Column Amounts of ClONO2, HCl, HNO3, and HF from Ground-Based FTIR Measurements Made Near Kiruna, Sweden, in Late Winter 1994

During SESAME phase I ground-based FTIR measurements were performed atEsrange near Kiruna, Sweden, from 28 January to 26 March 1994. Zenith columnamounts of ClONO₂, HCl, HF, HNO₃,O₃, N₂O, CH₄, and CFC-12 werederived from solar absorption spectra. Time series of ClONO₂and HCl indicate a chlorine activation at the end of January and around 1March. On 1 March a very low amount of HCl of 2.09times; 10¹⁵molec. cm^-2 was detected, probably caused by a second chlorineactivation phase starting from an already decreased amount of HCl. The ratioof column amounts of HCl to ClONO₂ decreased inside the vortexfrom about 1 in January to 0.4 in late March compared to values of about 2outside the vortex. Although the Arctic stratosphere was rather warm in winter1993/94 and PSCs occurred seldom, chlorine partitioning into its reservoirspecies HCl and ClONO₂ changed during that winter andClONO₂ is the major chlorine reservoir at the end of thewinter as in cold winters like 1991/92 and 1994/95.     

SD-WACCM模式对平流层化学组分的模拟研究

利用美国大气研究中心开发的全球气候模式,对2008年平流层的化学组分(HNO₃、HCl和O₃)进行了模拟研究,并结合了MLS卫星资料进行了对比分析。结果表明,模式可以较好地再现平流层的各化学组分的时空分布状况。并选取了8个区域,将模拟的2008—2009年O₃柱浓度与臭氧监测仪资料对比,结果表明,模式可以较好地再现全球O₃总量的季节变化情况。     

Laboratory spectroscopic studies of atmospherically important radicals using fourier transform spectroscopy

This paper describes laboratory experiments designed to obtain the infrared spectra of some atmospherically important radical species and related compounds. A Fourier transform spectrometer was used that was capable of yielding resolutions as great as 0.0024 cm^-1, and optical paths of up to 512 m were employed. The objective of the experiments was to obtain the spectra for subsequent application to remote sounding measurements in the atmosphere.Radicals were generated by a variety of chemical reactions involving atoms or other highly reactive precursors. Spectra of the ₃ band of NO₃, at ca. 1500 cm^-1, were obtained with up to 0.005 cm^-1 resolution using the reaction between NO₂ and O₃ to produce the radical. The most satisfactory source of ClO was found to be the reaction between Cl and O₃, and the (1-0) vibration-rotation band in the region 829–880 cm^-1 was recorded at a resolution of 0.02 cm^-1. We were unable to observe infrared absorption of HO₂ with any of the radical sources that we tested. High-resolution survey spectra were obtained of compounds used as reactants, or formed as side-products in the radical-generating processes. These compounds included N₂O₅, HNO₃, ClONO₂, FNO₂, Cl₂O, HO₂NO₂, and probably FO₂.The ability to monitor concentrations of the NO₃ radical in the visible region of the spectrum as well as the concentrations of reactants and other products in the infrared region allowed us to undertake a study of the time-dependent interactions occurring when NO₂ reacts with O₃. The results indicate the importance of heterogeneous processes, especially when traces of water are present, and lend credence to suggestions that heterogeneous mechanisms in the NO₃–N₂O₅–H₂O system might be a viable source of HNO₃ in the atmosphere.     

The heterogeneous formation of N2O in air containing NO2, O3 and NH3

In a nighttime system and under relatively dry conditions (about 15 ppm H₂O), the reaction mixture of NO₂, O₃, and NH₃ in purified air turns out to result in the formation of nitrous oxide (N₂O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm.N₂O is thought to arise through the heterogeneous reaction of gaseous N₂O₅ and absorbed NH₃ at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\]In principle, there is competition between this reaction and that of adsorbed H₂O with N₂O₅, resulting in the formation of HNO₃. At high water concentrations (RH>75%), no formation of N₂O was found. Although the rate constant of adsorbed NH₃ with gaseous N₂O₅ is much larger than that of the reaction of adsorbed H₂O with gaseous N₂O₅, the significance of the observed N₂O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H₂O and NH₃ on a surface. A number of NH₃ and H₂O adsorption measurements on several materials are discussed.     

