ALBERT

Description: Ozone Retrievals from the Solar Backscatter Ultraviolet (SBUV) Instrument on-board the Nimbus-7 Satellite have been reprocessed using an improved internal calibration. The resulting data set covering November, 1978 through January, 1987 has been archived at the National Space Science Data Center in Greenbelt, Maryland. The reprocessed SBUV total ozone data as well as recalibrated Total Ozone Mapping Spectrometer (TOMS) data are compared with total ozone measurements from a network of ground based Dobson spectrophotometers. The SBUV also measures the vertical distribution of ozone, and these measurements are compared with external measurements made by SAGE II, Umkehr, and Ozonesondes. Special attention is paid to long-term changes in ozone bias.

Description: SAGE II observations of ozone at sunrise and sunset (solar zenith angle = 90 deg) at approximately the same tropical latitude and on the same day exhibit larger concentrations at sunrise than at sunset between 55 and 65 km. Because of the rapid conversion between atomic oxygen and ozone, the onion-peeling scheme used in SAGE II retrievals, which is based on an assumption of constant ozone, is invalid. A one-dimensional photochemical model is used to simulate the diurnal variation of ozone particularly within the solar zenith angle of 80 deg - 100 deg. This model indicates that the retrieved SAGE II sunrise and sunset ozone values are both overestimated. The Chapman reactions produce an adequate simulation of the ozone sunrise/sunset ratio only below 60 km, while above 60 km this ratio is highly affected by the odd oxygen loss due to odd hydrogen reactions, particularly OH. The SAGE II ozone measurements are in excellent agreement with model results to which an onion peeling procedure is applied. The SAGE II ozone observations provide information on the mesospheric chemistry not only through the ozone profile averages but also from the sunrise/sunset ratio.

Description: The NOAA satellite ozone monitoring program was initiated by the National Environmental Satellite Data and Information Service (NESDIS) in December 1984, with the launch of the NOAA-9 spacecraft carrying the first operational Solar Backscatter Ultraviolet Spectrometer (SBUV/2). This instrument and its successor on NOAA-11, launched in 1988, are similar to the SBUV instrument launched by the NASA in 1978 on the Nimbus-7 research spacecraft. Measurements by the SBUV and SBUV/2 instruments overlap beginning in 1985. These instruments use measurements of the reflected ultraviolet solar radiation from the atmosphere to derive total ozone amounts and ozone vertical profiles. Since launch, the NOAA instruments and the derived products have been undergoing extensive evaluation by scientists of NOAA and NASA. Measurements obtained with these instruments are processed in real time by the NESDIS. These are reprocessed as the SBUV/2 instrument characterization is refined and as the retrieval algorithm for processing the data is improved. The NOAA-9 ozone data archive begins in March 1985 and continues through October 1990. The archive of NOAA-11 data begins in January 1989 and the data continues to be acquired in 1992.

Description: Following the success of the Sunphotometer Earth Atmosphere Measurement (SPEAM-I) experiment, a more involved experiment was developed to fly as part of the second set of Canadian Experiments (CANEX-2) which will fly on the US Space Shuttle in the fall of 1992. The instrument complement includes an IBM-PC compatible control computer, a hand-held diode array spectrophotometer, and an interference-filter, limb imaging radiometer for the measurement of the atmospheric airglow. The hand-held spectrometer will measure nitrogen dioxide, ozone and aerosols. The limb imaging radiometer will observe emissions from the O2(1 DELTA) and O2(1 SIGMA) airglow bands. Only the spectrophotometer will be discussed here.

Description: A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

Description: A new TOMS instrument (Total Ozone Mapping Spectrometer) was launched from the Plesetsk Cosomodrome, Russia on August 15, 1991. The purpose of the joint project between the U.S. and Russia was to continue the long-term record of ozone measurements from Nimbus-7/TOMS (launched in October 1978). Ozone data from the two satellites compare very closely. When the orbital positions were nearly the same, the comparison over the entire globe showed an offset of 2 percent with a standard deviation of 5 percent. Comparisons were made with several ground based M124 and Dobson stations showing good agreement in absolute value and with the day-to-day variations seen by the ground stations.

Description: Electrochemical concentration cell (ECC) ozone-sonde observations, made in recent years at ten stations whose locations range from the Arctic to Antarctica, have yielded a self-consistent ozone data base from which mean seasonal and annual latitudinal ozone vertical distributions to 35 km have been derived. Ozone measurement uncertainties are estimated, and results are presented in the Bass-Paur (1985) ozone absorption coefficient scale adopted for use with Dobson ozone spectrophotometers January 1, 1992. The data should be useful for comparison with model calculations of the global distribution of atmospheric ozone, for serving as apriori statistical information in deriving ozone vertical distributions from satellite and Umkehr observations, and for improving the satellite and Umkehr ozone inversion algorithms. Attention is drawn to similar results based on a less comprehensive data set published in Ozone in the Atmosphere, Proceedings of the 1988 Quadrennial Ozone Symposium where errors in data tabulations occurred for three of the stations due to inadvertent transposition of ozone partial pressure and air temperature values.

