Ozone depletion in the plume of a solid-fueled rocket

The local effects of the emission of a solid-fueled rocket on the stratospheric ozone concentration have been investigated by photochemical model calculations. A one-dimensional horizontal model has been applied which calculates the trace gas composition at a single atmospheric altitude spatially resolved around the exhaust plume. Different cases were tested for the emissions of the Space Shuttle concerning the composition of the exhaust and the effects of heterogeneous reactions on atmospheric background aerosol.The strongest depletion of ozone is achieved when a high amount of the emitted chlorine is Cl₂. If it is purely HCl, the effect is smallest, though in this case the heterogeneous reactions show their largest influence. From the results it may be estimated whether ozone depletion caused by rocket launches can be detected by satellite instruments. It appears that the chance of coincidental detection of such an event is rather small.     

Influence of strong sudden stratospheric warmings on ozone in the middle stratosphere according to millimeter wave observations

This paper reports the study data on variations in the ozone content in the middle stratosphere over Moscow based on millimeter wavelength observations during a range of midwinter sudden stratospheric warmings that occurred in the past two decades. The relation of ozone with planetary waves and the intensity of the polar stratospheric vortex has been established. The ozone vertical distribution has been monitored with a highly sensitive spectrometer with a two-millimeter wave band. The discovered phenomena of a relatively long-term lower ozone content in December in the considered cold half-year periods are related to the higher amplitude of the planetary wave with n = 1. Such phenomena preceded the development of strong midwinter stratospheric warmings, which, in turn, were accompanied by a significant increase in the ozone content in January. This ozone enrichment was related to the lower amplitude of the wave with n = 1 and higher amplitude of the wave with n = 2 and was accompanied by geopotential H _c.v. growth in the polar vortex center. Specific features of variations in the ozone content under the influence of the major atmospheric processes are observed not only in certain cold half-year periods but are also well seen in the general averaged pattern for winters with strong stratospheric warmings.     

Instantaneous global ozone balance including observed nitrogen dioxide

The catalytic destruction of stratospheric ozone by the oxides of nitrogen is believed to be an important part of the global ozone balance. The lack of sufficient measurements of NO _x concentrations has impeded efforts to quantify this process. Recent measurements of stratospheric nitrogen dioxide from ground-based stations as well as aircraft and balloons have provided a first approximation to a global distribution of NO₂ vertical columns at sunset. These observed vertical columns have been translated into time-dependent vertical NO₂ profiles by means of a one-dimensional atmospheric photochemical model. Using recent observations of air temperature and ozone along with this information, the independent instantaneous (one second) rates of ozone production from oxygen photolysis P(O₃), of ozone destruction from pure oxygen species (Chapman reactions) L(O _x ), and of ozone destruction by nitrogen oxides L(NO _x ) were estimated over the three-dimensional atmosphere. These quantities are displayed as zonal average contour maps, summed over various latitude zones, summed over various altitude bands, and integrated globally between 15 and 45 km. Although the global summation between 15 and 45 km by no means tells the complete story, these numbers are of some interest, and the relative values are: P(O₃), 100; L(O _x ), 15; L(NO _x ), 45±15. It is to be emphasized that this relative NO _x contribution to the integrated ozone balance is not a measure of the sensitivity of ozone to possible perturbations of stratospheric NO _x ; recent model results must be examined for current estimates of this sensitivity.     

A discussion of the chemistry of some minor constituents in the stratosphere and troposphere

A discussion is given of atmospheric reactions in the H₂O–CH₄–O₂–O₃–NO _x system. In the lower troposphere such reactions may lead to significant production of ozone. Their role in the odd hydrogen balance, especially of the troposphere and lower stratosphere, is discussed. CH₃OH may be an intermediate in the oxidation cycle of methane, especially in the cold stratosphere. Its photodissociation into H₂ and CH₂O may consequently provide an important source for stratospheric H₂. Catalytic photochemical chains of reactions involving NO _x and HO _x may also lead to tropospheric destruction of ozone. Due to lack of knowledge it is not possible at present to evaluate the importance of the before-mentioned reactions.With the aid of model calculations it is indicated that stratospheric ozone is most sensitive to changes in the adopted lower boundary values of N₂O and that an increase in water vapour concentrations in the lower stratosphere will indeed cause some increase in ozone as predicted.Fluctuations in the flux of solar radiation near 190 nm may cause significant variations in stratospheric ozone concentrations.     