Stratospheric Photolysis Frequencies: Impact of an Improved Numerical Solution of the Radiative Transfer Equation

Numerical schemes for the calculation of photolysis rates are usually employed in simulations of stratospheric chemistry. Here, we present an improvement of the treatment of the diffuse actinic flux in a widely used stratospheric photolysis scheme (Lary and Pyle, 1991). We discuss both the consequences of this improvement and the correction of an error present in earlier applications of this scheme on the calculation of stratospheric photolysis frequencies. The strongest impact of both changes to the scheme is for small solar zenith angles. The effect of the improved treatment of the diffuse flux is most pronounced in the lower stratosphere and in the troposphere. Overall, the change in the calculated photolysis frequencies in the region of interest in the stratosphere is below about 20%, although larger deviations are found for H₂O, O₂, NO, N₂O, and HCl.     

Radical variability determined from LIMS and SAMS satellite data

Using satellite data, the variability of a large number of stratospheric trace constituents can be estimated. These constituents need not themselves be measured by the satellite; their concentrations can be derived using photochemical steady-state relationships. The global coverage provided by the satellite over a long time period means that, for example, monthly zonal mean profiles can be derived. This has been done for H, OH, HO₂, H₂O₂, Cl, ClO, HCl, HOCl, ClONO₂, NO and O. The standard deviation of these quantities is a measure of their variability. We argue that comparing theoretical variability estimates with measurements is a better test of a photochemical theory than simply the comparison of single modelled and observed profiles.     

On the diffusivity of trace gases under stratospheric conditions

Transport of trace gases within the gas phase to a cloud or a sulphate aerosol droplet proceeds by molecular diffusion at the gas-liquid interface. An accurate determination of the molecular diffusion coefficient has a direct bearing on estimates of trace gas uptake and scavenging. A literature search revealed that this parameter is often chosen rather arbitrarily and the choice of a particular value is constrained by the availability of experimental data which are usually available at one atmospheric pressure under laboratory conditions. Since the process of trace gas transport to droplets occur at heights much above the ground level, it is important to determine an accurate value of the diffusion coefficient at varying levels in the atmosphere. This was achieved theoretically by estimating diffusivities for some important trace gases under stratospheric conditions by a Lennard-Jones method. Molecular diffusivity of 22 trace gases (including ClONO₂, HNO₃, SO₂ and H₂O₂ which may lead to heterogeneous reactions on various surfaces) have been estimated which can be used by modellers for improved scavenging estimates.     

High resolution simulation of recent Arctic and Antarctic stratospheric chemical ozone loss compared to observations

Simulations of polar ozone losses were performed using the three-dimensional high-resolution (1^∘ × 1^∘) chemical transport model MIMOSA-CHIM. Three Arctic winters 1999–2000, 2001–2002, 2002–2003 and three Antarctic winters 2001, 2002, and 2003 were considered for the study. The cumulative ozone loss in the Arctic winter 2002–2003 reached around 35% at 475 K inside the vortex, as compared to more than 60% in 1999–2000. During 1999–2000, denitrification induces a maximum of about 23% extra ozone loss at 475 K as compared to 17% in 2002–2003. Unlike these two colder Arctic winters, the 2001–2002 Arctic was warmer and did not experience much ozone loss. Sensitivity tests showed that the chosen resolution of 1^∘ × 1^∘ provides a better evaluation of ozone loss at the edge of the polar vortex in high solar zenith angle conditions. The simulation results for ozone, ClO, HNO₃, N₂O, and NO _y for winters 1999–2000 and 2002–2003 were compared with measurements on board ER-2 and Geophysica aircraft respectively. Sensitivity tests showed that increasing heating rates calculated by the model by 50% and doubling the PSC (Polar Stratospheric Clouds) particle density (from 5 × 10⁻³ to 10⁻² cm⁻³) refines the agreement with in situ ozone, N₂O and NO _y levels. In this configuration, simulated ClO levels are increased and are in better agreement with observations in January but are overestimated by about 20% in March. The use of the Burkholder et al. (1990) Cl₂O₂ absorption cross-sections slightly increases further ClO levels especially in high solar zenith angle conditions. Comparisons of the modelled ozone values with ozonesonde measurement in the Antarctic winter 2003 and with Polar Ozone and Aerosol Measurement III (POAM III) measurements in the Antarctic winters 2001 and 2002, shows that the simulations underestimate the ozone loss rate at the end of the ozone destruction period. A slightly better agreement is obtained with the use of Burkholder et al. (1990) Cl₂O₂ absorption cross-sections.     

