D. Perner

The Global Ozone Monitoring Experiment (GOME): Mission Concept and First Scientific Results

The Global Ozone Monitoring Experiment (GOME) is a new instrument aboard the European Space Agencys (ESA) Second European Remote Sensing Satellite(ERS-2), which was launched in April 1995. The main scientific objective of the GOME mission is to determine the global distribution of ozone and several other trace gases, which play an important role in the ozone chemistry of the earths stratosphere and troposphere. GOME measures the sunlight scattered from the earths atmosphere and/or reflected by the surface in nadir viewing mode in the spectral region 240-790 nm at a moderate spectral resolution of between 0.2 and 0.4 nm. Using the maximum 960-km across-track swath width, the spatial resolution of a GOME ground pixel is 40 3 320 km2 for the majority of the orbit and global coverage is achieved in three days after 43 orbits. Operational data products of GOME as generated by DLR-DFD, the German Data Processing and Archiving Facility (D-PAF) for GOME, comprise absolute radiometrically calibrated earthshine radiance and solar irradiance spectra (level 1 products) and global distributions of total column amounts of ozone and NO 2 (level 2 products), which are derived using the DOAS approach (Differential Optical Absorption Spectroscopy). (Under certain conditions and some restrictions, the operational data products are publically available from the European Space Agency via the ERS Helpdesk.) In addition to the operational data products, GOME has delivered important information about other minor trace gases such as OClO, volcanic SO2 ,H 2CO from biomass burning, and tropospheric BrO. Using an iterative optimal estimation retrieval scheme, ozone vertical profiles can be derived from the inversion of the UV/VIS spectra. This paper reports on the GOME instrument, its operation mode, and the retrieval techniques, the latter with particular emphasis on DOAS (total column retrieval) and advanced optimal estimation (ozone profile retrieval). Observation of ozone depletion in the recent polar spring seasons in both hemispheres are presented. OClO observed by GOME under twilight conditions provides valuable information on the chlorine activation inside the polar vortex, which is believed to be responsible for the rapid catalytic destruction of ozone. Episodes of enhanced BrO in the Arctic, most likely contained in the marine boundary layer, were observed in early and late spring. Excess tropospheric nitrogen dioxide and ozone have been observed during the recent Indonesian fire in fall 1997. Formaldehyde could also clearly be identified by GOME and is known to be a by-product resulting from biomass burning.