The impact of moderate-scale explosive eruptions on stratospheric gas injections

Volcanic gases such as SO ₂, H ₂S, HCl and COS emitted during explosive eruptions significantly affect atmospheric chemistry and therefore the Earth's climate. We have evaluated the dependence of volcanic gas emission into the atmosphere on altitude, latitude, and tectonic setting of volcanoes and on the season in which eruptions occurred. These parameters markedly influence final stratospheric gas loading. The latitudes and altitudes of 360 active volcanoes were compared to the height of the tropopause to calculate the potential quantity of volcanic gases injected into the stratosphere. We calculated a possible stratospheric gas loading based on different volcanic plume heights (6, 10, and 15 km) generated by moderate-scale explosive eruptions to show the importance of the actual plume height and volcano location. At a plume height of 15 km for moderate-scale explosive eruptions, a volcano at sea level can cause stratospheric gas loading because the maximum distance to the tropopause is 15–16 km in the equatorial region (0–30°). Eruptions in the tropics have to be more powerful to inject gas into the stratosphere than eruptions at high latitudes because the tropopause rises from ca. 9–11 km at the poles to 15–16 km in the equatorial region (0–30°N and S). The equatorial region is important for stratospheric gas injection because it is the area with the highest frequency of eruptions. Gas injected into the stratosphere in equatorial areas may spread globally into both hemispheres.     

Variations in the 557.7-nm atmospheric emission during stratospheric warming events under conditions of high and low solar activity

The effect of anomalously high average nighttime intensities of the atomic oxygen 557.7-nm atmospheric emission (luminescence heights 85–115 km) during sudden winter stratospheric warming events (SWEs) in Eastern Siberia is considered. Analysis of the variations in the 557.7-nm emission intensity (I _557.7) revealed the interdaily I _557.7-nm variations during SWEs and high average monthly I _557.7-nm values in the winter months in conditions of high solar activity. It has finally been found that the variations with periods of several days, at a maximum of which anomalously high daily values of I _557.7 are observed, are superposed on the average I _557.7-level during SWEs at high solar activity. A high average level of I _557.7 in the winter months in Eastern Siberia can be related to the fact that the atomic oxygen concentration at altitudes of the 557.7 nm emission luminescence increases by a factor of 2–3 in years of high solar activity.     

The characteristics of atmospheric CO<Subscript>2</Subscript> concentration variation of four national background stations in China

Atmospheric carbon dioxide is an important kind of greenhouse gas which influences global temperature. Its concentration variation could indicate the distribution of human and natural activities in various regions. Through the non-dispersive infrared method, flask sampling of atmospheric CO₂ concentration was measured weekly at four national background stations including Waliguan, Shangdianzi, Lin’an, and Longfengshan. Based on the data collected from September 2006 to August 2007, along with the Waliguan station’s experience on in situ observational data processing, the selection methods for sampling data through the atmospheric background CO₂ concentration analysis were preliminarily discussed. On the basis of this result, the variation features of the four typical regions’ atmospheric background CO₂ concentration was analyzed for the first time. The results show that the atmospheric CO₂ concentration at Waliguan, Shangdianzi, Lin’an, and Longfengshan is 383.5, 385.9, 387.8, and 384.3 ppm, respectively. During the research period, CO₂ concentration at the Waliguan station changed slightly. However, the CO₂ concentration changed sharply at the Shangdianzi and the Lin’an stations due to the great influence of human activities in the Jingjinji and the Changjiang Delta economic zones, and changed regularly with seasons at Longfengshan station under dual influences of human activities and plant photosynthesis. The results from this study can lay the foundation for more profound studies on atmospheric CO₂ concentration level of different areas in China, and could be used to improve the understanding of carbon source and sink distribution.     

