A mechanism for biologically-induced iodine emissions from sea-ice

International audienceOnly recently, ground- and satellite-based measurements have reported high concentrations of IO in coastal Antarctica. The sources of such a large iodine burden in the Antarctic atmosphere remain unknown. We propose a novel mechanism for iodine release from sea-ice surfaces. The release is triggered by the biological production of iodide (I-) and hypoiodous acid (HOI) from marine algae, contained within and underneath sea-ice, and their diffusion through sea-ice brine channels to accumulate in the quasi-liquid layer on the surface of sea-ice. A multiphase chemical model of polar atmospheric chemistry has been developed to investigate the biology-ice-atmosphere coupling in the polar environment. Model simulations were conducted to interpret recent observations of elevated IO in the coastal Antarctic springtime. The results show that the levels of inorganic iodine (i.e. I2, IBr, ICl) released from sea-ice through this mechanism account for the observed IO concentrations in the Antarctic springtime environment. 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 impact on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere

Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL): implications for NOx release from the Arctic and coastal Antarctic snowpack

We utilize a multiphase model, CON-AIR (<B>Con</B>densed Phase to <B>Air</B> Transfer Model), to show that the photochemistry of nitrate (NO₃^&minus;) in and on ice and snow surfaces, specifically the quasi-liquid layer (QLL), can account for NO_x volume fluxes, concentrations, and [NO]/[NO₂] (γ=[NO]/[NO₂]) measured just above the Arctic and coastal Antarctic snowpack. Maximum gas phase NO_x volume fluxes, concentrations and γ simulated for spring and summer range from 5.0&times;10⁴ to 6.4&times;10⁵ molecules cm^&minus;3 s^&minus;1, 5.7&times;10⁸ to 4.8&times;10⁹ molecules cm^&minus;3, and ~0.8 to 2.2, respectively, which are comparable to gas phase NO_x volume fluxes, concentrations and γ measured in the field. The model incorporates the appropriate actinic solar spectrum, thereby properly weighting the different rates of photolysis of NO₃^&minus; and NO₂^&minus;. This is important since the immediate precursor for NO, for example, NO₂^&minus;, absorbs at wavelengths longer than nitrate itself. Finally, one-dimensional model simulations indicate that both gas phase boundary layer NO and NO₂ exhibit a negative concentration gradient as a function of height although [NO]/[NO₂] are approximately constant. This gradient is primarily attributed to gas phase reactions of NO_x with halogens oxides (i.e. as BrO and IO), HO_x, and hydrocarbons, such as CH₃O₂

Validation of northern latitude Tropospheric Emission Spectrometer stare ozone profiles with ARC-IONS sondes during ARCTAS: sensitivity, bias and error analysis

We compare Tropospheric Emission Spectrometer (TES) versions 3 and 4, V003 and V004, respectively, nadir-stare ozone profiles with ozonesonde profiles from the Arctic Intensive Ozonesonde Network Study (ARCIONS, http://croc.gsfc.nasa.gov/arcions/ during the Arctic Research on the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field mission. The ozonesonde data are from launches timed to match Aura's overpass, where 11 coincidences spanned 44° N to 71° N from April to July 2008. Using the TES "stare" observation mode, 32 observations are taken over each coincidental ozonesonde launch. By effectively sampling the same air mass 32 times, comparisons are made between the empirically-calculated random errors to the expected random errors from measurement noise, temperature and interfering species, such as water. This study represents the first validation of high latitude (>70°) TES ozone. We find that the calculated errors are consistent with the actual errors with a similar vertical distribution that varies between 5% and 20% for V003 and V004 TES data. In general, TES ozone profiles are positively biased (by less than 15%) from the surface to the upper-troposphere (~1000 to 100 hPa) and negatively biased (by less than 20%) from the upper-troposphere to the lower-stratosphere (100 to 30 hPa) when compared to the ozonesonde data. Lastly, for V003 and V004 TES data between 44° N and 71° N there is variability in the mean biases (from −14 to +15%), mean theoretical errors (from 6 to 13%), and mean random errors (from 9 to 19%)

