Potential significance of photoexcited NO2 on global air quality with the NMMB/BSC chemical transport model

Atmospheric chemists have recently focused on the relevance of the NO2* + H2O → OH + HONO reaction to local air quality. This chemistry has been considered not relevant for the troposphere from known reaction rates until nowadays. New experiments suggested a rate constant of 1.7 × 10−13 cm3 molecule−1 s−1, which is an order of magnitude faster than the previously estimated upper limit of 1.2 × 10−14 cm3 molecule−1 s−1, determined by Crowley and Carl (1997). Using the new global model, NMMB/BSC Chemical Transport Model (NMMB/BSC-CTM), simulations are presented that assess the potential significance of this chemistry on global air quality. Results show that if the NO2* chemistry is considered following the upper limit kinetics recommended by Crowley and Carl (1997), it produces an enhancement of ozone surface concentrations of 4–6 ppbv in rural areas and 6–15 ppbv in urban locations, reaching a maximum enhancement of 30 ppbv in eastern Asia. Moreover, NO2 enhancements are minor (xemissions are present; however, differences are small in most parts of the globe

Diurnal Variation in Mars Equatorial Odd Oxygen Species: Chemical Production and Loss Mechanisms

Odd oxygen (O, O(¹D), O₃) abundance and its variability in the Martian atmosphere results from complex physical and chemical interactions among atmospheric species, which are driven mainly by solar radiation and atmospheric conditions. Although our knowledge of Mars’ ozone distribution and variability has been significantly improved with the arrival of several recent orbiters, the data acquired by such missions is not enough to properly characterize its diurnal variation. Thus, photochemical models are useful tools to assist in such a characterization. Here, both the Martian ozone vertical distribution and its diurnal variation for equatorial latitudes are studied, using the JPL/Caltech one-dimensional photochemical model and diurnally-variable atmospheric profiles. The chosen equatorial latitude-region is based on the recent and future plans of NASA and other agencies to study this region by different surface missions. A production and loss analysis is performed in order to characterize the chemical mechanisms that drive odd oxygen's diurnal budget and variability on Mars making use of the comprehensive chemistry implemented in the model. The diurnal variation shows large differences in the abundance between daytime and nighttime; and variable behavior depending on the atmospheric layer. The photolysis-driven ozone diurnal profile is obtained at the surface, whilst a sharp decrease is obtained in the upper troposphere at daytime, which originates from the large differences in atomic oxygen abundances between atmospheric layers. Finally, no clear anticorrelation between ozone and water vapor is found in the diurnal cycle, contrary to the strong correlation observed by orbiters on a seasonal timescale

Modeling the Sources and Chemistry of Polar Tropospheric Halogens (Cl, Br, and I) Using the CAM-Chem Global Chemistry-Climate Model

31 pags., 12 figs., 6 tabs. -- Open Access funded by Creative Commons Atribution Licence 4.0. -- jame20925-sup-0001_Supporting_Information.pdfCurrent chemistry climate models do not include polar emissions and chemistry of halogens. This work presents the first implementation of an interactive polar module into the very short-lived (VSL) halogen version of the Community Atmosphere Model with Chemistry (CAM-Chem) model. The polar module includes photochemical release of molecular bromine, chlorine, and interhalogens from the sea-ice surface, and brine diffusion of iodine biologically produced underneath and within porous sea-ice. It also includes heterogeneous recycling of inorganic halogen reservoirs deposited over fresh sea-ice surfaces and snow-covered regions. The polar emission of chlorine, bromine, and iodine reach approximately 32, 250, and 39 Gg/year for Antarctica and 33, 271, and 4 Gg/year for the Arctic, respectively, with a marked seasonal cycle mainly driven by sunlight and sea-ice coverage. Model results are validated against polar boundary layer measurements of ClO, BrO, and IO, and satellite BrO and IO columns. This validation includes satellite observations of IO over inner Antarctica for which an iodine “leapfrog” mechanism is proposed to transport active iodine from coastal source regions to the interior of the continent. The modeled chlorine and bromine polar sources represent up to 45% and 80% of the global biogenic VSL and VSL emissions, respectively, while the Antarctic sea-ice iodine flux is ~10 times larger than that from the Southern Ocean. We present the first estimate of the contribution of polar halogen emissions to the global tropospheric halogen budget. CAM-Chem includes now a complete representation of halogen sources and chemistry from pole-to-pole and from the Earth's surface up to the stratopause.This study has been funded by the European Research Council Executive Agency under the European Union′s Horizon 2020 Research and Innovation program (Project “ERC‐2016‐COG 726349 CLIMAHAL”) and supported by the Consejo Superior de Investigaciones Científicas (CSIC) of Spain. Computing resources, support, and data storage are provided and maintained by the Computational and Information System Laboratory from the National Center of Atmospheric Research (CISL,2017). R. P. F. would like to thank CONICET, ANPCyT (PICT 2015‐0714), UNCuyo (SeCTyP M032/3853), and UTN (PID 4920‐194/2018) for the financial support. Partial funding for this work was provided by the Korea Polar Research Institute (KOPRI) project (PE18200). The contributions of the University of Bremen have been supported by the State of Bremen, the German Research Foundation (DFG), the German Aerospace (DLR), and the European Space Agency (ESA). We gratefully acknowledge the funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) —Projektnummer 268020496—TRR 172, within the Transregional Collaborative Research Center “ArctiC Amplification: Climate Relevant Atmospheric and SurfaCe Processes,and Feedback Mechanisms (AC)3 ” in subproject C03 as well as the support by the University of Bremen Institutional Strategy Measure M8 in the framework of the DFG Excellence Initiative

