Gas phase measurements of hydrogen peroxide in Greenland and their meaning for the interpretation of H2O2 records in ice cores

The gas phase concentration of hydrogen peroxide at Summit, Central Greenland, has been measured continuously during June/July 1990 using a coil scrubber technique combined with liquid phase fluorometry. The concentrations ranged between 0.3 ppbv and 3.5 ppbv, which is considerably higher than expected from model calculations and can be explained by low deposition rates. The record shows pronounced diurnal variations with minimum concentrations during night and maximum concentrations in the afternoon. The nocturnal minima can be explained by scavenging of H₂O₂ by hoarfrost. The scavenging mechanisms of H₂O₂ by snow and the redistribution of H₂O₂ during firnification are discussed. There is indirect evidence, that H₂O₂ is uniformly distributed in the ice lattice and that the fractionation between H₂O₂ and H₂O is small during diffusional crystal growth from the vapor phase (co-condensation).     

Growth of monodisperse,submicron aerosol particles exposed to SO2, H2O2, and NH3

The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO₂ (0–860 ppb), H₂O₂ (0–150 ppb) and sometimes NH₃ (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH₄)₂SO₄ and Na₂SO₄ droplets. For (NH₄)₂SO₄ droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH₃ was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO₂ by H₂O₂, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH₃ evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.     

A comparison of the static and flow methods for the detection of ice nuclei

The use of the membrane-filter processing chamber to study ice nuclei concentrations has become wide-spread since its introduction by Bigg et al. in 1961. The technique is convenient because of the simplicity of its operation and because it could be run remote from the place of field study. It has however been found to suffer from a number of drawbacks, namely, the volume effect, the chamber height effect, the vapour depletion effect, etc.Comparison of the results obtained by running a traditional filter processor and a continuous flow chamber under identical temperature and humidity conditions for polluted Manchester air has shown that the latter technique detects more ice nuclei than the former one by a factor of about 14±4. These results confirm that the filter technique suffers from the vapour depletion effect. The present results are in agreement with Bigg et al., Mossop and Thorndike, and King.In the light of our findings the filter technique does not appear to be a standard method. Therefore the ice nuclei data obtained with the filter method should not be extended to clouds in order to study their microphysical properties.     

湍流通量计算方法和误差的比较研究

近地层的风、温、湿梯度以及辐射和土壤热通量资料在过去的几十年间被广泛地用于计算陆-气感热、潜热通量.然而,不同的计算方法之间存在一些差异,随意的选用可能会造成计算结果存在较大的误差.文中利用绿洲系统能量与水分循环过程观测试验的2005年6月甘肃金塔绿洲中部观测资料,在分析了观测期间近地层微气象特征的基础上,对鲍恩比法、空气动力学法(包含两种不同计算方案)和变分法计算的绿洲农田下垫面的湍流通量进行了比较,并通过敏感性实验和理论分析探讨了不同方法间计算结果的差异和误差的来源.结果表明:不同方法计算的湍流通量特征存在明显差异.鲍恩比法从理论上满足能量平衡关系,但在昼夜交替和夜晚时出现了计算不稳定现象,因此在这些时段不适用.变分法避免了鲍恩比法计算夜间湍流通量的不稳定性,而且二者计算的白天湍流通量有较好的相关性;同时变分法由于加入了辐射和土壤热通量信息,明显改善了空气动力学法白天的能量平衡状况;变分法计算得到的潜热通量对辐射和微气象条件有较为合理的响应;对数据误差的敏感性试验表明,鲍恩比法和空气动力学法应用于绿洲下垫面上对观测误差较为敏感,而变分法相对比较稳定.进一步的分析表明,鲍恩比法在-2<β<0的范围内由于方法本身局限而适用性较差;而空气动力学方法计算结果的差异和误差来源于所应用的相似性函数.因而与鲍恩比法和空气动力学法计算的湍流通量值相比较,变分法的计算结果更加合理和稳定,在绿洲下垫面有较好的适用性.该文研究方法和结果可为这些方法的使用提供参考.     

