Application of general circulation models to the study of stratospheric ozone

Summary Observations of the ozone distribution indicate that modifications are required to the photochemical theory. These modifications involve ozone destruction by hydrogen and nitrogen products and ozone transport (both vertical and horizontal) due to atmospheric motions in the stratosphere. If the photochemical terms in the ozone continuity equation are omitted, changes due to atmospheric transport alone can be evaluated.Numerical computations were made of the three-dimensional wind structure as derived from the 12-layer (0–36 km) General Circulation Model developed by NCAR. The results showed that ozone is transported from the equatorial stratosphere poleward and downward in both hemispheres. The horizontal transport is primarily by the Hadley Cell in the tropics and by large-scale eddies in mid and high latitudes. The dominant mechanism for ozone transport are found to be similar to those derived for the horizontal heat and momentum transport found in other general circulation studies.     

Systems modelling of stratospheric ozone transport and photochemistry

A scheme of a system of physical and chemical processes controlling the production, transport and destruction of ozone and its gaseous catalysts, as well as other related gases in the low and high stratosphere is presented. An account is made of temperature variations of the stratospheric layer resulting from changes in ozone content; also included is the effect of temperature variations on photochemical reaction rates and ozone and other gases transport between atmospheric layers. Parameters describing major relations of the system are inferred from the analysis of ozone and trace gas data and from the results of model calculations of interdependence between variations in temperature and ozone content of the layer.An analysis of minor fluctuations of the linearized system shows that photochemical processes are responsible for its aperiodic stability and that gas transport between atmospheric layers destabilizes the system.     

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.     

Ozone variation in the lower stratosphere and its mechanism

Seasonal variations of ozone are studied by taking into consideration both photochemical and dynamical processes. Assuming that the seasonal variations of total ozone amounts are linear combinations of photochemical equilibrium variations and those due to atmospheric motions, the observed variations of the total ozone amount seem reasonably to be explained.The concept mentioned above implies that the time scale of ozone might be rather short in the lower stratosphere. The order of the half restoration time was estimated to be 10 to 10² days in the lower stratosphere. Thus the estimated time scale of ozone must be somewhat longer than that of the temperature in the lower stratosphere, of which variation usually shows its maximum in the midwinter in middle latitudes, while that of ozone shows its maximum in the late winter or early spring. As the maximum values of both quantities would appear in the early summer without air motions, the similarity in the phase differences of temperature and ozone suggests the validity of the concept of this paper.     

The role of water-vapour photodissociation on the formation of a deep minimum in mesopause ozone

A one-dimensional atmospheric photochemical model with an altitude grid of about 1.5 km was used to examine the structure of the global mean vertical ozone profile and its night-time-to-daytime variation in the upper atmosphere. Two distinct ozone layers are predicted, separated by a sharp drop in the ozone concentration near the mesopause. This naturally occurring mesopause ozone deep minimum is primarily produced by the rapid increase in the destruction of water vapour, and hence increase in HO_x, at altitudes between 80 and 85 km, a region where water-vapour photodissociation by ultraviolet radiation of the solar Lyman-alpha line is significant, and where the supply of water vapour is maintained by methane oxidation even for very dry conditions at the tropospheric-stratospheric exchange region. The model indicates that the depth of the mesopause ozone minimum is limited by the efficiency with which inactive molecular hydrogen is produced, either by the conversion of atomic hydrogen to molecular hydrogen via one of the reaction channels of H with HO₂, or by Lyman-alpha photodissociation of water vapour via the channel that leads to the production of molecular hydrogen. The ozone concentration rapidly recovers above 85 km due to the rapid increase in O produced by the photodissociation of O₂ by absorption of ultraviolet solar radiation in the Schumann-Runge bands and continuum. Above 90 km, there is a decrease in ozone due to photolysis as the production of ozone through the three-body recombination of O₂ and O becomes slower with decreasing pressure. The model also predicts two peaks in the night-time/daytime ozone ratio, one near 75 km and the other near 110 km, plus a strong peak in the night-time/daytime ratio of OH near 110 km. Recent observational evidence supports the predictions of the model.     