200-year ice core bromine reconstruction at Dome C (Antarctica): observational and modelling results

Bromine enrichment (Brenr) has been proposed as an ice core proxy for past sea-ice reconstruction. Understanding the processes that influence bromine preservation in the ice is crucial to achieve a reliable interpretation of ice core signals and to potentially relate them to past sea-ice variability. Here, we present a 210 years bromine record that sheds light on the main processes controlling bromine preservation in the snow and ice at Dome C, East Antarctic plateau. Using observations alongside a modelling approach, we demonstrate that the bromine signal is preserved at Dome C and it is not affected by the strong variations in ultraviolet radiation reaching the Antarctic plateau due to the stratospheric ozone hole. Based on this, we investigate whether the Dome C Brenr record can be used as an effective tracer of past Antarctic sea ice. Due to the limited time window covered by satellite measurements and the low sea-ice variability observed during the last 30 years in East Antarctica, we cannot fully validate Brenr as an effective proxy for past sea-ice reconstructions at Dome C.</p

A mechanism for biologically induced iodine emissions from sea ice

Ground- and satellite-based measurements have reported high concentrations of iodine monoxide (IO) in coastal Antarctica. The sources of such a large iodine burden in the coastal Antarctic atmosphere remain unknown. We propose a mechanism for iodine release from sea ice based on the premise that micro-algae are the primary source of iodine emissions in this environment. The emissions are triggered by the biological production of iodide (I^&minus;) and hypoiodous acid (HOI) from micro-algae (contained within and underneath sea ice) and their diffusion through sea-ice brine channels, ultimately accumulating in a thin brine layer (BL) on the surface of sea ice. Prior to reaching the BL, the diffusion timescale of iodine within sea ice is depth-dependent. The BL is also a vital component of the proposed mechanism as it enhances the chemical kinetics of iodine-related reactions, which allows for the efficient release of iodine to the polar boundary layer. We suggest that iodine is released to the atmosphere via three possible pathways: (1) emitted from the BL and then transported throughout snow atop sea ice, from where it is released to the atmosphere; (2) released directly from the BL to the atmosphere in regions of sea ice that are not covered with snowpack; or (3) emitted to the atmosphere directly through fractures in the sea-ice pack. To investigate the proposed biology–ice–atmosphere coupling at coastal Antarctica we use a multiphase model that incorporates the transport of iodine species, via diffusion, at variable depths, within brine channels of sea ice. Model simulations were conducted to interpret observations of elevated springtime IO in the coastal Antarctic, around the Weddell Sea. While a lack of experimental and observational data adds uncertainty to the model predictions, the results nevertheless show that the levels of inorganic iodine (i.e. I₂, IBr, ICl) released from sea ice through this mechanism could account for the observed IO concentrations during this timeframe. The model results also indicate that iodine may trigger the catalytic release of bromine from sea ice through phase equilibration of IBr. Considering the extent of sea ice around the Antarctic continent, we suggest that the resulting high levels of iodine may have widespread impacts on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere

