Total column densities of tropospheric and stratospheric trace gases in the undisturbed Arctic summer atmosphere

Ground-based FTIR measurements have been performed in the Arctic summer in July 1993 and June 1994 at 79° N to study the zenith column densities of several trace gases in the undisturbed Arctic summer atmosphere. Zenith column densities of H₂O, N₂O, HNO₃, NO₂, NO, ClONO₂, ClO, HCl, HF, COF₂, OCS, SF₆, HCN, CH₄, C₂H₆, C₂H₂, CO, O₃, CFC-12, CFC-22, and CO₂ were retrieved by line-by-line calculations. The results are compared with winter and springtime observations measured at the same site, with column densities obtained in the Antarctic summer atmosphere, and with measurements at midlatitudes. For HCl the spectra give lower total zenith columns than expected, but the ratio HF/HCl agrees well with midlatitude literature data. Measurements of ClONO₂ give low total columns in agreement with observations at midlatitudes. In the undisturbed atmosphere HCl was found to be in excess of ClONO₂. The total columns of HNO₃, N₂O and the sum of NO and NO₂ agree with summer observations in Antarctica. Results for the tropospheric trace gas C₂H₆ are higher by 250% when compared with Antarctic observations. Contrary to N₂O and CH₄ the seasonal cycle of C₂H₆ and C₂H₂ give much higher total columns in winter/spring compared to the summer observations. This is assigned to transport of polluted airmasses from mid-latitudes into the Arctic.     

Multi-species chemical data assimilation with the Danish Eulerian hemispheric model: system description and verification

Satellite retrievals of atmospheric composition provide a wealth of data on a global scale. These complement results from atmospheric chemistry-transport models (CTMs), and can be combined using data assimilation. We present two assimilation schemes coupled to the Danish Eulerian Hemispheric Model (DEHM), a three-dimensional, off-line CTM with full photochemistry: a variant on the ensemble Kalman filter and the three-dimensional variational scheme. The aim of this paper is to describe the two schemes and present an initial assessment of their impacts on model skill. Retrievals of multiple atmospheric trace gases are assimilated, namely: NO₂ tropospheric column densities, CH₄ total column densities, and partial column concentrations of O₃, CO and CH₄; these data are retrieved from four satellite sensors. Data for each species are assimilated independently of one another, and other species are only adjusted indirectly via the model’s chemistry and dynamics. Assimilation results are compared with measurements from surface monitoring stations and other satellite retrievals, and preliminary validation results are presented.Reference simulations (without assimilation) grossly underestimate surface CO concentrations, and both assimilation schemes eliminate this large and systematic model bias. The assimilation improves the spatial correlation of modelled CO with surface observations, and improves the spatial correlation between forecasts and retrievals for CO, NO₂ and O₃. Results for CH₄ show a loss of skill due to a mismatch in model bias between two assimilated CH₄ data-sets. Finally, we discuss differences in methodology and results between this paper and a recent study on multi-species chemical data assimilation. Joint optimisation of initial conditions and emission rates offers a promising direction for improving modelled boundary-layer concentrations.     

整层大气甲烷总量季节变化的遥测

利用自行研制的一台用于探测大气成分的太阳红外光谱仪 ,在地面连续自动地记录了晴天的太阳红外光谱。用逐线积分法计算了整层大气的吸收 ,发现在 3.42 8μm波段主要是大气甲烷的吸收 ,从记录的该波段的太阳红外光谱中反演出整层大气中甲烷的总含量 ,经过近一年半的观测 ,得到了合肥地区大气甲烷垂直柱含量的季节变化规律。发现其变化规律与北半球背景对流层空气采样分析法测量的甲烷季节变化规律基本相同。文中详细介绍了测量仪器、测量原理和部分测量结果 ,并对结果进行了简单的讨论。     

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。     

Air pollutant emission rates and concentrations in medieval churches

A series of indoor air quality parameters were determined in two medieval churches, in Cyprus (temperature, relative humidity, total and UV solar radiation, CO₂ indoors and O₃, NO, NO₂ ^*, HNO₃ ^*, HCl, HCOOH, CH₃COOH indoors and outdoors). These data were used as input in a validated indoor air quality model to predict indoor air pollutant source strengths and species concentrations that resulted from dark or photochemical reactions. The NO and NO₂ emission rates due to the burning of incense or candles were estimated. Model results revealed that heterogeneous NO formation takes place simultaneously with the heterogeneous HONO formation. Also, model application has shown that indoor NO_x emissions resulted in decreased free radical concentrations, in contrast to the organic compound emissions, which increased free radical concentrations. This effect of indoor emissions on indoor radicals can partly explain the indoor enhancement/depression of indoor gaseous acid formation.     