Kinetics of isothermal and non-isothermal precipitation in an Al-6at%Si alloy

A novel theory which describes the progress of a thermally activated reaction under isothermal and linear heating conditions is presented. It incorporates nucleation, growth and impingement and takes account of temperaturedependent solubility. The model generally fits very well to isothermal calorimetry and differential scanning calorimetry data on precipitation in an Al-6 at.% Si alloy. Analysis of the data shows that two processes occur in this precipitation reaction: growth of large Si particles and growth of pre-existing small nuclei. Determination of the sizes of Si precipitates by transmission electron microscopy indicates that interfacial energy contributions are small and have a negligible influence on solubilit

Surface-Enhanced Nitrate Photolysis on Ice

Heterogeneous nitrates photolysis is the trigger for many chemical processes occurring in the polar boundary layer and is widely believed to occur in a quasi-liquid layer (QLL) at the surface of ice. The dipole forbidden character of the electronic transition relevant to boundary layer atmospheric chemistry and the small photolysis/photoproducts quantum yields in ice (and in water) may confer a significant enhancement and interfacial specificity to this important photochemical reaction at the surface of ice. Using amorphous solid water films at cryogenic temperatures as models for the disordered interstitial air/ice interface within the snowpack suppresses the diffusive uptake kinetics thereby prolonging the residence time of nitrate anions at the surface of ice. This approach allows their slow heterogeneous photolysis kinetics to be studied providing the first direct evidence that nitrates adsorbed onto the first molecular layer at the surface of ice are photolyzed more effectively than those dissolved within the bulk. Vibrational spectroscopy allows the ~3-fold enhancement in photolysis rates to be correlated with the nitrates’ distorted intramolecular geometry thereby hinting at the role played by the greater chemical heterogeneity in their solvation environment at the surface of ice than in the bulk. A simple 1D kinetic model suggests 1-that a 3(6)-fold enhancement in photolysis rate for nitrates adsorbed onto the ice surface could increase the photochemical NO[subscript 2] emissions from a 5(8) nm thick photochemically active interfacial layer by 30%(60)%, and 2-that 25%(40%) of the NO[subscript 2] photochemical emissions to the snowpack interstitial air are released from the top-most molecularly thin surface layer on ice. These findings may provide a new paradigm for heterogeneous (photo)chemistry at temperatures below those required for a QLL to form at the ice surface

An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3-4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively small boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future

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

The effect of the novel HO_2 + NO → HNO_3 reaction channel at South Pole, Antarctica

It is well established that the reaction of HO_2 with NO plays a central role in atmospheric chemistry, by way of OH/HO_2 recycling and reduction of ozone depletion by HO_x cycles in the stratosphere and through ozone production in the troposphere. Utilizing a photochemical box model, we investigate the impact of the recently observed HNO_3 production channel (HO_2+NO → HNO_3) on NO_x (NO + NO_2), HO_x (OH + HO_2), HNO_3, and O_3 concentrations in the boundary layer at the South Pole, Antarctica. Our simulations exemplify decreases in peak O_3, NO, NO_2, and OH and an increase in HNO_3. Also, mean OH is in better agreement with observations, while worsening the agreement with O_3, HO_2, and HNO_3 concentrations observed at the South Pole. The reduced concentrations of NO_x are consistent with expected decreases in atmospheric NO_x lifetime as a result of increased sequestration of NO_x into HNO_3. Although we show that the inclusion of the novel HNO_3 production channel brings better agreement of OH with field measurements, the modelled ozone and HNO_3 are worsened, and the changes in NO_x lifetime imply that snowpack NO_x emissions and snowpack nitrate recycling must be re-evaluated