Description: We have analyzed atmospheric thermal emission spectra obtained with the balloon-borne FIRS-2 far infrared Fourier transform spectrometer during balloon flights from Palestine, Texas on May 12-13, 1988 and from Fort Sumner, New Mexico on September 26-27, 1989 and on July 4-5, 1990. Seven and two pure rotational transition lines in 100-205 cm(exp -1) range are analyzed for deriving vertical profiles of stratospheric HCl and HF, respectively. We obtain both the daytime and nighttime average vertical profiles from 15 to 50 km. We compare these profiles with the ones obtained in June, 1983 with the first version of FIRS spectrometer during the Balloon Intercomparison Campaign (BIC-2). BIC-2 results were revised to be consistent with the present analysis which uses the latest spectral parameters. According to our comparison results no increase is recognized for HCl but about 3 percent per year increase for HF from 1983 to 1990, assuming a linear trend. These annual increase rates are smaller than those reported by other groups. Recently Rinsland et al. (1991) and Wallace and Livingston (1991) reported long term behavior of total HCl and HF observed on Kit Peak between 1977 and 1990. As Kit Peak is located near both balloon launching sites, Palestine and Fort Sumner, we think our results are favorably comparable with theirs. Comparison results with ours and ground-based measurements will be presented and discussed.

Description: A balloon-borne project for ozone layer measurements was undertaken using the MAST ozone sondes and ASTOR radiosondes. Previously published data on this series (Ilyas, 1984) was recently re-analyzed using a rigorous technique to evaluate correction factors (ranging between 1.2 to 1.4). The revised data presented here, show that at the tropospheric and lower stratospheric levels, the ozone concentrations at the equator are much lower than the mid-latitude concentrations. The layer of peak concentration is found to be shifted upward compared to the mid-latitude profile and above this the two profiles get closer.

Description: A small optical ozone instrument has been developed for a rocket-borne dropsonde to measure the altitude profile of stratospheric ozone. It consists of a four-color filter photometer that measures the attenuation of sunlight as a function of altitude at four wavelengths in the middle ultraviolet. The ozone dropsonde is launched aboard a meteorological rocket MT-135, providing the altitude profiles of ozone as well as atmospheric temperature and wind. The rocket launchings have been carried out five times since August 1990 at Uchinoura (31 deg N, 131 deg E), Japan to measure ozone concentration from 52 to 20 km altitudes during the slow fall of the dropsonde. The ozone profiles measured in summer (August 27, 1990; Sep. 11 and 12, 1991) were very stable above an altitude of 28km. where as those measured in winter (Feb. 9, and 11, 1991) showed considerable day-to-day variations at the stratospheric altitudes. Ozone, temperature and wind profiles measured simultaneously by both rocket and balloon ozonsondes are compared with CIRA 1986 model atmosphere.

Description: Regular balloon ozone soundings with electrochemical sondes have been performed at Uccle since 1969. More than 450 ozone soundings between 1985 and 1989 were used to calculate the altitudes Zs from the VIZ radiosonde data and the altitudes Zr deduced from the tracking of the balloon train with a primary wind-finding radar. The values of Zs at fixed times appeared to be systematically too low as compared to Zr. The differences Zr-Zs increase with altitude; at 30 km the annual mean values of Zr-Zs (plus or minus standard deviation) vary between 590 plus or minus 910 m and 1410 plus or minus 1160 m, according to the pressure calibration of different manufacturing series of radiosondes. From these results it is found that around the 30 km level the ozone concentrations calculated from soundings with VIZ sondes are too low by 7.5 to 14 percent, depending upon the manufacturing series of radiosondes. At least part of the discrepancy which has often been found between ozone profiles from balloon soundings and from other techniques such as rocket observations or Umkehr measurements may be explained by this effect. An altitude correction would have important consequences as to the climatology of ozone in the middle stratosphere as adopted at the moment. About half of the day-to-day variability of ozone observed from soundings with VIZ radiosondes above the 30 km level, is induced by the variability of Zr-Zs. The agreement between altitudes calculated from radar data and Vaisala radiosondes is much better; from 34 comparative soundings a mean difference (plus or minus standard deviation) of about -300 plus/minus 180 m was found at 30 km.

Description: The Umkehr method for retrieving the gross features of the vertical ozone distribution requires measurements of the ratio of zenith-sky radiances at two wavelengths in the near-UV region while the solar zenith angle (SZA) changes from 60 to 90 degrees. A Brewer spectrophotometer was used for taking such measurements extending the SZA range down to 96 degrees. Analyzed data from the Spring of 1991 imply that observations at twilight are of great significance in improving ozone retrievals in the upper stratosphere. Judged by the variance reduction for Umkehr layers 9 to 12 (25-30 percent for layer 11) and the increase in separation and amplitude of the averaging kernels for the relevant layers, the ozone retrievals in the upper stratosphere are shown to be in better agreement with climatological means.