Modelling the multiphase near-surface chemistry related to ozone depletions in polar spring

Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic reaction cycles involving reactive halogens are now recognized to be of main importance for ozone depletion events in the polar boundary layer. We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br₂, BrCl, or Cl₂ to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H₂O₂, DMS, Cl₂, C₂H₆, HONO, NO₂, and RONO₂ was investigated. Cases with elevated mixing ratios of HCHO, H₂O₂, DMS, Cl₂, and HONO induced a shift in bromine speciation from Br / BrO to HOBr/HBr, while high mixing ratios of C₂H₆ induced a shift from HOBr/HBr to Br/BrO. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). For all NO_y species studied (HONO, NO₂, RONO₂) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NO_x. The production of HNO₃ led to the acid displacement of HCl, and the release of chlorine out of salt aerosol (Cl₂ or BrCl) increased.     

Measurements of stratospheric chlorine monoxide (ClO) from groudbased FTIR observations

Infrared absorption features due to ClO in the lower stratosphere have been identified from groundbased solar absorption spectra taken from Aberdeen, U.K. (57° N, 2° W) on 20 January 1995. A vertical column abundance of 3.42 (±0.47)×10¹⁵ molec cm^-2 has been derived from 13 independent absorption features in the P and R branches of the (0–1) vibration-rotation band of ³⁵ClO, spanning the spectral region 817–855 cm^-1. The observed absorption features are consistent with very high levels of ClO (approximately 2.6 parts per billion by volume (ppbv)) in the altitude range 16–22 km. A comparison of this profile with a 3D chemical transport model profile indicates the observation was made inside the polar vortex and shows good qualitative agreement but the model underestimates the concentrations of ClO. Simultaneous measurements of other species were made including HCl, HF and ClONO₂. These columns yield a value for HCl+ClONO₂+ClO of 7.02±0.65×10¹⁵ molec cm^-2. This is lower than the total inorganic chlorine (ClO _y ) column of 10.7±1.6×10¹⁵ molec cm^-2 estimated from mean measured (HCl+ClONO₂)/HF ratios together with in-vortex HF measurements. The discrepancy is probably due to significant amounts of the ClO dimer (Cl₂O₂) in the lower part of the stratosphere. The measurements of highly elevated levels of ClO are used to estimate O₃ loss rates at the 400, 475 and 550 K levels making assumptions about the probable distribution of ClO and Cl₂O₂. These are compared with loss rates derived from ozone sonde data.     

Molecular Line Parameters for the “MASTER” (Millimeter Wave Acquisitions for Stratosphere/Troposphere Exchange Research) Database