Oxygen isotopic fractionation in the photochemistry of nitrate in water and ice

We recently reported the first multiple oxygen isotope composition of nitrate (NO_3^−) in ice cores (Alexander et al., 2004). Postdepositional photolysis and volatilization may alter the isotopic signatures of snowpack nitrate. Therefore the precise assessment of the geochemical/atmospheric significance of O-isotopic signatures requires information on the relative rates of photolysis (λ > 300 nm) of N^(16)O_3^−, N^(16)O_2^(17)O^−, and N^(16)O_2^(18)O^− in ice. Here we report on ^(17)O^- and ^(18)O^-fractionation in the 313-nm photolysis of 10-mM aqueous solutions of normal Fisher KNO3 (i.e., Δ17O = −0.2 ± 0.2‰) and 17O-enriched USGS-35 NaNO_3 (Δ^(17)O = 21.0 ± 0.4‰) between −30° and 25°C. We found that Fisher KNO_3 undergoes mass-dependent O-fractionation, i.e., a process that preserves Δ^(17)O = 0. In contrast, Δ^(17)O in USGS-35 NaNO_3 decreased by 1.6 ± 0.4‰ and 2.0 ± 0.4‰ at 25°C, 1.2 ± 0.4‰ and 1.3 ± 0.4‰ at −5°C, and 0.2 ± 0.4‰ and 1.1 ± 0.4‰ at −30°C, after 12 and 24 hours, respectively. Since the small quantum yield (∼0.2%) of NO_3^− photodecomposition into (NO_2 + OH) is due to extensive cage recombination of the primary photofragments rather than to intramolecular processes, the observed Δ^(17)O decreases likely reflect competitive O-isotope exchange of geminate OH-radicals with H_2O (Δ^(17)O = 0) and escape from the solvent cage, in addition to residual O-isotope mixing of the final photoproducts NO, NO_2, NO_2^−, with H_2O. At the prevailing low temperatures, photochemical processing will not impair the diagnostic value of O-isotopic signatures in tracing the chemical ancestry of nitrate in polar ice

An active nitrogen cycle on Mars sufficient to support a subsurface biosphere

Mars' total atmospheric nitrogen content is 0.2 mbar. One-dimensional (1D) photochemical simulations of Mars' atmosphere show that nitric acid (HNO_3(g)), the most soluble nitrogen oxide, is the principal reservoir species for nitrogen in its lower atmosphere, which amounts to a steady-state value of 6×10^(−2) kg or 4 moles, conditions of severe nitrogen deficiency. Mars could, however, support ∼10^(15) kg of biomass (∼1 kg N m^(−2)) from its current atmospheric nitrogen inventory. The terrestrial mass ratio of nitrogen in biomass to that in the atmosphere is ∼10^(−5); applying this ratio to Mars yields ∼10^(10) kg of total biomass – also, conditions of severe nitrogen deficiency. These amounts, however, are lower limits as the maximum surface-sink of atmospheric nitrogen is 2.8 mbar (9×10^(15) kg of N), which indicates, in contradistinction to the Klingler et al. (1989), that biological metabolism would not be inhibited in the subsurface of Mars. Within this context, we explore HNO_3 deposition on Mars' surface (i.e. soil and ice-covered regions) on pure water metastable thin liquid films. We show for the first time that the negative change in Gibbs free energy increases with decreasing HNO_3(g) (NO_3^−(aq)) in metastable thin liquid films that may exist on Mars' surface. We also show that additional reaction pathways are exergonic and may proceed spontaneously, thus providing an ample source of energy for nitrogen fixation on Mars. Lastly, we explore the dissociation of HNO_3(g) to form NO_3^−(aq) in metastable thin liquid films on the Martian surface via condensed phase simulations. These simulations show that photochemically produced fixed nitrogen species are not only released from the Martian surface to the gas-phase, but more importantly, transported to lower depths from the Martian surface in transient thin liquid films. A putative biotic layer at 10 m depth would produce HNO_3 and N_2 sinks of −54 and −5×10^(12) molecules cm^(−2) s^(−1), respectively, which is an ample supply of available nitrogen that can be efficiently transported to the subsurface. The downward transport as well as the release to the atmosphere of photochemically produced fixed nitrogen species (e.g. NO_2^−, NO and NO_2) suggests the existence of a transient but active nitrogen cycle on Mars