Tunable diode laser measurements of trace gases during the 1988 Polarstern cruise and intercomparisons with other methods

Measurements of NO₂, HCHO, and H₂O₂ were made by the highly specific method of mid infra-red absorption spectroscopy using tunable diode lasers (TDLAS) during the 1988 Polarstern expedition. The TDLAS data are compared to those obtained during the cruise using less direct methods. Southern Hemisphere NO₂ levels suggest nett photochemical destruction of O₃ in the boundary layer. Northern Hemisphere HCHO averaged 0.47±0.2 ppbv; the HCHO measurements are used in a simple calculation to estimate OH noontime maxima of 3–6×10⁶ cm^-3.     

Consequences of Incomplete Surface Energy Balance Closure for CO2 Fluxes from Open-Path CO2/H2O Infrared Gas Analysers

We present an approach for assessing the impact of systematic biases in measured energy fluxes on CO₂ flux estimates obtained from open-path eddy-covariance systems. In our analysis, we present equations to analyse the propagation of errors through the Webb, Pearman, and Leuning (WPL) algorithm [Quart. J. Roy. Meteorol. Soc. 106, 85–100, 1980] that is widely used to account for density fluctuations on CO₂ flux measurements. Our results suggest that incomplete energy balance closure does not necessarily lead to an underestimation of CO₂ fluxes despite the existence of surface energy imbalance; either an overestimation or underestimation of CO₂ fluxes is possible depending on local atmospheric conditions and measurement errors in the sensible heat, latent heat, and CO₂ fluxes. We use open-path eddy-covariance fluxes measured over a black spruce forest in interior Alaska to explore several energy imbalance scenarios and their consequences for CO₂ fluxes.     

Parameterization of the Absorption of the H2O Continuum, CO2, O2, and Other Trace Gases in the Fu-Liou Solar Radiation Program

The absorption properties of the water vapor continuum and a number of weak bands for H2O, O2, CO2, CO, N2O, CH4, and O3 in the solar spectrum are incorporated into the Fu-Liou radiation parameterization program by using the correlated k-distribution method (CKD) for the sorting of absorption lines. The overlap absorption of the H2O lines and the H2O continuum (2500-14500 cm^-1) are treated by taking the two gases as a single-mixture gas in transmittance calculations. Furthermore, in order to optimize the computation efforts, CO2 and CH4 in the spectral region 2850-5250 cm^-1 are taken as a new singlemixture gas as well. For overlap involving other absorption lines in the Fu-Liou spectral bands, the authors adopt the multiplication rule for transmittance computations under which the absorption spectra for two gases are assumed to be uncorrelated. Compared to the line-by-line (LBL) computation, it is shown that the errors in fluxes introduced by these two approaches within the context of the CKD method are small and less than 0.48% for the H20 line and continuum in the 2500-14500 cm^-1 solar spectral region, -1% for H2O (line) H2O (continuum) CO2 CH4 in the spectral region 2850-5250 cm^-1, and -1.5% for H2O (line) H2O (continuum) O2 in the 7700-14500 cm^-1 spectral region. Analysis also demonstrates that the multiplication rule over a spectral interval as wide as 6800 cm^-1 can produce acceptable errors with a maximum percentage value of about 2% in reference to the LBL calculation. Addition of the preceding gases increases the absorption of solar radiation under all sky conditions. For clear sky, the increase in instantaneous solar absorption is about 9%-13% (-12 W m^-2) among which the H20 continuum produces the largest increase, while the contributions from O2 and CO2 rank second and third, respectively. In cloudy sky, the addition of absorption amounts to about 6-9 W m^-2. The new, improved program with the incorporation of the preceding gases produces a smaller solar absorption in clouds due to the reduced solar flux reaching the cloud top.     

A comparison of local and non-local turbulence closure methods for the case of a cold air outbreak

Numerical experiments have shown that large-eddy-simulation models (LES) are able to reproduce the common features of convective boundary layers (CBL) quite well. Models which cannot resolve the convective motions due to their grid structure (1D-models or models with coarse horizontal and/or vertical resolution) have to take into account the effects of large eddies within their subgrid diffusion terms. Turbulent fluxes are frequently parameterized through first-order-closure methods (K-theory). Recently, non-local closure schemes have also been developed. In this paper we compare 1D-and 2D-models using different local and non-local first-order closure methods. The analysis is carried out for the case of an idealized cold air outbreak (CAO). One of the non-local closures is based on the so-called transilient turbulence theory. The reference states are given by a bulk-model and a 2D-model which resolves the large eddies explicitly. A comparison of the results is presented for characteristic quantities such as evolution of boundary-layer height and surface heat flux as well as mean wind and temperature profiles. It is found that simple local first-order closure does not give good agreement with the reference models. The results of the transilient turbulence model shows that a non-local closure is able to parameterize the effects of the large eddies. Comparable results are produced by a local closure where eddy diffusivities are parameterized by dimensionless gradient-functions.     