The Nitrate Radical: Physics, Chemistry and the Atmosphere

Abstract This review surveys the present state of knowledge of the nitrate (NO 3 radical. Laboratory data on the physics and chemistry of the radical and atmospheric determination of the concentrations of the radical are both considered. One aim of the review is to highlight the relationship between the laboratory and the atmospheric studies. Although the emphasis of the review is on gas-phase processes, relevant studies conducted in condensed phases are mentioned because of their potential importance in the interpretation of cloud and aerosol chemistry. The spectroscopy, structure, and photochemistry of the radical are examined. Here, the object is to establich the spectroscopic basis for detection of the radical and measurement of its concentration in the laboratory and in the atmosphere. Infrared, visible, and paramagnetic resonance spectra are considered. An important quantity discussed is the absorption cross section in the visible region, which is required for quantitative measurements. Interpretation of the spectroscopic features requires an understanding of the geometrical and electronic structure of the radical in its ground and excited states; there is still some controversy about the groundstate geometry, but the most recent experimental evidence 9eg from laser induced fluorescence) and theoretical calculations suggest that the radical has D 3h symmetry. Photodissociation of the radical is important in the atmosphere, and the product channels, quantum yields, and dissociation dynamics are discussed. A short examination of the thermodynamics (heat and entropy of formation) of the radical is presented. The main exposition of laboratory studies of the chemistry of the nitrate radical is preceded by a consideration of the techniques used for kinetic and mechanistic studies. Methods for the generation and detection of the radical and the kinetic tools employed are all presented. The exact nature of the technique used in individual studies has some relevance to the way in which data must be analysed, and to the type of mechanistic information that can be extracted. Continuous and stopped flow, flash photolysis and pulse radiolysis, molecular modulation, and static reactor techniques can all provide absolute kinetic data, while relative rate measurements have been a further rich source of information. The treatment of the chemical reactions of the nitrate radical is formally divided into the interactions with non-radical inorganic (deemed to include NO and NO 2 ) and organic species, and with atoms and free radicals. In general, the reactions with open-shell species are much more rapid than those with closed-shell reactants. With the closed-shell partners, addition reactions are faster than abstraction reactions. An attempt is made to consider critically the published data on most reactions of importance, and to tabulate rate constants and temperature dependences where possible. However, it is not the objective of this review to provide recommendations for rate parameters. Evidence for the products of the reactions is sought, and for the branching ratios into the various channels where more than one exists. One theme of this part of the review is the elucidation of correlations of reactivity with structure and with the reactions of other radical species such as OH. The review turns next to a consideration of the role of NO 3 in the atmosphere, of its atmospheric sources and sinks, and of field measurements of concentrations of the radical. Long-path visible-absorption spectroscopy and matrix-isolation ESR have both been used successfully in field measurements in the troposphere as well as the stratosphere. Balloon-borne instruments and ground-based remote sensing have been used to obtain stratospheric concentrations. Two of the most important implications of the measurements are that the stratospheric profiles are consistent with accepted chemistry (and, in particular, do not require the postulation of an unidentified scavenging mechanism that had, at one stage, been proposed), and that the highly variable night-time tropospheric concentrations imply that NO 3 is a reactive tropospheric constituent. The inter-relation between laboratory studies and atmospheric observations, and the problems in extrapolating laboratory data to atmospheric conditions, are both explored. Initiation of night-time chemical transformations by NO 3 and the possible production of OH are considered. The available information is then brought together to see how far NO 3 is a sensitive indicator of the state of the atmosphere, and some speculations are presented about the involvement of NO 3 (or N 2 O 5 ) in damage to trees and plants. The final section of the review suggests some issues that remain unresolved concerning the NO 3 radical which is directly or indirectly relevant to a better knowledge of the part played by the radical in the atmosphere. Amongst the requirements noted are improved data for the heat of formation of the radical, its absorption cross section in the visible region (and, especially, the temperature dependence of the cross section), and the details of its photochemistry. There is also still a need for a definitive determination of the equilibrium constant and its temperature dependence for the association with NO 2 and the reverse dissociation of N 2 O 5 . A series of chemical reactions deserves further investigation, especially with regard to elucidation of product channels, and overall oxidation mechanisms also need to be defined better. Future atmospheric studies that are desirable include study of basic NO 3 chemistry in the field to understand the influence of humidity on the conversion (probably on surfaces) of N 2 O 5 to HNO 3 , and thus on NO 3 concentrations. In addition, a study of the chemistry of NO 3 in the presence of volatile organic compounds and at elevated concentrations of the oxides of nitrogen should help in the understanding of, for example, polluted marine coasts, forests, and urban areas.

Observations of nitrous acid in the Los Angeles atmosphere and implications for predictions of ozone-precursor relationships.

Direct measurements of nitrous acid (HONO) were made in downtown Los Angeles and Riverside, CA, during night and early morning hours of July/August 1980 using a long-path differential optical absorption spectrometer. Up to 8 ppb of HONO were observed in Los Angeles, approximately twice the maximum levels previously measured in Riverside during the summer of 1979. Possible sources of the observed HONO are discussed. If the observed HONO levels are included in initial NO, concentration, EKMA isopleth calculations predict that more rigorous control of NO, emissions (especially a t low HC/NO, levels) or of hydrocarbons emissions is necessary to reduce ozone maxima by a given amount compared with predictions based on calculations neglecting initial HONO. Moreover, including HONO in the starting NO, leads to predictions of accelerated rates of oxidant production which results in much larger predicted O3 doses at elevated O3 levels. For example, the predicted O3 dosage at levels above 0.3 ppm ozone in the case of NMHC = 1 ppm and [NO,], = 0.12 ppm is increased by over 250% when 10 ppb of HONO is taken to be initially present.

Free radicals and fast photochemistry during BERLIOZ

The free radicals OH, HO2, RO2, and NO3 are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date. We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation — Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals. In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses. In addition considerable night-time peroxy radical production related to VOC reactions with NO3 and O3 could be quantified.

Differential optical absorption spectroscopy instrument for stratospheric balloonborne trace-gas studies.