Description: Stratospheric ozone has been measured using infrared emission spectroscopy of the 9.6 micron band. Thermal emission spectra of the zenith sky were measured from the ground. The spectra show the presence of the 1020 cm(exp -1) spectral feature of ozone on clear days. The spectra were measured with a BOMEM model 100 emission interferometer with a resolution of 4 cm(exp -1). The feature corresponds to a mixing ratio of 5 ppmv if the ozone is assumed to be uniformly distributed in the stratosphere from 25 to 35 km. The development of an inversion algorithm to derive the altitude distribution of the ozone in 3 layers is described. These measurements have been conducted from Peterborough, Ontario since June 1991; further investigations are planned to study the comparisons with Dobson and LIDAR ozone measurements.

Description: The Aberystwyth MST radar has been used as part of the TOASTE program to study the structure of the tropopause in cut-off-low system with an aim to identifying regions where stratosphere-troposphere exchange are taking place. Theory predicts that the vertical gradient in reflected power is proportional to the static stability of the reflecting region, and should therefore resolve tropopause structure. Comparisons of MST power profiles with radiosonde data are presented and show good agreement, revealing regions of indefinite tropopauses, where stratosphere-troposphere exchange is thought to take place. The continuous nature of MST data allows an estimation of the size of these regions.

Description: The numerical modeling of the changes of the concentration of trace gases in the atmosphere during the eclipse shows that the NO2 total content in the vertical column increases approximately by 80 percent. The first observations of the NO2 total content during the eclipse of 1981 have given 60 plus or minus 20 percent. In the observations of 1990 the more precise methods and instruments for stratospheric NO2 measurements were used. The surface ozone, NO, and NO2 concentrations were under control. The results of the observations give the increasing of the stratospheric NO2 during the eclipse by 55 plus or minus 6 percent. The maximum increasing of the NO2 content is observed at the moment of the maximum phase.

Description: Measurements of stratospheric composition have been made with a novel star-pointing spectrometer. The instrument consists of a telescope that focuses light from stars, planets, or the moon onto a spectrometer and two dimensional CCD array detector. Atmospheric absorptions can be measured, from which atmospheric columns of several gases can be determined. The instrument was deployed in Abisko, 69 deg N, during the European Arctic Stratospheric Ozone Experiment (EASOE). The instrument has the potential for measuring O3, OClO, NO2, and NO3. In this paper, a method for the retrieval of vertical columns is described, and some examples of ozone measurements given.

Description: Regular measurements of stratospheric ozone concentration profiles have been made at Table Mountain, California, since January 1988. During the period to December 1991, 435 independent profiles were measured by the differential absorption lidar technique. These long-term results, and an evaluation of their quality, is presented in this paper.

Description: An FTIR spectrometer was installed at Arrival Heights, Antarctica (78 deg S, 167 deg E) in February 1991 to measure the evolution of stratospheric HNO3 during the year. In particular, it was the intention to make the first observations of HNO3 trends during autumn, concurrently with ongoing measurements of column NO2 made with a grating spectrometer. The time-series of NO2 in the Antarctic shows a rapid decline in the column amount during autumn, and a slow recovery in spring, as the photochemical conditions move the species to and from higher storage reservoirs. The new nitric acid data show for the first time that during autumn the vertical column increases from approximately 1.9 x 10(exp 16) molecule cm(exp -2) at day 30 to approximately 3.1 x 10(exp 16) molecule cm(exp -2) by day 100. When the sun returns in spring, it is found that the column amount has fallen to about half the value at the end of autumn. Spring amounts are variable, but as found in the data from previous years remain low inside the vortex. The autumn increase is attributed to the heterogeneous conversion of N2O5 to gas-phase HNO3 on background aerosols. Low nitric acid column amounts at the start of spring suggest that the HNO3 has moved from the gas to the condensed phase on polar stratospheric clouds with the advent of low temperatures during the polar night.

Description: The evolution of ozone anomalies over the middle and high latitudes of the Northern Hemisphere during the winter 1991-1992 is studied in this work. The largest monthly mean negative deviations in the middle latitudes of the Northern Hemisphere were about 10 percent in November and December, and up to 20 percent in January, February, and March over Eurasian territories, and much smaller over the Canadian sector. At the end of January, on individual days, total ozone values of 190-210 D.U. were observed over Eastern Europe and European part of Russia, that is 40-45 percent below normal. On the whole, the 1991-1992 winter was one of the most anomalous over all the period of ozone observations. Finally, an attempt is made to quantify the contribution of transport in the ozone layer changes over Europe during this period.

Description: A light, relatively cheap and easy to operate balloonborne UV-visible spectrometer was designed for investigating ozone photochemistry in the Arctic winter. The instrument was flown 11 times during the European Arctic Stratospheric Ozone Experiment (EASOE) in winter 1991-92 in Northern Scandinavia. The first simultaneous measurements of vertical distributions of aerosols, PSC's, O3, NO2 and OClO inside the vortex during flight no. 6 on 16 January, in cold conditions are reported, which show that nitrogen oxides were almost absent (lower than 100 ppt) in the stratosphere below 22 km, while a layer of relatively large OClO concentration (15 ppt) was present at the altitude of the minimum temperature.