Field Measurements of Atmospheric Photolysis Frequencies for O3, NO2, HCHO, CH3CHO, H2O2, and HONO by UV Spectroradiometry

A calibrated spectroradiometer was used for the measurement of spectra of the absolute actinic flux F during the POPCORN field campaign in Pennewitt (53.8° N, 11.7° E, sea level) in August 1994. The obtained set of actinic flux spectra was used to determine the photolysis frequencies J(O1D), J(NO2), J(HCHO), J(H2O2), J(HONO), and J(CH3CHO), using molecular photodissociation data from literature. The accuracy of the actinic flux measurement was about ±5%. The accuracy of the photolysis frequency determination is limited by the uncertainties of the molecular absorption cross section and quantum yield data. A good agreement within the experimental uncertainties was found in comparison with measurements of J(O1D) and J(NO2) by filterradiometer which were calibrated absolutely against chemical actinometer. A comparison of this work's photolysis frequency measurements at 40° solar zenith angle with respective measured and modeled data from the literature also shows good agreement for most of the processes considered in this work. However, in the case of J(NO2) data reported in the literature as a function of solar zenith angle differences up to a factor of 1.6 with respect to this work's J(NO2) data are observed. Since this is far beyond the estimated experimental uncertainties, other atmospheric variables, such as aerosols, seem to affect J(NO2) to an extent that is underestimated by now and make indirect comparisons of J(NO2) measurements difficult.     

A comparison between natural and anthropogenic emissions of the reduced sulfur compounds H2S, COS, and CS2 in a tropical industrialized region

Extensive ambient concentration and flux measurements have been performed in the heavily polluted region of Cubatão/Brazil. Substantial contribution of anthropogenic sources to the local reduced sulfur burden has been observed. As a result of this atmospheric sulfur burden average gas exchange between vegetated soils and the atmosphere shows net deposition. Based mainly on own field measurements a local budget for H₂S, COS, and CS₂ has been made up in order to calculate anthropogenic emissions. All major sources and sinks in the chosen atmospheric reservoir (24×20×1 km) have been taken into account. Due to the small reservoir size fluxes across its boundaries are dominant sources and sinks. The differences between outflux and influx therefore account for the unknown anthropogenic emissions which have been determined to be 80±10 (H₂S), 66±15 (COS), and 29±6 Mmol year^-1 (CS₂). Other sources and sinks like natural emissions, chemical conversion, and dry deposition turned out to be of minor importance on a local scale. In fact, inside the investigated reservoir natural emissions were below 0.5% of anthropogenic emissions. Anthropogenic emissions of H₂S, COS, and CS₂ quantified in this work have been compared with global emission estimates for these compounds made by other authors. We conclude that global anthropogenic emissions of reduced sulfur compounds especially of COS and CS₂ are currently under-estimated.     

利用HALOE资料分析中层大气中水汽和甲烷的分布特征

利用1991年12月至2004年5月的HALOE资料，分析了中层大气中微量气体水汽和甲烷的垂直和水平分布特征。垂直分布特征是:水汽混合比在对流层顶和平流层底达到极小值（此极小值区被称为湿层顶），平流层里水汽混合比随高度增加，在平流层上层和中间层低层混合比出现明显的扰动，在中间层顶再次达到极小值，向上混合比又随高度增加。甲烷混合比从100 hPa附近向上混合比一直减少。经向分布特征主要表现为:平流层中下层水汽混合比低值区在热带地区上拱，水汽混合比自低纬向高纬递增；而该气层甲烷混合比则是高值区在热带地区上拱，甲烷混合比自低纬向高纬递减。在低平流层副热带20°S～30°S（20°N～30°N）附近二者混合比水平梯度相对偏大。平流层中上层二者等值线在北半球夏季变成双峰形势，北半球冬季仍是单峰形势。中间层二者都主要表现为冬、夏季分布形势相反。在北半球夏季30°N，平流层中下层水汽和甲烷混合比纬向梯度很小，对流层上层以及中间层二者混合比纬向梯度明显。     