Influence of the vertical motion field on ozone concentration in the stratosphere

Computations of the mean meridional motion field in the stratosphere are applied to ozone distributions to evaluate the associated ozone concentration changes. These changes are compared with those produced by photochemical and quasi-horizontal eddy processes. For the period January–April 1964 there is a cooperative action between the mean and eddy motions with mean subsidence in middle latitudes supplying ozone to be carried polawards and equatorwards by quasi-horizontal eddy processes. At low latitudes mean horizontal motions offset the eddy transport while at high latitudes mean rising motion is the offsetting term. The mean ozone flux through 50 mb, 3.5×10²⁹ molecules sec^–1, is comparable with the fluxes evaluated by other techniques.The spring maximum is thought to be due to a modulation of the energy supply to the stratospheric eddies which, in turn, force the mean motions. Longer-term changes are to be expected; for example during Ice Ages when increased tropospheric eddy activity is anticipated there should be higher total ozone.     

Polar stratospheric cloud microphysics and chemistry

The solid and liquid particles which constitute polar stratospheric clouds (PSCs) are of manifold importance to the meteorology of the stratosphere. The heterogeneous reactions which take place on and within these particles release halogens from relatively inert reservoir species into forms which can destroy ozone in the polar spring. In addition, solid PSC particles are instrumental in the physical removal of nitrogen oxides (denitrification) and water (dehydration) of regions of the polar stratosphere. Denitrification, in particular, allows extended ozone destruction by slowing the conversion of chlorine radicals back into reservoir species.We review the historical development of PSC studies, with particular emphasis on results from the last decade, encompassing developments in observations, in laboratory experiments, and in theoretical treatments. The technical challenge of measuring sufficient of the parameters describing any given PSC, to allow its microphysics to be understood, has driven forward balloon-borne, aircraft, and satellite instrumentation. The technical challenge of finding suitable laboratory proxies for PSCs, in order to observe the microphysics under controlled conditions, has resulted in a wide variety of experimental designs, some of which maximise the probability of observing phase change, others which mimic the surface–volume ratios of PSCs more closely. The challenge to theory presented by PSCs has resulted in improvements in the thermodynamics of concentrated inorganic solutions of volatile compounds, and a new general theory of freezing of water ice from concentrated aqueous solutions. Of the major processes involving PSCs, heterogeneous reaction probabilities for ternary HNO₃/H₂SO₄/H₂O solutions, and heterogeneous freezing to produce nitric-acid hydrates, are the least well understood.     

Instantaneous photochemical rates in the global stratosphere

Starting with the average actual distribution of ozone (Dütsch [15]) and temperature in the stratosphere, we have calculated the solar intensity as a function of wavelength and the instantaneous rates (molecules cm^–3 sec^–1) for each Chapman reaction and for each of several reactions of the oxides of nitrogen. The calculation is similar to that ofBrewer andWilson [5]. These reaction rates were calculated independently in each volume element in spherical polar coordinates defined by R=1 km from zero to 50, =5° latitude, and ø=15° longitude (thus including day and night conditions). Calculations were made for two times: summer-winter (January 15) and spring-fall (March 22). As input data we take observed solar intensities (Ackerman [1]) and observed, critically evaluated. constants for elementary chemical and photochemical reactions; no adjustable parameters are employed. (These are not photochemical equilibrium calculations.) According to the Chapman model, the instantaneous, integrated, world-wide rate of formation of ozone from sunlight is about five times faster than the rate of ozone destruction, and locally (lower tropical stratosphere) the rate of ozone formation exceeds the rate of destruction by a factors as great as 1000. The global rates of increase of ozone are more than 50 times faster thanBrewer andWilson's [5] estimate of the average annual transfer rate of ozone to the troposphere. The rate constants of the Chapman reactions are believed to be well-enough known that it is highly improbable that these discrepancies are, due to erroneous rate constants. It is concluded that something else besides neutral oxygen species is very important in stratospheric ozone photochemistry. The inclusion of a uniform concentration of the oxides of nitrogen (NO_x as, NO and NO₂) averaging 6.6×10^–9 mole fraction gives a balance between global ozone formation and destruction rates. The inclusion of a uniform mole fraction of NO_x at 28×10^–9 also gives a global balance. These calculations support the hypethesis (Crutzen [10],Johnston [24]) that the oxides of nitrogen are the most important factor in the global, natural ozone balance. Several authors have recently evaluated the natural source strength of NO_x in the stratosphere; the projected fleets of supersonic transports would constitute an artificial source of NO_x about equal to the natural value, thus promising more or less to double an active natural stratospheric ingredient.     