Estimation of heterogeneous reaction rates for stratospheric trace gases with particular reference to the diffusional uptake of HCl and ClONO2 by polar stratospheric clouds

The stratosphere holds a variety of particulates like polar stratospheric clouds (PSCs) and sulphate aerosols which catalyse chemical reactions. These reactions cause changes in the composition of the stratosphere, including the redistribution of active chlorine which might lead to ozone destruction. As a result during recent years a lot of effort has been directed towards the quantification of the uptake of trace gases like ClONO₂, HCl, etc. into these particulates. However, it has been observed that many of the two and three dimensional models used in such studies are constrained by the lack of adequate rate constant data. This paper describes a theoretical approach to estimate the reaction rate constants for 23 gases on both types of polar stratospheric clouds (type I and II). It is found that for gases like N₂O₅, ClONO₂ and HCl, diffusional uptake is important and contributes significantly to the heterogeneous reaction rate. A complete Lennard-Jones calculation is used to accurately compute the trace gas diffusion coefficients.     

Temperature disturbances in the subauroral lower thermosphere during winter stratospheric warming

Irregular variations in the temperature of the subauroral lower thermosphere during the winter stratospheric warming, which began in the first decade of December 2001 and continued to the end of the observational season (February 19, 2002), have been analyzed. The temperature measurements were based on the thermal broadening of the 557.7 nm oxygen emission measured during moonless nights at Maimaga optical station in the vicinity of Yakutsk (?=63°N, λ=129.7° E) using the Fabry-Pérot spectrometer. Isolated fragments of the map of contour lines of the horizontal temperature field and the globally averaged height-time section of the temperature at the levels of the 1, 2, 5, 10, 30, 50, and 70 hPa isobaric surfaces, obtained by the NOAA Meteorological Satellite Systems, as well as the F _10.7 and Ap indices have been used to analyze the cause-effect relation between the variations in the temperature of the subauroral lower thermosphere and winter stratospheric warming events. It is shown that, when warming is detected at heights of the lower thermosphere, the temperature can become higher than its model values by up to 20 K, which indicates that the planetary waves can penetrate to heights of the lower thermosphere and then propagate downward. In this case the atmosphere cools at heights of the lower thermosphere and tends to heat up above 10 hPa and to cool below 30 and 50 hPa; i.e., we observe the well-known fact of vertical alternation of cold and warm atmospheric regions detected during winter stratospheric warming events.     

Monitoring air pollution in China from geostationary satellite: A synthetic study using simulated observations

We simulated geostationary satellite observations to assess the potential for high spatial-and temporal-resolution monitoring of air pollution in China with a focus on tropospheric ozone(O_3), nitrogen dioxide(NO_2), sulfur dioxide(SO_2), and formaldehyde(HCHO). Based on the capabilities and parameters of the payloads onboard sun-synchronous satellites, we simulated the observed spectrum based on a radiative transfer model using a geostationary satellite model. According to optimal estimation theory, we analyzed the sensitivities and retrieval uncertainties of the main parameters of the instrument for the target trace gases. Considering the retrieval error requirements of each trace gas, we determined the major instrument parameter values(e.g., observation channel, spectral resolution, and signal-to-noise ratio). To evaluate these values, retrieval simulation was performed based on the three-dimensional distribution of the atmospheric components over China using an atmospheric chemical transportation model. As many as 90% of the experiments met the retrieval requirements for all target gases. The retrieval precision of total-column and stratospheric O_3 was 2%. In addition, effective retrieval of all trace gases could be achieved at solar zenith angles larger than 70°. Therefore, the geostationary satellite observation and instrument parameters provided herein can be used in air pollution monitoring in China. This study offers a theoretical basis and simulation tool for improving the design of instruments onboard geostationary satellites.     

