospheric methyl, ethyl, and propyl nitrate chemistry in a global chemical transport model (GEOS‐Chem). We show that the model can reproduce the spatial and seasonal variability seen in a 20‐year ensemble of airborne observations. Methyl nitrate accounts for 17 Gg N globally, with maxima over the tropical Pacific and Southern Ocean. Propyl nitrate is enhanced in continental boundary layers, but its global impact (6 Gg N) is limited by a short lifetime (8 days, versus 26 days for methyl nitrate and 14 days for ethyl nitrate) that inhibits long‐range transport. Ethyl nitrate has the smallest impact of the three species (4 Gg N). We find that methyl nitrate is the dominant form of reactive nitrogen (NOy) in the Southern Ocean marine boundary layer, where its addition to the model corrects a large NOy underestimate in austral winter relative to recent aircraft data. RONO2 serve as a small net NOx source to the marine troposphere, except in the northern mid‐latitudes where the continental outflow is enriched in precursors that promote NOx loss via RONO2 formation. Recent growth in NOx emissions from East Asia has enhanced the role of RONO2 as a source of NOx to the remote free troposphere. This relationship implies projected future NOx emissions growth across the southern hemisphere may further enhance the importance of RONO2 as a NOx reservoir