Impact of biogenic very short-lived bromine on the Antarctic ozone hole during the 21st century

Active bromine released from the photochemical decomposition of biogenic very short-lived bromocarbons (VSL_Br ) enhances stratospheric ozone depletion. Based on a dual set of 1960-2100 coupled chemistry-climate simulations (i.e. with and without VSL Br ), we show that the maximum Antarctic ozone hole depletion increases by up to 14% when natural VSLBr are considered, in better agreement with ozone observations. The impact of the additional 5 pptv VSL Br on Antarctic ozone is most evident in the periphery of the ozone hole, producing an expansion of the ozone hole area of ~5 million km 2 , which is equivalent in magnitude to the recently estimated Antarctic ozone healing due to the implementation of the Montreal Protocol. We find that the inclusion of VSL Br in CAM-Chem does not introduce a significant delay of the modelled ozone return date to 1980 October levels, but instead affect the depth and duration of the simulated ozone hole. Our analysis further shows that total bromine-catalysed ozone destruction in the lower stratosphere surpasses that of chlorine by year 2070, and indicates that natural VSL Br chemistry would dominate Antarctic ozone seasonality before the end of the 21 st century. This work suggests a large influence of biogenic bromine on the future Antarctic ozone layer.Fil: Fernandez, Rafael Pedro. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; España. Universidad Tecnologica Nacional. Facultad Regional Mendoza. Secretaría de Ciencia, Tecnología y Postgrado; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: 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: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; Españ

A negative feedback between anthropogenic ozone pollution and enhanced ocean emissions of iodine

Naturally emitted from the oceans, iodine compounds efficiently destroy atmospheric ozone and reduce its positive radiative forcing effects in the troposphere. Emissions of inorganic iodine have been experimentally shown to depend on the deposition to the oceans of tropospheric ozone, whose concentrations have significantly increased since 1850 as a result of human activities. A chemistry-climate model is used herein to quantify the current ocean emissions of inorganic iodine and assess the impact that the anthropogenic increase in tropospheric ozone has had on the natural cycle of iodine in the marine environment since pre-industrial times. Our results indicate that the human-driven enhancement of tropospheric ozone has doubled the oceanic inorganic iodine emissions following the reaction of ozone with iodide at the sea surface. The consequent build-up of atmospheric iodine, with maximum enhancements of up to 70% with respect to pre-industrial times in continental pollution outflow regions, has in turn accelerated the ozone chemical loss over the oceans with strong spatial patterns. We suggest that this ocean-atmosphere interaction represents a negative geochemical feedback loop by which current ocean emissions of iodine act as a natural buffer for ozone pollution and its radiative forcing in the global marine environment.Fil: Prados Roman, C.. 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 Superior de Investigaciones Científicas. Instituto de Química Física; España. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Kinnison, Douglas E.. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Lamarque, Jean Francoise. National Center For Atmospheric Research. Amospheric Chemistry División; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; Españ

First observations of iodine oxide from space

We present retrievals of IO total columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) satellite instrument. We analyze data for October 2005 in the polar regions to demonstrate for the first time the capability to measure IO column abundances from space. During the period of analysis (i.e. Southern Hemisphere springtime), enhanced IO vertical columns over 3 × 10^(13) molecules cm^(−2) are observed around coastal Antarctica; by contrast during that time in the Artic region IO is consistently below the calculated instrumental detection limit for individual radiance spectra (2–4 × 10^(12) molecules cm^(−2) for slant columns). The levels reported here are in reasonably good agreement with previous ground‐based measurements at coastal Antarctica. These results also demonstrate that IO is widespread over sea‐ice covered areas in the Southern Ocean. The occurrence of elevated IO and its hitherto unrecognized spatial distribution suggest an efficient iodine activation mechanism at a synoptic scale over coastal Antarctica

Photolysis of frozen iodate salts as a source of active iodine in the polar environment

Reactive halogens play a key role in the oxidation capacity of the polar troposphere. However, sources and mechanisms, particularly those involving active iodine, are still poorly understood. In this paper, the photolysis of an atmospherically relevant frozen iodate salt has been experi mentally studied using infrared (IR) spectroscopy. The sam ples were generated at low temperatures in the presence of different amounts of water. The IR spectra have confirmed that, under near-ultraviolet–visible (UV–Vis) radiation, io date is efficiently photolysed. The integrated IR absorption coefficient of the iodate anion on the band at 750 cm−1 has been measured to be A = 9.8 ± 0.5 × 10−17 cm molecule−1 . The photolysis rate of the ammonium iodate salt was measured by monitoring the decay of ammonium or iodate IR bands (1430 and 750 cm−1 respectively) in the presence of a solar simulator. The absorption cross section of the liquid solutions of ammonium iodate at wavelengths relevant for the troposphere (250 to 400 nm) has been obtained and used to estimate the photolytic quantum yield for the frozen salt. Finally, using an atmospheric model, constrained with the experimental data, we suggest that the photolysis of iodate in frozen salt can potentially provide a pathway for the release of active iodine to the polar atmosphere