A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile

Atmospheric chemical composition is crucial in determining a planet's atmospheric structure, stability, and evolution. Attaining a quantitative understanding of the essential chemical mechanisms governing atmospheric composition is nontrivial due to complex interactions between chemical species. Trace species, for example, can participate in catalytic cycles - affecting the abundance of major and other trace gas species. Specifically, for Mars, such cycles dictate the abundance of its primary atmospheric constituent, carbon dioxide (CO2), but also for one of its trace gases, ozone (O3). The identification of chemical pathways/cycles by hand is extremely demanding; hence, the application of numerical methods, such as the Pathway Analysis Program (PAP), is crucial to analyze and quantitatively exemplify chemical reaction networks. Here, we carry out the first automated quantitative chemical pathway analysis of Mars' atmosphere with respect to O3 . PAP was applied to JPL/Caltech's 1-D updated photochemical Mars model's output data. We determine all significant chemical pathways and their contribution to O3 production and consumption (up to 80 km) in order to investigate the mechanisms causing the characteristic shape of the O3 volume mixing ratio profile, i.e. a ground layer maximum and an ozone layer at ~50 km. These pathways explain why an O3 layer is present, why it is located at that particular altitude and what the different processes forming the near-surface and middle atmosphere O3 maxima are. Furthermore, we show that the Martian atmosphere can be divided into two chemically distinct regions according to the O(3P):O3 ratio. In the lower region (below approximately 24 km altitude) O3 is the most abundant Ox (= O3 + O(3P)) species. In the upper region (above approximately 24 km altitude), where the O3 layer is located, O(3P) is the most abundant Ox species. Earlier results concerning the formation of O3 on Mars can now be explained with the help of chemical pathways leading to a better understanding of the vertical O3 profile

200-year ice core bromine reconstruction at Dome C (Antarctica): observational and modelling results

Abstract. Bromine enrichment (Brenr) has been proposed as an ice core proxy for past sea-ice reconstruction. Understanding the processes that influence bromine preservation in the ice is crucial to achieve a reliable interpretation of ice core signals and to potentially relate them to past sea-ice variability. Here, we present a 210 years bromine record that sheds light on the main processes controlling bromine preservation in the snow and ice at Dome C, East Antarctic plateau. Using observations alongside a modelling approach, we demonstrate that the bromine signal is preserved at Dome C and it is not affected by the strong variations in ultraviolet radiation reaching the Antarctic plateau due to the stratospheric ozone hole. Based on this, we investigate whether the Dome C Brenr record can be used as an effective tracer of past Antarctic sea ice. Due to the limited time window covered by satellite measurements and the low sea-ice variability observed during the last 30 years in East Antarctica, we cannot fully validate Brenr as an effective proxy for past sea-ice reconstructions at Dome C. </jats:p

Impact of Photoexcited NO2 on Global Air Quality with the NMMB/BSC Chemical Transport Model

Postprint (published version

Sources and chemistry of polar tropospheric halogens (Cl, Br, I) using the CAM-Chem Global Chemistry-Climate Model, links to netCDF files

Here, we present the first implementation of an interactive polar module into the halogen version of the CAM-Chem model with the intention of expanding the model applicability to the polar regions, besides its widely usage for atmospheric studies throughout the tropics and mid-latitudes. The state-of-the-art polar module considers full gas-phase and heterogeneous inorganic chlorine, bromine and iodine chemistry and sources, which adds up to the organic halogen emissions from the ocean surface (the so-called very short-lived (VSL) substances). The online sea-ice halogen sources depend on the seasonal variation of different types of icy surfaces and the intensity of radiation reaching the polar surface. Our results indicate that the contribution of polar halogen sources represents between 45 and 80% of the global biogenic VSL bromine and chlorine emissions, respectively; and that the Antarctic iodine sea-ice annual flux is ~10 times larger than the total iodine source arising from the Southern Ocean. This work provides, for the first time, quantitative estimates of the annual and seasonal flux strength of each halogen family from the Arctic and Antarctic, as well as their contribution to the global tropospheric halogen budget, highlighting the importance of including the contribution of polar tropospheric halogens in global chemistry-climate models