A comparison study of the methods of conditional nonlinear optimal perturbations and singular vectors in ensemble prediction

The authors apply the technique of conditional nonlinear optimal perturbations (CNOPs) as a means of providing initial perturbations for ensemble forecasting by using a barotropic quasi-geostrophic (QG) model in a perfect-model scenario. Ensemble forecasts for the medium range (14 days) are made from the initial states perturbed by CNOPs and singular vectors (SVs). 13 different cases have been chosen when analysis error is a kind of fast growing error. Our experiments show that the introduction of CNOP provides better forecast skill than the SV method. Moreover, the spread-skill relationship reveals that the ensemble samples in which the first SV is replaced by CNOP appear superior to those obtained by SVs from day 6 to day 14. Rank diagrams are adopted to compare the new method with the SV approach. The results illustrate that the introduction of CNOP has higher reliability for medium-range ensemble forecasts.     

Modelling Fluxes and Concentrations of CO 2 , H 2 O and Sensible Heat Within and Above a Mountain Meadow Canopy: A Comparison of Three Lagrangian Models and Three Parameterisation Options for the Lagrangian Time Scale

Two simple analytical Lagrangian and a Lagrangian random walk model,together with three options for the parameterisation of the Lagrangian timescale, are compared in their ability to predict fluxes and scalar concentrationsof CO₂, H₂O and sensible heat within and above a mountain meadowin the eastern Alps. Results indicate that both scalar concentrations and ecosystemfluxes exhibit little sensitivity to the differences between the investigated modelsand may be predicted satisfactorily by one of the simpler models so long as thesource/sink strength is parameterised correctly. Model results also show littlesensitivity to the parameterisation of the vertical variation of the Lagrangiantime scale, yet the increase of the Lagrangian time scale towards the groundpredicted by one of the three investigated parameterisation options resulted inless agreement with measurements as compared to the other two, which assumedthe Lagrangian time scale to be either constant with height or to decay towardszero at the ground surface. Correspondence between simulated and measuredfluxes and scalar concentrations of CO₂, H₂O and sensible heat weregenerally satisfactory, except for shortly after the meadow was cut, when thesignificant increase of respiratory carbon losses could not be captured by themodel.     

On the scavenging of SO2 by cloud and rain drops: IV. A wind tunnel and theoretical study of the absorption of SO2 in the ppb(v) range by water drops in the presence of H2O2

An experimental study involving the Mainz vertical wind tunnel is described where the rate of SO₂ removed from the air by freely suspended water drops was measured for SO₂ concentrations in the gas phase ranging between 50 and 500 ppb, and for various H₂O₂ concentrations in the liquid phase. In a first set of experiments, the pH inside the SO₂ absorbing drops was monitored by means of colour pH indicators added to the drops. In a second set of experiments, the amount of SO₂ scavenged by the drops was determined as sulfate by an ionchromatograph after the drops had been removed from the vertical air stream of the wind tunnel after various times of exposure to SO₂. The results of our experimental study were compared with the theoretical gas diffusion model of Walcek and Pruppacher which was reformulated for the case of SO₂ concentrations in the ppbv(v) range for which the main resistance to diffusion lies in the gas phase surrounding the drop. Excellent agreement between experiment and theory was obtained. Encouraged by this agreement, the theory was used to investigate the rate of sulfate production inside a drop as a function of pH. The sulfate production rate, which includes transport and oxidation, was compared with the production rate based on bulk equilibrium, as cited in the literature.     

The equilibrium constant of NO2 with N2O4 and the temperature dependence of the visible spectrum of NO2: A critical review and the implications for measurements of NO2 in the polar stratosphere