In order to investigate the upper troposphere/lower stratosphere (UTLS) region of the earth's atmosphere, ESA/ESTEC (European space agency) is considering the opportunity to develop the spaceborne limb sounding millimeter sensor “MASTER” (millimeter wave acquisitions for stratosphere/troposphere exchange research). This instrument is part of the “atmospheric composition explorer for chemistry and climate interactions” (ACECHEM) project. In addition, ESA/ESTEC is developing the “MARSCHALS” (millimeter-wave airborne receiver for spectroscopic characterization of atmospheric limb sounding) airborne instrument which will demonstrate the feasibility of MASTER. The present paper describes the line-by-line database which was generated in order to meet at best the needs of the MASTER (or MARSCHALS) instrument. The linelist involves line positions, line intensities, line broadening and line shift parameters in the 294–305, 316–325, 342–348, 497–506 and 624–626 GHz spectral microwindows. This database was first generated for the target molecules for MASTER (H₂O, O₃, N₂O, CO, O₂, HNO₃, HCl, ClO, CH₃Cl, BrO). In addition, ten additional molecules (SO₂, NO₂, OCS, H₂CO, HOCl, HCN, H₂O₂, COF₂, HO₂ and HOBr) had also to be considered in the database as “possible interfering species” for the retrieval of the target molecules of MASTER. The line parameters were derived, depending on their estimated accuracy, (i) from a combination of spectral parameters included in the JPL and HITRAN catalogs (ii) from data taken into the literature or (iii) using data obtained through experimental measurements (and/or) calculations performed during the present study.     

Flow reactor and triple quadrupole mass spectrometer investigations of negative ion reactions involving nitric acid: Implications for atmospheric HNO3 detection by chemical ionization mass spectrometry

Atmospheric nitric acid measurements by ACIMS (Active Chemical Ionization Mass Spectrometry) are based on ion-molecule reactions of CO₃ ^-(H₂O) _n and NO₃ ^-(H₂O) _n with HNO₃. We have studied these reactions in the laboratory using a flow tube apparatus with mass spectrometric detection of reactant and product ions. Both product ion distributions and rate coefficients were measured. All reactions were investigated in an N₂-buffer (1–3 hPa) at room temperature. The reaction rate coefficients of OH^-, O₂ ^-, O₃ ^-, CO₄ ^-, CO₃ ^-, CO₃ ^-H₂O, NO₃ ^-, and NO₃ ^-H₂O were measured relative to the known rate k=3.0×10^-9 cm³ s^-1 for the reaction of O^- with HNO₃. The main product ion of the reaction of CO₃ ^-H₂O with HNO₃ was found to be (CO₃HNO₃)^- supporting a previous suggestion made on the basis of balloon-borne ACIMS measurements. For the reaction of bare CO₃ ^- with HNO₃ three product ions were observed, namely NO₃ ^-, (NO₃OH)^-, and (CO₃HNO₃)^-. The reaction rate coefficients for CO₃ ^-H₂O (1.7×10^-9 cm³ s^-1) and NO₃ ^-H₂O (1.6×10^-9 cm³ s^-1) were found to be close to the collision rate. The measured k values for bare CO₃ ^- (1.3×10^-9 cm³ s^-1) and NO₃ ^- (0.7×10^-9 cm³ s^-1) are somewhat smaller. The collisional dissociations of CO₃ ^-(H₂O) _n , NO₃ ^-(H₂O) _n (n=1, 2), (CO₃HNO₃)^- and (NO₃HNO₃)^-, occasionally influencing ACIMS measurements, were also studied. Fragment ion distributions were measured using a triple quadrupole mass spectrometer. The results showed that previous stratospheric nitric acid measurements were unimpaired from collisional dissociation processes whereas these processes played a major role during previous tropospheric measurements leading to an underestimation of nitric acid concentrations. Previous ACIMS HNO₃ detection was also affected by the conversion of CO₃ ^-(H₂O) _n to NO₃ ^-(H₂O) _n due to ion source-produced neutral radicals. A novel ACIMS ion source was developed in order to avoid these problems and to improve the ACIMS method.     