Annual and semiannual oscillations of stratospheric ozone

The global structures of annual oscillation (AO) and semiannual oscillation (SAO) of stratospheric ozone are examined by applying spherical harmonic analysis to the ozone data obtained from the Nimbus-7 solar backscattered UV-radiation (SBUV) measurements for the period November 1978 to October 1980. Significant features of the results are: (1) while the stratospheric ozone AO is prevalent only in the polar regions, the ozone SAO prevails both in the equatorial and polar stratospheres; (2) the vertical distribution of the equatorial ozone SAO has a broad maximum of the order of 0.5 (mixing ratio in g/g) and the maximum appears earlier at high altitude (shifting from May [and November] at 0.3 mb [60 km] to November [and May] at 40 mb); (3) above the 40 km level, the maximum of the polar ozone SAO shifts upward towards later phase with altitude with a rate of approximately 10 km/month in both hemispheres; (4) vertical distributions of the polar ozone AOs and SAOs show two peaks in amplitude with a minimum (nodal layer) in between and a rapid phase change with altitude takes place in the respective nodal layers; and (5) the heights of the ozone AO- and SAO-peaks decrease with latitude. The main part of AOs and SAOs of stratospheric ozone including hemispheric asymmetries is ascribable to: (i) temperature dependent ozone photochemistry in the upper stratosphere and mesosphere, (ii) variations of radiation field in the lower stratosphere affected by the annual cycle of solar illumination and temperature in the upper stratosphere and (iii) meridional ozone transport by dynamical processes in the lower stratosphere.     

The structure of the natural stratosphere and the impact of chlorofluoromethanes on the ozone layer investigated in a 2-D time dependent model

two-dimensional time dependent model of the stratosphere incorporating the major interactions between radiative-photochemical and dynamical processes is described. The main prognostic equations considered are the thermodynamic equation and the general conservation equation for the minor chemical constituents representing the odd oxygen (O _x =O+('D)+O₃), odd hydrogen (HO _x =HO+HO₂), N₂O, odd nitrogen (NO _x =NO+NO₂+HNO₃), CF₂Cl₂, CFCl₃ and odd chlorine (Cl _x =Cl+ClO+HCl). The zonal wind and mean meridional circulations are determined diagnostically by the integration of the thermal wind equation and the stream function equation in the meridional plane espectively. The large scale eddy processes are parameterized in terms of zonal mean quantities using the generalized diffusion formulation on a sloping surface. The radiative heating and cooling and the hotochemical sources and sinks are incorporated in a form which allows for the major interactions among the minor trace constituents, temperature and mean circulation.Two integrations consisting of natural stratosphere and a stratosphere contaminated by the chlorofluoromethanes through lower boundary fluxes are carried out for 23 model years by changing the declination of the sun every day and using 6-hour time step. The model simulations of temperature, mean circulation, ozone, HO _x , N₂O and NO _x in the meridional plane for the normal stratosphere, show satisfactory agreement with the available observations. Based on the results of second integration it is found that the injection of chlorofluoromethanes in the atmosphere at the estimated current production rates can lead to significant changes in the meridional distribution of ozone, temperature and NO _x in the middle and upper stratosphere. The results also indicate that the percentage total ozone depletion increases from tropics to high latitudes and from summer to winter high latitudes. Also discussed are the results of additional experiments incorporating the reaction of HO₂ with NO and the reactions involving ClNO₃.     