Measurements of stratospheric NO₂ by ground-based visible spectrometers rely on laboratory measurements of absorption cross-sections. We review low-temperature laboratory measurements, which disagree by amounts claimed to be significant. Our recalculation of their errors shows that in general disagreements are not significant and that errors in the ratios of cross-sections at low to room temperature are between ±3% and ±8.8%. Of these errors, up to ±3.5% was contributed by errors in the equilibrium constant,K _p, in those measurements where the pressure was above 0.1 mbar.We review measurements and calculations ofK _p, which were accurate to ±5% from 300 to 233 K. Each method was potentially flawed. For example, infrared measurements of the partial pressure of NO₂ ignored the dependence of absorption on total pressure. From thermodynamic theory, formulae forK _pcan be derived from expressions for the variation of heat capacity with temperature. Contrary to common belief, coefficients in the formulae used by spectroscopists were not derived from the thermodynamic quantities. Rather, they were fitted to measurements or to calculations. Hence, they are empirical and it is dangerous to extrapolate below 233 K, the lowest temperature of the measurements.There are no measurements of NO₂ cross-sections below 230 K. Extrapolation of these cross-sections to analysis of measurements of NO₂ at the low temperatures of the Arctic and Antarctic stratosphere is also dangerous. For satisfactory analysis of polar spectra, the NO₂ cross-sections should be measured at temperatures down to 190 K with a relative accuracy of ±1%. This difficult experiment would need a cell of minimum length 32 m whose length can be adjusted. Because their effects are circular, many errors cannot be removed simply. Although circular errors also arise in the measurements ofK _pand of the infrared spectrum, their weights differ from those in the visible spectrum. The optimum experiment might therefore simultaneously measure the visible and infrared spectra andK _p.     

一次层状云系水分收支和降水机制的数值研究

对2002年10月18—20日河南省层状云系的水分收支和降水机制用MM5模式模拟的结果表明,河南省域以外的水物质主要通过西和南边界输送到区域内,19日降水主要时段总水物质通量在水平方向上为净流入。对河南省域水汽、水凝物和总水物质的水分平衡等式中各项的估算表明该区域水物质基本达到收支平衡。估算的河南省域总水物质降水效率、凝结率、凝华率和水凝物降水效率及水汽降水效率分别约33.1%、27.7%、13.1%、69.7%和31.1%,总水物质降水效率与水汽降水效率接近是由于参与的水物质总量中水汽占绝大部分。约58.2%以上的冰晶转化为雪,超过82.1%的雪融化,不到11.1%的雪转化为霰,霰粒子几乎完全融化。冰晶通过凝华过程增长。雪主要由冰晶转化产生,凝华增长率比撞冻增长率高得多。雨水由暖云和冷云过程产生和增长,雨水碰并云水量和冰粒子融化量对雨水的贡献相近,云雨自动转化量小。可见,在主要降水时段,降水是由冷云和暖云过程共同产生的。冰粒子凝华增长对雨水的贡献最大超过35%,撞冻增长的贡献最高不足12%,可见水汽对降水粒子增长重要。催化层、冰水混合层和液水层对降水的贡献分别约为15%—27%、45%—50%和23%—38%,表明此"催化-供给"云中冰粒子在冰水混合层的增长对降水的贡献相当大。     

A comparison of PMIP2 model simulations and the MARGO proxy reconstruction for tropical sea surface temperatures at last glacial maximum

Results from multiple model simulations are used to understand the tropical sea surface temperature (SST) response to the reduced greenhouse gas concentrations and large continental ice sheets of the last glacial maximum (LGM). We present LGM simulations from the Paleoclimate Modelling Intercomparison Project, Phase 2 (PMIP2) and compare these simulations to proxy data collated and harmonized within the Multiproxy Approach for the Reconstruction of the Glacial Ocean Surface Project (MARGO). Five atmosphere–ocean coupled climate models (AOGCMs) and one coupled model of intermediate complexity have PMIP2 ocean results available for LGM. The models give a range of tropical (defined for this paper as 15°S–15°N) SST cooling of 1.0–2.4°C, comparable to the MARGO estimate of annual cooling of 1.7 ± 1°C. The models simulate greater SST cooling in the tropical Atlantic than tropical Pacific, but interbasin and intrabasin variations of cooling are much smaller than those found in the MARGO reconstruction. The simulated tropical coolings are relatively insensitive to season, a feature also present in the MARGO transferred-based estimates calculated from planktonic foraminiferal assemblages for the Indian and Pacific Oceans. These assemblages indicate seasonality in cooling in the Atlantic basin, with greater cooling in northern summer than northern winter, not captured by the model simulations. Biases in the simulations of the tropical upwelling and thermocline found in the preindustrial control simulations remain for the LGM simulations and are partly responsible for the more homogeneous spatial and temporal LGM tropical cooling simulated by the models. The PMIP2 LGM simulations give estimates for the climate sensitivity parameter of 0.67°–0.83°C per Wm⁻², which translates to equilibrium climate sensitivity for doubling of atmospheric CO₂ of 2.6–3.1°C.     