Chemical interactions between ship-originated air pollutants and ocean-emitted halogens

Ocean-going ships supply products from one region to another and contribute to the world's economy. Ship exhaust contains many air pollutants and results in significant changes in marine atmospheric composition. The role of Reactive Halogen Species (RHS) in the troposphere has received increasing recognition and oceans are the largest contributors to their atmospheric burden. However, the impact of shipping emissions on RHS and that of RHS on ship-originated air pollutants have not been studied in detail. Here, an updated WRF-Chem model is utilized to explore the chemical interactions between ship emissions and oceanic RHS over the East Asia seas in summer. The emissions and resulting chemical transformations from shipping activities increase the level of NO and NO2 at the surface, increase O3 in the South China Sea, but decrease O3 in the East China Sea. Such changes in pollutants result in remarkable changes in the levels of RHS as well as in their partitioning. The abundant RHS, in turn, reshape the loadings of air pollutants and those of the oxidants with marked patterns along the ship tracks. We, therefore, suggest that these important chemical interactions of ship-originated emissions with RHS should be considered in the environmental policy assessments of the role of shipping emissions in air quality and climate.Fil: Li, Qinyi. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael P.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Mahan, Anoop. No especifíca;Fil: Lopez, Ana Isabel. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Shanshan, Wang. Key Laboratory Atmospheric Particle Pollution Research; ChinaFil: Puliafito, Salvador Enrique. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Cuevas, Carlos A.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Saiz Lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaEGU General Assembly 2021AustriaEuropean Geosciences Unio

Role of Iodine Recycling on Sea-Salt Aerosols in the Global Marine Boundary Layer

Heterogeneous uptake of hypoiodous acid (HOI), the dominant inorganic iodine species in the marine boundary layer (MBL), on sea-salt aerosol (SSA) to form iodine monobromide and iodine monochloride has been adopted in models with assumed efficiency. Recently, field measurements have reported a much faster rate of this recycling process than previously assumed in models. Here, we conduct global model simulations to quantify the range of effects of iodine recycling within the MBL, using Conventional, Updated, and Upper-limit coefficients. When considering the Updated coefficient, iodine recycling significantly enhances gaseous inorganic iodine abundance (similar to 40%), increases halogen atom production rates (similar to 40% in I, >100% in Br, and similar to 60% in Cl), and reduces oxidant levels (-7% in O-3, -2% in OH, and -4% in HO2) compared to the simulation without the process. We appeal for further direct measurements of iodine species, laboratory experiments on the controlling factors, and multiscale simulations of iodine heterogeneous recycling.Peer reviewe

Detection of IO in subtropical Free Troposphere

Póster elaborado para la EGU General Assembly celebrada los del 3 al 8 de abril de 2011 en Viena

Seasonal impact of biogenic very short-lived bromocarbons on lowermost stratospheric ozone between 60° N and 60° S during the 21st century