On the effect of emissions from aircraft engines on the state of the atmosphere

Emissions from aircraft engines include carbon dioxide, water vapour, nitrogen oxides, sulphur components and various other gases and particles. Such emissions from high-flying global civil subsonic air traffic may cause anthropogenic climate changes by an increase of ozone and cloudiness in the upper troposphere, and by an enhanced greenhouse effect. The absolute emissions by air traffic are small (a few percent of the total) compared to surface emissions. However, the greenhouse effect of emitted water and of nitrogen oxides at cruise altitude is potentially large compared to that of the same emissions near the earth’s surface because of relatively large residence times at flight altitudes, low background concentrations, low temperature, and large radiative efficiency. Model computations indicate that emission of nitrogen oxides has doubled the background concentration in the upper troposphere between 40○N and 60○N. Models also indicate that this causes an increase of ozone by about 5-20%. Regionally, the observed annual mean change in cloudiness is 0.4%. It is estimated that the resultant greenhouse effect of changes in ozone and thin cirrus cloud cover causes a climatic surface temperature change of 0.01-0.1 K. These temperature changes are small compared to the natural variability. Recent research indicates that the emissions at cruise altitude may increase the amount of stratospheric aerosols and polar stratospheric clouds and thereby have an impact on the atmospheric environment. Air traffic is increasing about 5-6% per year, fuel consumption by about 3%, hence the effects of the related emissions are expected to grow. This paper surveys the state of knowledge and describes several results from recent and ongoing research.     

Further ozone transport calculations and the spring maximum in ozone amount

Summary Calculations of the covariance between ozone amounts and meridional wind in the lower stratosphere are presented for all stations in the northern hemisphere for the IGY-IGC. Northward ozone transport occurs by large-scale quasi-horizontal transient and standing eddies and the transport is a maximum early in the year. It is suggested that the transport is governed by the exchange of energy between the troposphere and stratosphere and data are presented on the energy transformations within the lower stratosphere and the transfer of energy into the region which support this suggestion. The vertical flux of energy is also calculated from tropospheric data and its seasonal changes are seen to be in the correct phase to explain the spring maximum in ozone amount.The research reported in this article was sponsored by the Atomic Energy Commission under Contract AT (30-1)2241.     

On the theoretical model for vertical ozone density distributions in the mesosphere and upper stratosphere

Diurnal variations in the vertical ozone density distribution have been calculated for the height range 40–150 km by extending our existing computer programs. The steady-state profiles were first calculated for fifteen constituents in the original program and three additional constituents (CH₄, CO and CO₂); the result was used as the initial condition for the time-dependent solution. The profile of the eddy diffusion coefficient used in this study was determined by comparing the model profile with the observations for CH₄, whose density distribution is verysenstive to the eddy diffusion coefficient The effects of hydrogen and nitrogen compounds on the ozone density are discussed somewhat quantitatively; they reduce the ozone density mainly in the mesosphere and stratosphere, respectively. Special attention is given to the large depression of the ozone density at around 70–85 km, which has been obtained in many theoretical models but has neither been explained nor definitely confirmed by observations. Our time-dependent model indicates that the depression develops at night by the effect of hydrogen-oxygen and nitrogen-oxygen reactions and of eddy diffusion transports. The latter effect also produces an increase of the ozone density after midnight at some heights in the depression region.     

Impact on ozone of high-speed stratospheric aircraft: effects of the emission scenario

A photochemical-transport two-dimensional model has been used to assess the impact of a projected fleet of high-speed stratospheric aircraft using different emissions scenarios. It is shown that the presence in the background atmosphere of nitric acid trihydrate aerosols is responsible for a lower stratospheric denoxification in addition to that caused by the sulfate aerosol layer. This has the effect of further decreasing the relative role of the odd nitrogen catalytic cycle for ozone destruction, so that the lower stratosphere is primarily controlled by chlorine species. The effect of aircraft injection of nitric oxides is that of decreasing the level of ClO, so that the lower stratospheric ozone (below about 20–25 km altitude) increases. The net effect on global ozone is that of a small increase even at Mach 2.4, and is enhanced by adopting emission scenarios including altitude restriction at 15 or 18 km. Reductions of the emission index (EI) of nitric oxides below relatively small values (about 15) are shown to reduce the aircraft-induced ozone increase, because of the associated smaller decrease of ClO. This conclusion is no more valid when the emission index is raised at the present values (about 45).     