Description: The NASA Langley airborne differential absorption lidar system was operated from the NASA Ames DC-8 aircraft during the 1992 Airborne Arctic Stratospheric Expedition to investigate the distribution of stratospheric aerosols and ozone (O3) across the Arctic vortex from January to March 1992. Aerosols from the Mt. Pinatubo eruption were found outside and inside the Arctic vortex with distinctly different scattering characteristics and spatial distributions in the two regions. The aerosol and O3 distributions clearly identified the edge of the vortex and provided additional information on vortex dynamics and transport processes. Few polar stratospheric clouds were observed during the AASE-2; however, those that were found had enhanced scattering and depolarization over the background Pinatubo aerosols. The distribution of aerosols inside the vortex exhibited relatively minor changes during the AASE-2. Ozone depletion inside the vortex as limited to less than or equal to 20 percent in the altitude region from 15-20 km.

Description: We have studied the development of the austral ozone hole using a 3-D spectral chemical transport model at R15 resolution for the period 15th September to 15th October, 1991. The model is driven by objectively analyzed wind fields obtained from the Canadian Meteorological Center and uses the chemical module developed by Kaminski (1992). Although extensive processing of NO(y) and Cl(x) occurs within the model, the ozone hole that develops appears shallow and ephemeral. Analysis of the results indicate that the meridional transport of ozone is sufficient to overwhelm the substantial chemical depletion that does occur. We suggest that the low resolution objectively analyzed data used is unable to capture the essential isolated nature of the vortex.

Description: A three-dimensional radiative-dynamical-chemical model has been developed and used to study some aspects of modeling the polar lower stratosphere. The model includes a comprehensive gas-phase chemistry scheme as well as a treatment of heterogeneous reactions occurring on the surface of polar stratospheric clouds. Tracer transport is treated by an accurate, nondispersive scheme with little diffusion suited to the representation of strong gradients. Results from a model simulation of early February 1990 are presented and used to illustrate the importance of the model transport scheme. The model simulation is also used to examine the potential for Arctic ozone destruction and the relative contributions of the chemical cycles responsible.

Description: Stratospheric ozone and aerosol data recorded at Spitsbergen (79 deg N, 12 deg E) from 1988 to 1992 are presented. Strong dynamical influences like seasonal variations and annual cycles in the ozone concentrations are described. Polar Stratospheric Clouds were detected above Spitsbergen in January 1989 and 1990, but not in the next two years. Volcanic aerosols, attributed to the Mt. Pinatubo eruption, appeared as early as August 1991 above Spitsbergen and were a constant feature of the lower Arctic stratosphere in winter 1991/92.

Description: A four wavelength depolarization backscattering lidar has been operated during the European Arctic Stratospheric Ozone Experiment (EASOE) in Sodankyl, in the Finnish Arctic. The lidar performed measurements during the months of December 1991, January, February and March 1992. The Finnish Meteorological Institute during the same period launched regularly three Radiosondes per day, and three Ozone sondes per week. Both Mt. Pinatubo aerosols and Polar Stratospheric Clouds were measured. The use of four wavelengths, respectively at 355 nm, 532 nm , 750 nm, and 850 nm permits an inversion of the lidar data to determine aerosol particle size. The depolarization technique permits the identification of Polar Stratospheric Clouds. Frequent correlation between Ozone minima and peaks in the Mt. Pinatubo aerosol maxima were detected. Measurements were carried out both within and outside the Polar Vortex.

Description: It is now clear that heterogeneous reactions play an important role in controlling the concentration of ozone in the stratosphere. In this work, the loss of N2O5 on ice substrates has been studied in a flow reactor in an attempt to gain a more fundamental understanding of these reactions. The apparent reaction probability in this system was found to decrease as the substrate was exposed to N2O5. A model which corrected for the loss of surface sites was developed and although it appears to fit the data for a given experiment quite well, it is concluded that the loss of reactive sites is not the full explanation. In addition, the results of an experimental and modeling study suggest that reaction on the internal surface of the ice substrates is not a major loss mechanism for N2O5 in the current work.

Description: Previous laboratory studies have established the stability conditions of nitric acid trihydrate (NAT), of which type 1 polar stratospheric cloud (PSC 1) particles are thought to be composed. However, NAT samples in lab studies were almost always formed under conditions very different from those of the stratosphere. In order to better understand the in situ growth of PSC 1 particle populations, samples of water and nitric acid were deposited under conditions of temperature and pressure which more closely approximate the polar stratosphere. The compositions of the solids, measured shortly after deposition, depended on the H2O:HNO3 ratio in the vapor from which the solids were condensed. Solids formed from vapor mixtures that approached stratospheric contained significantly less HNO3 than the 25 mol percent expected of NAT.