大气中O3和CO2增加对大豆复合影响的试验研究

利用OTC-1型开顶式气室,对大豆"中黄14"进行了长时期不同O3和CO2处理的接触试验,模拟研究CO2和O3浓度倍增及其交互作用对大豆发育期、黄叶率和绿叶率、根瘤、生物量及其分配、产量结构、籽粒品质及叶片膜保护系统的影响,结果表明:单独O3浓度倍增,发育期明显提前;生物量最多可减少近一半,产量最多减产60%以上;粗蛋白含量增加6.2%,粗脂肪含量降低7.6%;叶片脂膜过氧化加剧.单独CO2浓度倍增,开花后发育期有所延迟;对生物量及产量有明显的正效应,成熟时总生物量和籽粒产量分别比T5增加21.0%和20.3%;粗蛋白和粗脂肪含量分别下降3.3%和1.6%;结荚前叶片脂膜过氧化反应减轻.CO2和O3持续倍增和逐渐达到倍增交互作用处理,在生物量、产量方面表现为CO2的影响大于O3,在叶片膜保护系统方面表现为O3的影响大于CO2,粗蛋白含量下降,粗脂肪含量上升,叶片脂质过氧化加剧.熏气处理均可造成:黄叶率上升,绿叶率下降,凋落物增加,且单独O3浓度倍增的处理最明显,通气仅10天黄叶率就高于50%;超氧化物歧化酶活性增强;气孔阻力增加,蒸腾速率下降,且单独CO2浓度倍增的处理最明显,尤其在高湿阴天,气孔阻力和蒸腾速率变化最高分别可达增加234.0%和下降58.5%.     

Synthesizing a policy-relevant perspective from the three IPCC “Worlds”—A comparison of topics and frames in the SPMs of the Fifth Assessment Report

The paper investigates topics, emphases, frames and absences in the Summary for Policymakers parts of the three Working Group reports in the IPCC 5th Assessment Report and the Summary for Policymakers of the Synthesis Report. It explores similarities and differences by using various tools of lexical and discourse analysis, combining quantitative and qualitative methods. The main results are these: First, each Working Group’s Summary reflects not only the Working Group’s distinctive mandate but also a distinctive intellectual framing. Second, although there are some significant differences in the emphases given to different themes from the Working Groups, the Synthesis Summary covers the main topics of the three other Summaries, and constitutes a relatively integrated summary of the complete Assessment Report. Third, we find though that the Synthesis Summary centrally follows up the risk framing and language which are prominent in Working Group II but semi-absent in the other Working Groups, as part of constructing a policy-relevant statement from the three distinctive reports. In addition, the Synthesis Summary makes use of linguistic devices which contribute to ‘amplify’ the strength of statements, as part of transferring messages effectively from the scientific context to a policy-maker audience. Fourth, we find that the style and tone of the IPCC Summaries conduce also to important absences and imbalances in emphasis: main victims of climate change (particular groups of vulnerable people) remain virtually invisible in the Summaries, unlike the impacts in nature and ecological systems or the aggregate economic impacts, and correspondingly the challenges, options and opportunities for action remain relatively underdeveloped in the analysis.     

A model study of ATMOS observations and the heterogeneous loss of N2O5 by the sulphate aerosol layer

The heterogeneous removal of N₂O₅ by sulphuric acid aerosols as been invoked to explain the decline of mid-latitude ozone in the last decade. We have used a photochemical model to study measurements of odd-nitrogen made by Spacelab 3. The gas-phase photochemical model overestimates the amount of N₂O₅ present. The loss of N₂O₅ by aerosols does reduce N₂O₅, but is likely to be slower than assumed in WMO (1992). The sunset measurements at 25.5 km cannot be explained by heterogeneous loss of N₂O₅ and is more likely to be due to a faster photolysis than assumed. New absorption cross-sections of HNO₃ reduce the photolysis of HNO₃ so that the model with gas-phase chemistry only gives better agreement at 19 km, than a model including heterogeneous chemistry.