A Proposed Method to Estimate In Situ Dissolved Gas Concentrations in Gas‐Saturated Groundwater

Gas‐saturated groundwater forms bubbles when brought to atmospheric pressure, preventing precise determination of its in situ dissolved gas concentrations. To overcome this problem, a modeling approach called the atmospheric sampling method is suggested here to recover the in situ dissolved gas concentrations of groundwater collected ex situ under atmospheric conditions at the Horonobe Underground Research Laboratory, Japan. The results from this method were compared with results measured at the same locations using two special techniques, the sealed sampler and pre‐evacuated vial methods, that have been developed to collect groundwater under its in situ conditions. In gas‐saturated groundwater cases, dissolved methane and inorganic carbon concentrations derived using the atmospheric sampling method were mostly within ±4 and ±10%, respectively, of values from the sealed sampler and pre‐evacuated vial methods. In gas‐unsaturated groundwater, however, the atmospheric sampling method overestimated the in situ dissolved methane concentrations, because the groundwater pressure at which bubbles appear (P_critical) was overestimated. The atmospheric sampling method is recommended for use where gas‐saturated groundwater can be collected only ex situ under atmospheric conditions.     

Variability of planetary waves as a signature of possible climatic changes

The long-term variability of stationary and traveling planetary waves in the lower stratosphere has been investigated using the data of NCEP/NCAR reanalysis. The results obtained show that during the last decades winter-mean amplitude of the stationary planetary wave with zonal wave number 1 (SPW1) increases at the higher middle latitudes of the Northern Hemisphere. It has been suggested that the observed increase in the SPW1 amplitude should be accompanied by the growth in the magnitude of the stratospheric vacillations. The analysis of the SPW1 behavior in the NCEP/NCAR data set supports this suggestion and shows a noticeable increase with time in the SPW1 intra-seasonal variability. The amplitudes of the long-period normal atmospheric modes, the so-called 5-, 10- and 16-day waves, diminish. It is supposed that one of the possible reasons for this decrease can be a growth of radiative damping rate caused, for instance, by the increase of CO₂. To investigate a possible climatic change of the middle atmosphere dynamics caused by observed changes in the tropospheric temperature, two sets of runs (using zonally averaged temperature distributions in the troposphere typical for January 1960 and 2000) with the middle and upper atmosphere model (MUAM) have been performed. The results obtained show that on average the calculated amplitude of the SPW1 in the stratosphere increased in 2000 and there is also an increase of its intra-seasonal variability conditioned by nonlinear interaction with the mean flow. This increase in the amplitudes of stratospheric vacillations during the last four decades allows us to suggest that stratospheric dynamics becomes more stochastic.     

Detailed PSC formation in a two-dimensional chemical transport model of the stratosphere

A new two-dimensional zonal model of the stratosphere, based on a formulation in an isentropic framework, with complete chemistry has been coupled with a high resolution detailed microphysical model for polar stratospheric clouds (PSCs). The 2D model chemistry includes all presently known heterogeneous processes on sulfate aerosols and PSCs. The coupling of these two models, with inherently different time scales, is discussed. It is demonstrated that in order to obtain a realistic interrelationship between NO_y and N₂O an accurate simulation of the sedimentation by PSC particles is necessary. A good agreement of model PSC presence and observations is found for the Antarctic polar winter without the need to impose additional artificial temperature variations in the model. The calculated occurrence of polar stratospheric clouds and resulting heterogeneous chemistry during the Antarctic winter are discussed. Sensitivity of the polar stratospheric chemical composition and cloud formation for different perturbations is investigated by studying the effects of transport across the polar vortex boundary and heterogeneous processing by an enhanced sulfate aerosol load. The importance of including sedimentation for all cases is also discussed.     

Development of a chemistry module for GCMs: first results of a multiannual integration