Description: It is expected from theoretical considerations that synoptic-scale variations in total ozone should be correlated with the absolute vorticity field near the tropopause. This paper tests the theory, using TOMS total ozone fields and vorticity derived from ECMWF analyses. A good correlation is found, except during winter - suggesting that other sources of variability in total ozone are active at this time. The correlation with potential vorticity is also investigated. This shows two maxima in the correlation coefficient in winter and spring, one near the tropopause and the other in the region of 420K. A study of the residuals from a linear regression of vorticity with total ozone during January reveals a similar structure to the 450K potential vorticity field.

Description: The SBUV instrument, on Nimbus-7, measures the backscatter ultraviolet radiance at 12 wavelengths. The radiance data from these wavelengths was used to deduce the ozone profile and the total column ozone. In February 1987, there was an instrument malfunction. The purpose of this paper is to describe the malfunction, to determine the effect of the malfunction on the data quality, and if possible, to correct for the effects of the malfunction on the data from the SBUV instrument.

Description: More than 2000 ozone soundings and a large number of Dobson observations have been performed since 1967 in a unique procedure. The achieved very homogeneous data sets were used to evaluate significant long-term trends both in the troposphere and the stratosphere. The trend amounts to about plus 2 percent per year in the troposphere and to about minus 0.5 percent per year in the stratosphere. Extremely low ozone records obtained during winter 1991/92 are discussed in the light of the long term series. The winter mean of the ozone column is the lowest one of the series. The ozone deficit occurred mainly in the lower stratosphere. One cause may be the Pinatubo cloud. Even compared with the extreme winter mean following the El Chichon eruption the ozone content was lower. Additionally ozone was reduced by dynamical effects due to unusual weather situations.

Description: Concentrations of tropospheric O3, NO2, H2CO, and SO2 have been measured on the Campus of the 'Universite Libre de Bruxelles' on a routine basis since October 1990. The long path system consists of a source lamp, a first 30 cm f/8 Cassegrain type telescope which collimates the light onto a slightly parabolic mirror placed on the roof of a building situated 394 m away from the laboratory. The light is sent back into a second 30 cm Cassegrain telescope. This telescope has been modified so that the output beam is a 5 cm diameter parallel beam. This beam is then focused onto the entrance aperture of the BRUKER IFS120HR fourier transform spectrometer. The two telescopes are mounted on alignment devices and the external mirror is equipped with a driving system operated from the laboratory. The choice of the light source (either a 1000 W high pressure 'ozone free' xenon lamp or a 250 W tungsten filament) and of the detector (either a solar blind UV-diode or a silicon diode) depended on the spectral region studied. These regions lie respectively from 26,000 cm(exp -1) to 30,000 cm(exp -1) (260-380 nm) and from 14,000 cm(exp -1) to 30,000 cm(exp -1) (330-700 nm). The spectra have been recorded at the resolution of 16 cm(exp -1) and with a dispersion of 7.7 cm(exp -1). They have been measured during the forward and the backward movements of the mobile mirror, in double sided mode; each spectrum is an average of 2000 scans. The time required to record a spectrum is about 45 minutes. The shape of the raw spectra in the two investigated regions are represented.

Description: A tropopause fold developed on the western flank of a trough in the 300 mb flow on 6 Oct. 1990. Radiosonde ascents over western Europe showed very dry stable layers beneath the jet stream in the potential temperature range 310 to 315 K. These were evident on profiles from 12h on 6 Oct. to 00h on 8 Oct. ECMWF model assimilations were examined for this period to determine how well the model represented the radiosonde observations. Humidity fields were found to give better agreement than potential vorticity, probably because the PV is affected by the limited vertical resolution of the model. Isentropic trajectories were calculated for the air in the fold as represented by the ECMWF assimilation at 00h on 7 Oct. Those on the western edge of the fold split from the main flow and transferred to the troposphere, while those on the eastern side ended up in the cut-off low. A lower bound of 1.1 x 10(exp 14) kg is estimated for the amount of stratospheric air transferred into the troposphere by this fold.

Description: A study of ozone transfer to the troposphere has been performed during two phases of the evolution of a cut-off low using both ozone vertical profiles and objective analysis of the ECMWF to compute potential vorticity distributions and air mass trajectories. Ozone profiles were measured by a ground based lidar system at the Observatoire de Haute Provence (OHP, 43 deg 55 N, 5 deg 42 E). A stratospheric ozone transport into the troposphere has been observed during a tropopause fold which occurred at the beginning of the cut-off low formation and during the erosion phase of the cut-off low. From the estimate of the maximum ozone content transferred to the troposphere, both mechanisms have the same order of magnitude of influence on the ozone flux to the troposphere. On a time scale of a few days, the correlation is very good between the potential vorticity and the ozone time evolution in the vicinity of the upper level frontal system.

Description: Large-scale summertime (July-August) distributions of O3 and aerosols were observed in a broad range of atmosphere conditions over the tundra, ice, and ocean regions near Alaska in 1988 and over the lowlands and boreal forests of Canada in 1990. The tropospheric O3 budget in the high-latitude regions was found to be strongly influenced by stratospheric intrusions, and deposition at the surface was found to be the main sink for O3 in the troposphere. Enhanced levels of O3 were observed in plumes from fires in Alaska and Canada. This paper discusses the large-scale variability of O3 and aerosols observed in the high-latitude regions during these field experiments.