GHOST – A Novel Airborne Gas Chromatograph for In Situ Measurements of Long-Lived Tracers in the Lower Stratosphere: Method and Applications

A novel fully-automated airborne gas chromatograph for in situmeasurements of long-lived stratospheric tracers hasbeen developed, combining the high selectivity of a megabore PLOTcapillary column with recently developed sampling and separationtechniques. The Gas cHromatograph for theObservation of Stratospheric Tracers (GHOST)has been successfully operated during three STREAM campaigns(Stratosphere TRoposphere Experiment byAirborne Measurement) onboard a Cessna Citation IIaircraft in two different modes: Either N₂O andCF₂Cl₂(CFC-12) or CFC-12 and CFCl₃ (CFC-11) have been measuredsimultaneously, with a time resolution of 2 min for both modes.Under flight conditions the instrument precision (1) forthese species is better than 0.9%, and the accuracy(1) is better than 2.0% of the tropospheric values ofall measured compounds. The detection limits (3) arebelow 28 ppb for N₂O, 14 ppt for CFC-12, and 8 ppt forCFC-11, respectively, i.e., well below 10 % of the troposphericvalues of all measured compounds. Post-mission optimization of thechromatographic separation showed a possible enhancement of thetime resolution by up to a factor of 2, associated with acomparable increase in precision and detection limit. As test ofactual performance of GHOST results from an in-flight N₂Ointercomparison with a tunable diode laser absorptionspectrometer (TDLAS) are presented. They yield an excellentagreement between both instruments. Furthermore, on the basis ofthe hitherto most extensive set of upper tropospheric and lowerstratospheric data, the relative stratospheric N₂2O lifetime isre-assessed. When referenced to the WMO reference CFC-11 lifetimeof 45 ± 7 years an N₂O lifetime of 91 ± 15 yearsis derived, a value substantially smaller than the WMO referencelifetime of 120 years. Moreover, this value implies astratospheric N₂O sink strength of 16.3 ± 2.7 Tg (N)yr^–1 which is 30% larger than previous estimates.     

A budget analysis of NO x column losses over the Korean peninsula

In this study, the chemical and physical losses of nitrogen oxides (NO_x) over the Korean peninsula were discussed in order to better understand the effects of the NO_x losses on the tropospheric NO₂ columns. Initially, it was found that the physical loss processes due to dry and wet depositions had almost negligible impacts on the NO_x loss processes over the Korean peninsula. In contrast, the hourly NO_x chemical column losses were large at ??10¹⁴ molecules cm^?2 h^?1. The amounts of NO_x removed for 1 hour account for approximately 33?C35% of the episode-averaged tropospheric NO₂ columns during summer over the Korean peninsula. The NO_x chemical column loss rates were 24.1?C70.9 times larger than the NO_x physical column loss rates. In a budget analysis of the NO_x chemical column losses, HNO₃ formation via the reaction of OH + NO₂ had the largest contribution toward the NO_x chemical losses (42?C55% during fall and winter seasons; 76?C77% during spring; 92?C93% during summer). Large amounts of NO_x were also removed by heterogeneous nitrate formation via N₂O₅ condensation during the cold seasons (42?C56%) over the Korean peninsula. The columnar NO_x chemical losses took place mainly due to the two chemico-physical reaction processes, and also showed seasonal variations. PAN (Peroxyacetyl Nitrate) is another NO₂ reservoir of potential importance. If the influence of the PAN-related chemistry on the NO_x budget is considered, it can result in an approximate 69% increase in the NO_x chemical column loss during summer. Such increases in the amounts of NO_x removed for 1 hour due to the formation of PAN were equivalent to 56?C58% of the episode-averaged tropospheric NO₂ columns during summer over the Korean peninsula. Such active NO_x chemical losses during summer are another main factor for the tropospheric NO₂ columns exhibiting their smallest values during summer.     