A newly developed UV-visible instrument for differential optical absorption spectroscopic measurements of atmospheric trace gases from balloon platforms is described. Direct solar light at daytime in the near-ultraviolet (320.6-422.6-nm) and the visible (417.6-670.7-nm) spectral ranges can be simultaneously analyzed for the atmospheric column abundances or profiles of O(3), NO(2), NO(3), BrO, OClO, O(4), H(2)O, and possibly other species (HNO(2), IO, CH(2)O). Compared with previously used balloonborne UV-visible spectrometers, the instrument has the superior properties of low mass (42 kg), low power consumption (30 W), decreased spectral drift that is caused by temperature and pressure changes, low detector dark current, and low spectrometer stray light. The three last-named characteristics are achieved by enclosure of the entire spectrometer in a pressurized and thermostated container and by inclusion of separately thermostated photodiode array detectors. The optical setup is simplified to reduce its weight. The spectral stray light is reduced by suppression of the higher-order and zero-order grating reflections by use of light traps and in the UV by addition of a dispersive prism preanalyzer. The major instrumental design characteristics and the instrumental performance as tested in the laboratory and during several stratospheric balloon flights are reported.

Corrections for zenith scattered light DOAS

A variety of physical processes can influence the accuracy of the results obtained by Zenith Scattered Light - Differential Optical Absorption Spectroscopy (ZSL-DOAS) measurements of stratospheric species (like NO2, OClO, BrO and O3). The magnitude of errors that may result, if these effects are ignored, as well as correction methods are discussed.

NO3 at Helgoland during the NORDEX campaign in October 1996

Nighttime observations of NO3, O3, NO2, and aerosol distributions were made at Helgoland in October 1996. Frequently polluted air was observed. Air transport from the mainland over the sea takes several hours, and lifetimes for NO3 and N2O5 can be determined. Those lifetimes are compared with aerosol size distributions measured simultaneously. The lifetimes of N2O5 show clear correlations with total aerosol surface and mean aerosol size, indicating that the most likely sink of NO3 is hydrolysis of N2O5 on wet aerosols of varying composition. The range of possible uptake coefficients is calculated from the measurements and compared with literature data.

Global distribution of atmospheric bromine-monoxide from GOME on earth observing satellite ERS-2

The remote sensing spectro-photometer GOME installed on board of the polar orbiting ESA satellite ERS-2 collects nadir scattered sunlight. The spectral intensity in the UV-VIS-region is measured and various atmospheric trace gases can be identified in the UV-spectra. In this work BrO and NO2 have been followed. They are globally present and absolute column absorptions are obtained for BrO by comparison with direct sun light not having passed through the atmosphere. Average vertical columns of (3.1±1) × 1013 molec/cm² BrO are found in the equatorial region around noon. The omnipresence of BrO has some bearing on the global ozone depletion.

Comparison of measured and modeled stratospheric BrO: Implications for the total amount of stratospheric bromine

Stratospheric BrO was spectroscopically monitored by its UV absorption in direct sunlight on 8 balloon flights that were conducted at middle and high latitudes in 1996 through 2000 [e.g. Ferlemann et al., 1998, 2000]. For conditions where detailed photochemical model calculations [Chipper field, 1999] correctly predict other measured chemical (e.g., NO 2 , O 3 ) and dynamical (e.g. N 2 O, F12, et cetera) tracers, the total stratospheric bromine (organic and inorganic) amount (Bry) is inferred. An excellent agreement between measured and modeled stratospheric BrO is found, assuming JPL-97 kinetics and Bry=20 ppt in the photochemical model. As the BrO absorption cross section (σ BrO ) is the only external parameter used in the measurement, our finding tightly constrains the amount of total inorganic bromine (Br in y ). 20±2.5 ppt above 25 km in 1996/97, as well as the photochemistry of stratospheric bromine.

Ground‐based UV‐VIS spectroscopy: Diurnal OCIO‐profiles during January 1990 above Søndre Strømfjord, Greenland

Considerable amounts of chlorine dioxide, OClO, were observed from 5 January through 2 February, 1990 in the stratosphere above Soendre Stroemfjord showing a highly perturbed chlorine chemistry. Photolysis and simultaneous formation of the OClO leads to a typical concentration minimum at noon. Its changes in concentration indicate the release of the OClO precursors BrO and ClO from their respective reservoir substances in the morning. Two incidences of increased OClO production occur repeatedly at 92{degree} and 89{degree} solar zenith angle (SZA). Furthermore, in the beginning of January OClO morning values exceed those found at dusk for comparable SZA whereas towards the end of the month the morning values become depressed compared to the evening. The twilight vertical column densities of OClO often reach about 1.6 {times} 10{sup 13} molec/cm{sup 2} and a comparison shows an increase from 1988 to 1990.