Description: It is found from model simulations of trace gas and meteorological data from aircraft campaigns that deep convection may enhance the potential for photochemical ozone production in the middle and upper troposphere by up to a factor of 60. Examination of half a dozen individual convective episodes show that the degree of enhancement is highly variable. Factors affecting enhancement include boundary layer NO(x) mixing ratios, differences in the strength and structure of convective cells, as well as variation in the amount of background pollution already in the free troposphere.

Description: Clouds, although only occupying a relatively small fraction of the troposphere volume, can have a substantial impact on the chemistry of the troposphere. In newly formed clouds, or in clouds with air rapidly flowing through, the chemistry is expected to be far more active than in aged clouds with stagnant air. Thus, frequent cycling of air through shortlived clouds, i.e. cumulus clouds, is likely to be a much more efficient media for altering the composition of the atmosphere than an extensive cloud cover i.e. frontal cloud systems. The impact of clouds is tested out in a 2-D channel model encircling the globe in a latitudinal belt from 30 to 60 deg N. The model contains a detailed gas phase chemistry. In addition physiochemical interactions between the gas and aqueous phases are included. For species as H2O2, CH2O, O3, and SO2, Henry's law equilibria are assumed, whereas HNO3 and H2SO4 are regarded as completed dissolved in the aqueous phase. Absorption of HO2 and OH is assumed to be mass-transport limited. The chemistry of the aqueous phase is characterized by rapid cycling of odd hydrogen, (H2O2, HO2, and OH). O2(-) (produced through dissociation of HO2) reacting with dissolved O3 is a major source of OH in the aqueous phase. This reaction can be a significant sink for O3 in the troposphere. In the interstitial cloud air, odd hydrogen is depleted, whereas NO(x) remains in the gas phase, thus reducing ozone production due to the reaction between NO and HO2. Our calculations give markedly lower ozone levels when cloud interactions are included. This may in part explain the overpredictions of ozone levels often experienced in models neglecting cloud chemical interactions. In the present study, the existence of clouds, cloud types, and their lifetimes are modeled as pseudo random variables. Such pseudo random sequences are in reality deterministic and may, given the same starting values, be reproduced. The effects of cloud interactions on the overall chemistry of the troposphere are discussed. In particular, tests are performed to determine the sensitivity of cloud frequencies and cloud types.

Description: A simple quasi 2-D model is used to study the zonal distribution of NO(x). The model includes vertical transport in form of eddy diffusion and deep convection, zonal transport by a vertically uniform wind, and a simplified chemistry of NO, NO2 and HNO3. The NO(x) sources considered are surface emissions (mostly from the combustion of fossil fuel), lightning, aircraft emissions, and downward transport from the stratosphere. The model is applied to the latitude band of 40 deg N to 50 deg N during the month of June; the contributions to the zonal NO(x) distribution from the individual sources and transport processes are investigated. The model predicted NO(x) concentration in the upper troposphere is dominated by air lofted from the polluted planetary boundary layer over the large industrial areas of Eastern North America and Europe. Aircraft emissions are also important and contribute on average 30 percent. Stratospheric input is minor about 10 percent, less even than that by lightning. The model provides a clear indication of intercontinental transport of NO(x) and HNO3 in the upper troposphere. Comparison of the modelled NO profiles over the Western Atlantic with those measured during STRATOZ 3 in 1984 shows good agreement at all altitudes.

Description: A 3-D regional photochemical tracer/transport model for Europe and the Eastern Atlantic has been developed based on the NASA/GISS CTM. The model resolution is 4x5 degrees latitude and longitude with 9 layers in the vertical (7 in the troposphere). Advective winds, convection statistics and other meteorological data from the NASA/GISS GCM are used. An extensive gas-phase chemical scheme based on the scheme used in our global 2D model has been incorporated in the 3D model. In this work ozone formation in the troposphere is studied with the 3D model during a 5 day period starting June 30. Extensive local ozone production is found and the relationship between the source regions and the downwind areas are discussed. Variations in local ozone formation as a function of total emission rate, as well as the composition of the emissions (HC/NO(x)) ratio and isoprene emissions) are elucidated. An important vertical transport process in the troposphere is by convective clouds. The 3D model includes an explicit parameterization of this process. It is shown that this process has significant influence on the calculated surface ozone concentrations.

Description: Results from surface ozone measurements at Penang (5.5 deg N, 100 deg E) over 1980-88 period are presented. The study indicates the ozone concentrations undergoing significant diurnal and seasonal variations. The peak concentration are observed at around mid-day (up to 35 nb) but the O3 concentration generally drops to zero level in the early evening and remains unchanged until mid-morning. Monthly-averaged daily 1-h average concentrations are generally small (4-13 nb) and decrease continually from the early part of the year to the end. Frequently, varying local weather conditions seem to influence the O3 concentrations.