The comprehensive chemistry module CHEM has been developed for application in general circulation models (GCMs) describing tropospheric and stratospheric chemistry, including photochemical reactions and heterogeneous reactions on sulphate aerosols and polar stratospheric clouds. It has been coupled to the spectral atmospheric GCM ECHAM3. The model configuration used in the current study has been run in an –off-line mode, i.e. the calculated chemical species do not affect the radiative forcing of the dynamic fields. First results of a 15-year model integration indicate that the model ECHAM3/CHEM runs are numerically efficient and stable, i.e. that no model drift can be detected in dynamic and chemical parameters. The model reproduces the main features regarding ozone, in particular intra- and interannual variability. The ozone columns are somewhat higher than observed (approximately 10%), while the amplitude of the annual cycle is in agreement with observations. A comparison with HALOE data reveals, however, a serious model deficiency regarding lower-stratosphere dynamics at high latitudes. Contrary to what is concluded by observations, the lower stratosphere is characterized by slight upward motions in the polar regions, so that some of the mentioned good agreements must be considered as fortuitous. Nevertheless, ECHAM3/CHEM well describes the chemical processes leading to ozone reduction. It has been shown that the mean fraction of the northern hemisphere, which is covered by polar stratospheric clouds (PSCs) as well as the temporal appearance of PSCs in the model, is in fair agreement with observations. The model results show an activation of chlorine inside the polar vortex which is stronger in the southern than in the northern winter hemisphere, yielding an ozone hole over the Antarctic; this hole, however, is also caused to a substantial degree by the dynamics. Interhemispheric differences concerning reformation of chlorine reservoir species HCl and ClONO₂ in spring have also been well reproduced by the model.     

The effect of peat structure on the spatial distribution of biogenic gases within bogs

Northern peatlands are a large source of atmospheric methane (CH₄) and both a source and a sink of atmospheric carbon dioxide (CO₂). The rate and temporal variability in gas exchanges with peat soils is directly related to the spatial distribution of these free‐phase gases within the peat column. In this paper, we present results from surface and borehole ground‐penetrating radar surveys – constrained with direct soil and gas sampling – that compare the spatial distribution of gas accumulations in two raised bogs: one in Wales (UK), the other in Maine (USA). Although the two peatlands have similar average thickness, physical properties of the peat matrix differ, particularly in terms of peat type and degree of humification. We hypothesize that these variations in physical properties are responsible for the differences in gas distribution between the two peatlands characterized by (1) gas content up to 10.8% associated with woody peat and presence of wood layers in Caribou Bog (Maine) and (2) a more homogenous distribution with gas content up to 5.7% at the surface (i.e. <0.5 m deep) in Cors Fochno (Wales). Our results highlight the variability in biogenic gas accumulation and distribution across peatlands and suggest that the nature of the peat matrix has a key role in defining how biogenic gas accumulates within and is released to the atmosphere from peat soils. © 2015 The Authors. Hydrological Processes published by John Wiley & Sons Ltd.     

Solar UV variability: Effects on stratospheric ozone,trace constituents and thermal structure

The effect of long-term (11-year solar cycle) solar UV variability on stratospheric chemical and thermal structure has been studied using a time-dependent one-dimensional model. Previous studies have suggested substantial variations in local and total ozone, and in stratospheric thermal structure from solar minimum to solar maximum. It is shown here that significant variations also occur in some of the trace constituents. Members of the HO _x family and N₂O exhibit the largest variations, and these changes, if detected, may provide additional means of verifying the presence of solar UV variability and its effects. Some of the species show large phase differences with the assumed solar flux variation. The role of chemical and transport time constants on the time variations of the trace species is examined. Comparisons with reported ozone and temperature data show reasonable agreement for the period 1960 to 1972.     

CO2 Capture and Geologic Storage: The Possibilities

Carbon dioxide (CO₂) capture and geologic storage has been postulated as one possible method to stabilize the atmospheric concentration of CO₂ by injecting and storing it in deep geologic formations. This issue paper analyzes the viability of capture and geologic storage of becoming an effective method to aid in stabilizing the atmospheric concentration of CO₂. It is herein shown that such viability is contingent on overcoming major obstacles that are hydrogeological, technical, and economic in nature. Our analysis indicates that capture and geologic storage is likely to have negligible success in reducing the atmospheric buildup of CO₂ in the coming decades. The magnitude of the anthropogenic emissions of CO₂ indicates that a transition of the world economy away from reliance on fossil fuels might be the only path to stabilize its atmospheric concentration.     