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.     

Controls on stable isotopic characteristics of water vapour over Thailand

This study examined the weekly water vapour isotopic composition (δ¹⁸O_v) in Thailand. The water vapour was cryogenically collected from eight sites across the country. Two observational samples were collected over one 24-h period each week (a daytime and a night-time sample), from September 2013 to September 2014. The primary aim was to investigate the environmental factors influencing water vapour isotopes. The results revealed differences in water vapour isotopic values between day and night samples. Three periods of depleted δ¹⁸O_v were associated with large-scale convective systems in September, December, and May. The statistical relationship between the climate variables and water vapour isotopes indicated that the amount of precipitation and relative humidity were the primary controls on both diurnal and seasonal isotopic variability. The temperature did not affect the δ¹⁸O_v, mainly because the atmospheric processes are a function of vertical convection rather than temperature in tropical regions. The water vapour deuterium excess (d-excess) showed greater variability in 2013 than in 2014. The d-excess variation reflected the differences in convection occurring in the day and night. In addition, the vapour phase data were combined with the local meteoric water line to identify the local water vapour line and the interaction between the isotopic composition of water vapour and liquid water. The water vapour isotopic patterns paralleled the precipitation isotopes on rainy days because of equilibrium isotopic exchange. Water vapour and precipitation were isotopically similar under low humidity but showed greater differences from each other under wetter conditions. The study results provide insight into water vapour isotopic characteristics in tropical regions and constrain the role of large-scale atmospheric processes relative to isotopic variability of water vapour in Thailand and nearby countries.     

平流层O3、O动力系统的平衡性质及南极平流层O3季节变化规律的研究

本文首次利用常微分方程定性理论对平流层O₃、O动力系统的平衡性质进行了讨论.结果表明,如果在平流层O₃的主要分布高度内,大气扩散作用小于光化学作用,那么平流层的O₃层处于稳定状态;反之,平流层的O₃层将遭到破坏.利用这一机制,我们可以解释南极平流层O₃的季度变化规律和每年9-10月份出现的南极O₃洞.     

Biased estimates of the isotope ratios of steady‐state evaporation from the assumption of equilibrium between vapour and precipitation

Stable water isotope ratios are measured as a tracer of environmental processes in materials such as leaves, soils, and lakes. Water in these archives may experience evaporation, which increases the abundance of heavy isotopologues proportionally to the gradients in humidity and isotope ratio between the evaporating water and the surrounding atmosphere. The isotope ratio of the atmosphere has been difficult to measure until recently, and measurements remain scarce. As a result, several assumptions have been adopted to estimate isotope ratios of atmospheric water vapour. Perhaps the most commonly employed assumption in terrestrial environments is that water vapour is in isotopic equilibrium with precipitation. We evaluate this assumption using an eight‐member ensemble of general circulation model (GCM) simulations that include explicit calculation of isotope ratios in precipitation and vapour. We find that across the model ensemble, water vapour is typically less depleted in heavy isotopologues than expected if it were in equilibrium with annual precipitation. Atmospheric vapour likely possesses higher‐than‐expected isotope ratios because precipitation isotope ratios are determined by atmospheric conditions that favour condensation, which do not reflect atmospheric mixing and advection processes outside of precipitation events. The effect of this deviation on theoretical estimates of isotope ratios of evaporating waters scales with relative humidity. As a result, the equilibrium assumption gives relatively accurate estimates of the isotope ratios of evaporating waters in low latitudes but performs increasingly poorly at increasing latitudes. Future studies of evaporative water pools should include measurements of atmospheric isotope ratios or constrain potential bias with isotope‐enabled GCM simulations.