Description: Surface ozone concentration at three Indian stations - New Delhi (28.6 deg N), Pune (18.5 deg N) and Thiruvananthapuram (formerly Trivandrum (8.3 deg N) - has been measured since 1973 with the help of an electrochemical continuous ozone recorder. These stations show diurnal, seasonal and annual cycles in surface ozone. Daily changes show that the minimum value occurs at sunrise and maximum in the afternoon. As regards seasonal variations, Thiruvananthapuram and Pune have a minimum value during monsoon season (June to August) while at New Delhi the minimum value occurs in January. However, New Delhi also records low ozone amount during monsoon season identical to the amounts show at Thiruvananthapuram and Pune. The annual cycles at these stations have been compared with similar measurements in the northern and southern hemispheres. The Indian measurements agree well with the annual cycles at these stations. Further, the analysis of the Indian data indicates that the major contribution in surface ozone comes from the natural sources like stratospheric-tropospheric exchange, turbulence, and mixing in the boundary layer; however, a small contribution from anthropogenic sources cannot be ruled out at Pune and probably at New Delhi, especially in winter and summer seasons.

Description: From a network of surface ozone monitoring sites distributed primarily over the Atlantic and Pacific Oceans, the seasonal, day-to-day, and diurnal patterns are delineated. At most of the NH (Northern Hemisphere) sites there is a spring maximum and late summer or autumn minimum. At Barrow, AK (70 deg N) and Barbados (14 deg N), however, there is a winter maximum, but the mechanisms producing the maximum are quite different. All the sites in the SH (Southern Hemisphere) show winter maxima and summer minima. At the subtropical and tropical sites, there are large day-to-day variations that reflect the changes in flow patterns. Air of tropical origin has much lower ozone concentrations than air from higher latitudes. At the two tropical sites (Barbados and Samoa), there is a marked diurnal ozone variation with highest amounts in the early morning and lowest values in the afternoon. At four of the locations (Barrow, AK; Mauna Loa, HI; American Samoa; and South Pole), there are 15- through 20-year records which allow us to look at longer term changes. At Barrow there has been a large summer increase over the 20 years of measurements. At South Pole, on the other hand, summer decreases have led to an overall decline in surface ozone amounts.

Description: Ground-based measurements of ozone have been carried out at three stations in the German alps (47 deg N, 11 deg E, altitudes 740, 1776, and 2962 m a.s.l.) as well as at the coastal station Cape Point (34 deg S, 18 deg E). For the mountain sites (at 1776 and 2962 m), trend calculations based on monthly means have yielded O3 growth rates of 0.8 and 0.9 ppbv yr(exp -1), respectively, over the period 1978-91. Seasonally differentiated data sets have yielded higher rates for summer than for winter. The impact of near-ground photochemical O3 production on the observed O3 concentration is shown. No significant long-term O3 trend has been observed at 740 m (valley floor) as well as at the southern hemispheric station Cape Point. Evidence exists for a close relationship between the amplitude variations of the annual cycles of O3 and CO at Cape Point.

Description: A seven year (1984-90) climatology of tropospheric vertical ozone soundings, performed by electrochemical sondes at the OHP (44 deg N, 6 deg E, 700 m ASL) in Southern France, is presented. Its seasonal variation shows a broad spring/summer maximum in the troposphere. The contribution of photochemical ozone production and transport from the stratosphere to this seasonal variation are studied by a correlative analysis of ozone concentrations and meteorological variables, with emphasis on potential vorticity. This analysis shows the impact of dynamical and photochemical processes on the spatial and temporal ozone variability. In particular, a positive correlation (r = 04.0, significance greater than 99.9 percent) of ozone with potential vorticity is observed in the middle troposphere, reflecting the impact of stratosphere-troposphere exchange on the vertical ozone distribution.

Description: In August of 1986 a program was initiated to measure atmospheric ozone profiles at mid-latitudes in the Southern Hemisphere by flying ECC ozonesondes on a regular basis from the DSIR Physical Sciences Atmospheric Laboratory at Lauder, New Zealand, 45 deg S. Flights since that time have been performed on a regular basis at the rate of two flights per week during the 5 month period August to December, the time of maximum variability at mid-latitudes, and once per week for the remainder of the year. These data, consisting now of more than 400 profiles has been analyzed and the free troposphere portion of the profiles binned as 1km slabs. These data have been combined to form a seasonal average values for each season of each year in 2 km slabs and the variation observed in these seasonal averages is the basis of this paper. A biennial component is apparent in these data and the lack of any increasing trend over this 5 year period is contrasted with that measured at similar latitudes in the Northern Hemisphere over the same period.

Description: Transmission spectra of three ferric oxides (two alpha-Fe2O3 samples and one gamma-Fe2O3 sample) and two ferric oxyhydroxides (alpha-FeOOH and gamma-FeOOH) were measured. This preliminary study has demonstrated that crystalline ferric oxides and ferric oxyhydroxides exhibit complex spectral features at thermal wavelengths. Some of these features suggest that thermal infrared observations of Mars can provide significant insight into the ferric mineralogy of that planet. The results of this study suggest that emissivity spectra of crystalline ferric oxides and ferric oxyhydroxides may prove quite important for the interpretation of thermal infrared spectral observations of Mars.