The partitioning of nitrogen oxides in the lower Arctic troposphere during spring 1988

Surface observations of several nitrogen oxides in the Canadian high Arctic during the period March-April 1988 are reported. These include data on NO₂, the inorganic nitrates HNO₃ and particulate nitrate, and the organic nitrates PAN and C₃–C₇ alkyl-nitrates. It is found that the organic nitrates make up 70–80% of the sum of the measured nitrogen oxides. Based on concurrently measured sulphur oxides, the period of observation was divided into two halves with the first half representing less polluted, more aged air than the second. The preponderance of the organic nitrates was less in the first period than the second. In contrast, there was little difference in the inorganic nitrates and NO₂ concentrations. The dominant inorganic nitrate shifted from particulate nitrate in the first period towards gaseous HNO₃ in the second. No correlation between the nitrates (inorganic or organic) and O₃ was observed; although some indication of a positive correlation between NO₂ and O₃ has been reported earlier (Bottenheimet al., 1990). Possible explanations for these observations are proposed. A survey of other potential nitrogen oxides that may be present in the Arctic air but not measured in these experiments suggests that the nitrogen oxides not measured here constitute a minor fraction of the total reactive nitrogen (NO _y ).Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

Measurements of Trace Substances in the Arctic Troposphere as Potential Precursors and Constituents of Arctic Haze

During two measuring campaigns in early spring 1994 and 1995 (March/April) and one campaign in summer 1994, measurements of ozone, PAN, sulfur dioxide, nitric acid, and particulate nitrate, sulfate, and ammonium (only 1995) were recorded in the Arctic. Observations were made by aircraft at various sites in the eastern and western Arctic. Ozone concentrations showed a steady increase with altitude both in spring and summer. During five flights in springtime, low ozone events (LOEs) could be observed near the surface and up to altitudes of 2000 m. SO₂ background concentrations, ranging from detection limit (0.5 nmol/m³) to 5 nmol/m³, were observed during both spring and summer. Distinct maxima up to 55 nmol/m³ in lower altitudes were only obtained in springtime. Concentrations of the organic nitrate PAN were within a similar range as those of the inorganic nitrate HNO₃ during spring campaigns. In contrast, concentrations of particulate nitrate were one half an order of magnitude lower. HNO₃ concentrations increased significantly with altitude. Evidently, HNO₃ was intruded from the stratosphere into the troposphere. Sulfate concentrations ranged between 5 and 30 nmol/m³; ammonium concentrations were obtained within a range from 10 to 50 nmol/m³.     

Observations of NO2 and O3 during thunderstorm activity using visible spectroscopy

Simultaneous observations for the total column densities of NO2, O3 and H2O were carried on using the porta-ble Spectrometer (438-450 nm and 400-450 nm) and the visible Spectrometer (544.4-628 nm) during premonsoon thunderstorms and embedded hail storm activity at Pune (18o32’N & 73o51’E), India. These observations confirm the fact that there is an increase in O3 and NO2 column densities during thunderstorms. The increase in O3 was observed following onset of thunderstorm, while the increase in NO2 was observed only after the thunder flashes occur. This implies that the production mechanisms for O3 and NO2 in thunderstorm are different. The observed column density of NO2 value (1 to 3 × 1017molecules · cm-2) during thunderstorm activity is 10 to 30 times higher than the value (1 × 1016molecules · cm-2) of a normal day total column density. The spectrometric observations and observations of thunder flashes by electric field meter showed that 6.4 × 1025molecules / flash of NO2 are produced. The increased to-tal column density of ozone during thunderstorm period is 1.2 times higher than normal (clear) day ozone concentra-tion. The multiple scattering in the clouds is estimated from H2O and O2 absorption bands in the visible spectral re-gion. Considering this effect the calculated amount of ozone added in the global atmosphere due to thunderstorm ac-tivity is 0.26 to 0.52 DU, and the annual production of ozone due to thunderstorm activity is of the order of 4.02 × 1037 molecules /year. The annual NO2 production may be of the order of 2.02 × 1035molecules / year.     

Modified HNO3 seasonality in volcanic layers of a polar ice core: Snow-pack effect or photochemical perturbation?

Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO₃ chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO ₄ ^2– and NO ₃ ^– , were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO ₃ ^– deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H₂SO₄ particles in the stratosphere may have favored condensation and removal of HNO₃ from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO₃ during summer, caused by direct consumption of OH through oxidation of volcanic SO₂.