A modified profile method for determining the vertical fluxes of NO,NO2, ozone,and HNO3 in the atmospheric surface layer

A modified profile method for determining the vertical deposition (or/and exhalation) fluxes of NO, NO₂, ozone, and HNO₃ in the atmospheric surface layer is presented. This method is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these trace gases. The analysis (aerodynamic profile method) includes a detailed determination of the micrometeorological quantities (such as the friction velocity, the fluxes of sensible and latent heat, the roughness length and the zero plane displacement), and of the height-invariant fluxes of the composed chemically conservative trace gases with group concentrations c ₁=[NO]+[NO₂]+[HNO₃], c ₂=[NO₂]+[O₃]+3/2·[HNO₃], and c ₃=[NO]–[O₃]–1/2·[HNO₃]. The fluxes of the individual species are finally determined by the numerical solution of a system of coupled nonlinear ordinary differential equations for the concentrations of ozone and HNO₃ (decoding method). The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The model requires only the vertical profile data of wind velocity, temperature and humidity and concentrations of NO, NO₂, ozone, and HNO₃.The method has been applied to vertical profile data obtained at Jülich (September 1984) and collected in the BIATEX joint field experiment LOVENOX (Halvergate, U.K., September 1989).     

CALCULATION OF AIR-MASS FACTORS FOR O3

In conversion of the integrated slant column amount of atmospheric ozone(O₃) measured by the ground-based spectrometer technique during twilight to the vertical quantity,the air-mass factor(AMF) is an important parameter.In this work,calculations of AMF for ozone were performed for different atmospheres.It is shown that the O₃ AMF has seasonal variations with the minimum at the beginning of spring and the maximum in summer due to the seasonal change in the vertical distributions of O₃.A parameterization relation is obtained between O₃ AMF and optical thickness of stratospheric volcanic aerosols based on the Monte-Carlo radiative transfer simulations.     

MEASUREMENT OF CARBON MONOXIDE COLUMN CONTENT AND OTHER ATMOSPHERIC TRACE GASES FROM INFRARED SPECTRA*

The measurement of column content of carbon monoxide,methane,and other atmospheric traces gases as well as aerosols has been conducted during the fall of 1992 and 1997,using an infrared spectrometer of moderate resolution in the cooperation of the Laboratory for Middle Atmosphere and Global Environment Observation(LAGEO),Institute of Atmospheric Physics,Chinese Academy of Sciences,with the Institute of Atmospheric Physics,Russian Academy of Sciences.The variation characteristics of atmospheric CO column content in Beijing area are presented.The analysis of the measurement shows that the CO column concentration of 0.10 mg cm^-2 can be considered as the background over Beijing area.and the concentration as high as 0.75 mg cm^-2 was observed under some unfavorable meteorological situations.     

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.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at     

Evaluation of the tungsten oxide denuder tube technique as a method for the measurement of low concentrations of nitric acid in the troposphere

The applicability of the tungsten oxide denuder tube technique for the measurement of nitric acid in the rural troposphere was investigated. The technique is based on selective chemisorption of HNO₃ from the gas stream, thermal desorption, conversion to NO, and analysis by NO–O₃ chemiluminescence. Ammonia, which is also collected and desorbed as NH₃ and NO, was separated from the HNO₃-derived NO by linear temperature-programed thermal desorption. Possible interferences by NO₂, HCN, PAN, and n-propyl nitrate (NPN) were tested and found to be significant under conditions found in the lower troposphere. Simultaneous ambient measurements of HNO₃ were made with the tungsten oxide denuder tube and nylon filter methods at a rural site in the Colorado mountains (Niwot Ridge, CO). Nitric acid levels measured by the tungsten oxide denuder tube averaged a factor of 3 higher than levels measured by the nylon filter technique. Tests involving the placement of nylon materials in front of the tungsten oxide denuder tube show that there are species, as yet unidentified, present in the atmosphere that interfere with the measurement of HNO₃ by the tungsten oxide technique.     