A new method for sampling and analyzing volcanic sublimates — application to Merapi volcano, Java

A new method for the sampling of sublimates from high-temperature volcanic gases has been used at Merapi volcano, Java, in 1978. The sublimates were collected on the inner walls of silica tubes introduced into fumarolic vents. Volcanic gases were allowed to move freely through the tubes and as they cooled, a fraction of the volatile components condensed on the inner walls of the tubes along the temperature gradient. The sublimates were then analyzed by a combination of light microscopy, scanning electron microscopy, electron microprobe and X-ray diffraction.Six successive zones of different compositions and mineralogical associations have been identified along the covered range of temperatures (900° to around 400°C). From the high to the low temperatures, these zones are composed of: (1) cristobalite, magnetite, hercynite; (2) molybdenite; (3) acmite; (4) halite, sylvite; (5) sphalerite, pyrite; and (6) galena. Equilibrium calculations show that these crystalline phases are stable for pS₂, pC₁, and pO₂, values typical of magma-buffered gases that have not been contaminated by atmospheric oxygen.The deposits observed in the tubes may be useful in aiding the understanding of the mechanisms acting during the cooling of the gaseous phase on its way to the surface and before its emission into the atmosphere.     

Source apportionment and secondary organic aerosol estimation of PM2.5 in an urban atmosphere in China

PM2.5 is the key pollutant in atmospheric pollution in China.With new national air quality standards taking effect,PM2.5 has become a major issue for future pollution control.To effectively prevent and control PM2.5,its emission sources must be precisely and thoroughly understood.However,there are few publications reporting comprehensive and systematic results of PM2.5 source apportionment in the country.Based on PM2.5 sampling during 2009 in Shenzhen and follow-up investigation,positive matrix factorization(PMF)analysis has been carried out to understand the major sources and their temporal and spatial variations.The results show that in urban Shenzhen(University Town site),annual mean PM2.5 concentration was 42.2μg m?3,with secondary sulfate,vehicular emission,biomass burning and secondary nitrate as major sources;these contributed30.0%,26.9%,9.8%and 9.3%to total PM2.5,respectively.Other sources included high chloride,heavy oil combustion,sea salt,dust and the metallurgical industry,with contributions between 2%–4%.Spatiotemporal variations of various sources show that vehicular emission was mainly a local source,whereas secondary sulfate and biomass burning were mostly regional.Secondary nitrate had both local and regional sources.Identification of secondary organic aerosol(SOA)has always been difficult in aerosol source apportionment.In this study,the PMF model and organic carbon/elemental carbon(OC/EC)ratio method were combined to estimate SOA in PM2.5.The results show that in urban Shenzhen,annual SOA mass concentration was 7.5μg m?3,accounting for 57%of total organic matter,with precursors emitted from vehicles as the major source.This work can serve as a case study for further in-depth research on PM2.5 pollution and source apportionment in China.     

Continuous monitoring of distal gas emanations at Vulcano,southern Italy

The increasing activity of Vulcano Island (Italy) since 1985 led to the initiation of continuous geochemical monitoring of the lateral soil gas emissions. On the basis both of their relative geochemical characteristics and of local considerations, three gaseous components were selected for monitoring, namely CO₂, He and ²²²Rn. Monitoring has been performed by means of specific analysers. Gases extracted from a water well located at the foot of the active cone were selected for monitoring, on the basis of their geochemical and isotopic characters that indicate their genetic link with central high temperature fumarolic gases emitted at the crater. Very strong variations of gas composition can be observed within one day (from 1 to about 94% for CO₂). Some variations display a daily character and can be correlated with that of atmospheric pressure. The three monitored gases are highly correlated, suggesting very high kinetics of gas transfer in the system. Because of these considerable variations of chemical composition, bulk concentrations obviously are not suitable for monitoring at Vulcano. However, the evolution with time of ratios such as ²²²Rn/CO₂ and He/CO₂ (the latter being corrected for atmospheric contamination) supplies numerical parameters that the expected to characterize the intensity of the degassing process. A new input of magmatic gases, that would lead to an increase in the ²²²Rn/CO₂ and He/CO₂ ratios, should therefore be detected by such a monitoring station.