Biogenic very short-lived bromocarbons (VSLBr) currently represent ∼25 % of the total stratospheric bromine loading. Owing to their much shorter lifetime compared to anthropogenic long-lived bromine (e.g. halons) and chlorine (e.g. chlorofluorocarbons), the impact of VSLBr on ozone peaks in the lowermost stratosphere, which is a key climatic and radiative atmospheric region. Here we present a modelling study of the evolution of stratospheric ozone and its chemical loss within the tropics and at mid-latitudes during the 21st century. Two different experiments are explored: considering and neglecting the additional stratospheric injection of 5 ppt biogenic bromine naturally released from the ocean. Our analysis shows that the inclusion of VSLBr results in a realistic stratospheric bromine loading and improves the agreement between the model and satellite observations of the total ozone column (TOC) for the 1980?2015 period at mid-latitudes. We show that the overall ozone response to VSLBr at mid-latitudes follows the stratospheric evolution of long-lived inorganic chlorine and bromine throughout the 21st century. Additional ozone loss due to VSLBr is maximized during the present-day period (1990?2010), with TOC differences of −8 DU (−3 %) and −5.5 DU (−2 %) for the Southern Hemisphere and Northern Hemisphere mid-latitudes (SH-MLs and NH-MLs), respectively. Moreover, the projected TOC differences at the end of the 21st century are ∼50 % lower than the values found for the present-day period.We find that seasonal VSLBr impact on lowermost stratospheric ozone at mid-latitude is influenced by the seasonality of the heterogeneous inorganic-chlorine reactivation processes on ice crystals. Indeed, due to the more efficient reactivation of chlorine reservoirs (mainly ClONO2 and HCl) within the colder SH-ML lowermost stratosphere, the seasonal VSLBr impact shows a small but persistent hemispheric asymmetry through the whole modelled period. Our results indicate that, although the overall VSLBr-driven ozone destruction is greatest during spring, the halogen-mediated (Halogx-Loss) ozone loss cycle in the mid-latitude lowermost stratosphere during winter is comparatively more efficient than the HOx cycle with respect to other seasons. Indeed, when VSLBr are considered, Halogx-Loss dominates wintertime lowermost stratospheric ozone loss at SH-MLs between 1985 and 2020, with a contribution of inter-halogen ClOx?BrOx cycles to Halogx-Loss of ∼50 %.Within the tropics, a small (<−2.5 DU) and relatively constant (∼−1 %) ozone depletion mediated by VSLBr is closely related to their fixed emissions throughout the modelled period. By including the VSLBr sources, the seasonal Halogx-Loss contribution to lowermost stratospheric ozone loss is practically dominated by the BrOx cycle, reflecting the low sensitivity of very short-lived (VSL) bromine to background halogen abundances to drive tropical stratospheric ozone depletion. We conclude that the link between biogenic bromine sources and seasonal changes in heterogeneous chlorine reactivation is a key feature for future projections of mid-latitude lowermost stratospheric ozone during the 21st century.Fil: Barrera, Javier Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; Argentina. Consejo Superior de Investigaciones Científicas; España. Universidad Tecnológica Nacional; ArgentinaFil: Iglesias Suarez, Fernando. Consejo Superior de Investigaciones Científicas; EspañaFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas; EspañaFil: Lamarque, Jean Francois. National Center for Atmospheric Research; Estados UnidosFil: Saiz-lopez, Alfonso. Consejo Superior de Investigaciones Científicas; Españ

A nocturnal atmospheric loss of CH2I2 in the remote marine boundary layer

This is the final version of the article. It was first available from Springer via http://dx.doi.org/10.1007/s10874-015-9320-6Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH?I?) and chloro-iodomethane (CH?ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH?I? and CH?ICl in air and of CH?I? in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH?I? was lower in amplitude than that of CH?ICl, despite its faster photolysis rate. We speculate that night-time loss of CH?I? occurs due to reaction with NO? radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k_(CH?I?+NO?) of ?4 ? 10??? cm? molecule?? s??; a previous kinetic study carried out at ?100 Torr found k_(CH?I?+NO?) of 4 ? 10??? cm? molecule?? s??. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/? 0.8 nmol m?? d?? for CH?I? and 3.7 +/? 0.8 nmol m?? d?? for CH?ICl), we show that the model overestimates night-time CH?I? by >60 % but reaches good agreement with the measurements when the CH?I?+ NO? reaction is included at 2?4 ? 10??? cm? molecule?? s??. We conclude that the reaction has a significant effect on CH?I? and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.LJC acknowledges NERC (NE/J00619X/1) and the National Centre for Atmospheric Science (NCAS) for funding. The laboratory work was supported by the NERC React-SCI (NE/K005448/1) and RONOCO (NE/F005466/1) grants

A 120 000-year record of sea ice in the North Atlantic?

Although it has been demonstrated that the speed and magnitude of recent Arctic sea ice decline is unprecedented for the past 1,450 years, few records are available to provide a paleoclimate context for Arctic sea ice extent. Here we present a 120 kyr record of bromine enrichment from the RECAP ice core, coastal East Greenland, and reconstruct past sea ice conditions in the North Atlantic as far north as the entrance of the Arctic Ocean (50–85° N). Bromine enrichment has been previously employed to reconstruct first-year sea ice (FYSI) in the Canadian Arctic over the last glacial cycle. We find that during the last deglaciation, the transition from multi-year sea ice (MYSI) to FYSI started at ∼ 17.6 kyr, synchronous with sea ice reductions observed in the eastern Nordic seas (Müller and Stein, 2014; Hoff et al., 2016) and with the increase of North Atlantic ocean temperature (Dokken and Jansen, 1999). FYSI reached its maximum extent at 12.4–11.8 kyr, after which open-water conditions started to dominate, as supported by sea ice records from the eastern Nordic seas and the North Icelandic shelf. Our results show that over the last 120,000 years, sea ice extent was greatest during Marine Isotope Stage (MIS) 2 and MIS4, with decreased levels during MIS3 and the onset of the last glacial period (late-MIS5). Sea ice extent during the last 10 kyr (Holocene/MIS1) has been less than at any time in the last 120 kyr