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.     

Particulate matter and gaseous pollutants during a tropical storm and air pollution episode in Southern Taiwan

Gaseous pollutants and PM_2.5 aerosol particles were investigated during a tropical storm and an air pollution episode in southern Taiwan. Field sampling and chemical analysis of particulate matter and gaseous pollutants were conducted in Daliao and Tzouying in the Kaohsiung area, using a denuder-filter pack system during the period of 22 October to 3 November 2004. Sulfate, nitrate and ammonium were the major ionic species in the PM_2.5, accounting for 46 and 39% of the PM_2.5 for Daliao and Tzouying, respectively. Higher PM_2.5, Cl^?, NO₃^? and NH₄⁺, HNO₂ and NH₃ concentrations were found at night in both stations, whereas higher HNO₃ was found during the day. In general, higher PM_2.5, HCl, NH₃, SO₂, Cl^?, NO₃^?, SO₄^2? and NH₄⁺ concentrations were found in Daliao. The synoptic weather during the experiment was first influenced by Typhoon NOCK-TEN, which resulted in the pollutant concentrations decreasing by about two-thirds. After the tropical thunderstorm system passed, the ambient air quality returned to the previous condition in 12 to 24 h. When there was a strong subsidence accompanied by a high-pressure system, a more stable environment with lower wind speed and mixing height resulted in higher PM_2.5, as well as HNO₂, NH₃, SO₄^2?, Cl^?, NO₃^?, NH₄⁺ and K⁺ concentrations during the episode days. The rainfall is mainly a scavenger of air pollutants in this study, and the stable atmospheric system and the high emission loading are the major reasons for high air pollutant concentrations.     

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.     

High atmospheric NO x levels and multiple photochemical steady states

Previous zero-dimensional photochemical calculations indicate that multiple tropospheric steady states may exist, in which different NO _x (NO+NO₂) levels could be supported by the same source of NO _x . To investigate this possibility more closely, a one-dimensional photochemical model has been used to estimate the rate of removal of atmospheric NO _x compounds at different NO _x levels. At low NO _x levels NO _x is photochemically converted to HNO₃, which is removed by either wet or dry deposition. At high NO _x levels formation of HNO₃ is inhibited, and NO _x is removed by a variety of other processes, including rainout of N₂O₄ and N₂O₅, surface deposition of NO and NO₂, and direct dissolution of NO and NO₂ in rainwater. Multiple steady states are possible if surface deposition of NO _x is relatively inefficient. The NO _x source required to trigger high atmospheric NO _x levels is approximately 10 to 15 times the present global emission rate-less than half the source strength predicted by the zero-dimensional model. NO _x mixing ratios in excess of 10^-7 would cause severe damage to the ozone layer and could result in either a climatic warming or cooling, depending upon the amount of NO₂ present.     

Observed Trends in Total Vertical Column Abundances of Atmospheric Gases from IR Solar Spectra Recorded at the Jungfraujoch

Since 1984, about 15000 high quality infrared solar spectra have beenrecorded with state-of-the-art grating and Fourier transform spectrometersat the International Scientific Station of the Jungfraujoch, Switzerland.Nonlinear least squares spectral curve fitting of selected microwindowscontaining isolated and well characterized lines of 20 telluric gases haveallowed to retrieve their total vertical column abundances above thestation, leading to observational data bases essential to derive long- andshort-term changes experienced by these species during the last 12 years. Inthis paper, we focus on atmospheric gases of particular interest within thecontext of the EUROTRAC/TOR (Tropospheric Ozone Research) project; secularevolution as well as seasonal cycles of the minor constituentsCH₄, CO and of the trace gasesC₂H₆, OCS, C₂H₂, HCNand H₂CO are reported and discussed. The long-livedN₂O is included as a tracer of the dynamic activity of theatmosphere.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.