Description: Few contest that mass extinctions have punctuated the history of life, or that those events were so pervasive environmentally, taxonomically, and geographically that physical forcing factors were probably involved. However, consensus remains elusive on the nature of those factors, and on how a given perturbation - impact, volcanism, sea-level change, or ocean anoxic event - could actually generate the observed intensity and selectivity of biotic losses. At least two basic problems underlie these long-standing disagreements: difficulties in resolving the fine details of taxon ranges and abundances immediately prior to and after an extinction boundary and the scarcity of simple, unitary cause-and-effect relations in complex biological systems.

Description: Since the beginning of regular space geodetic measurements, Satellite Laser Ranging (SLR) has routinely provided polar motion and length of day solutions. At the present time, Global Positioning Systems (GPS) regularly produces daily polar motion solutions with 0.4 mas accuracy, equivalent to the routine 1-day VLBI experiments and SLR solutions using 3 days of Lageos-1 data. This rapid progress of the GPS technique forces a review of any resource allocations for VLBI and SLR measurements of Earth orientation.

Description: Since a VLBI station cannot operate in isolation and since simultaneous operation of the entire VLBI network is impractical, it is necessary to design observing programs with periodic observing sessions using networks of 3-7 stations that, when treated together, will have the necessary interstation data and network overlaps to determine the desired rates of change. Thus, there has been a mix of global, intercontinental, transcontinental, and regional networks to make measurements ranging from plate motions to deformation over a few hundred km. Over time, even networks focusing on regional deformation using mobile VLBI included large stations removed by several thousand km to increase sensitivity, determine EOP more accurately, and provide better ties to the terrestrial reference frame (TRF). Analysis products have also evolved, beginning with baseline components, and then to full three-dimensional site velocities in a global TRF.

Description: The inherent precision of the doubly differenced phase measurement and the low cost of instrumentation made GPS the space geodetic technique of choice for regional surveys as soon as the constellation reached acceptable geometry in the area of interest: 1985 in western North America, the early 1990's in most of the world. Instrument and site-related errors for horizontal positioning are usually less than 3 mm, so that the dominant source of error is uncertainty in the reference frame defined by the satellites orbits and the tracking stations used to determine them. Prior to about 1992, when the tracking network for most experiments was globally sparse, the number of fiducial sites or the level at which they could be tied to an SLR or VLBI reference frame usually, set the accuracy limit. Recently, with a global network of over 30 stations, the limit is set more often by deficiencies in models for non-gravitational forces acting on the satellites. For regional networks in the northern hemisphere, reference frame errors are currently about 3 parts per billion (ppb) in horizontal position, allowing centimeter-level accuracies over intercontinental distances and less than 1 mm for a 100 km baseline. The accuracy of GPS measurements for monitoring height variations is generally 2-3 times worse than for horizontal motions. As for VLBI, the primary source of error is unmodeled fluctuations in atmospheric water vapor, but both reference frame uncertainties and some instrument errors are more serious for vertical than horizontal measurements. Under good conditions, daily repeatabilities at the level of 10 mm rms were achieved. This paper will summarize the current accuracy of GPS measurements and their implication for the use of SLR to study regional kinematics.

Description: The stations of the Global Laser Tracking Network have significantly contributed to the measurement of plate kinematics. The expanding network of progressively improved instruments clearly demonstrates the systems' centimeter positioning accuracy. Several satellite laser ranging (SLR) analysis groups have adopted techniques to distill geodynamic information from the Lageos-1 satellite observations using orbital arc lengths from an hour to a decade. SLR observations now provide the scale for the International Terrestrial Reference System and help to define the Earth's polar motion in this system. Agreement between positions separately determined with SLR, VLBI and GPS systems has been established at the level of a few centimeters in position and a few millimeters per year in horizontal velocity.

Description: Redistribution of mass within the Earth system changes its gravitational field, and thus changes the orbits of Earth satellites. While these variations are small, Satellite Laser Ranging (SLR) to precise geodetic satellites such as Lageos-1, Lageos-2, Starlette, Ajisai, and Stella can detect these changes at their broadest spatial scales (currently greater than 10,000 km). The satellites sense only the combined variation in the solid Earth-ocean-atmosphere system; however, modeling of these different components has led to detection of long-wavelength variations in the distribution of atmospheric mass, changes in the amplitudes of atmospheric and oceanic tides, and secular variations caused by the post-glacial adjustment of the Earth's crust. The unambiguous detection of ocean mass redistribution by SLR has not been verified due largely to inadequacies in current ocean models. Great progress has been made in recent years in the determination of luni-solar tides and the braking they induce in the Earth-Moon-Sun system (leading to secular changes in the length-to-day and lengthening of the lunar orbit period) using a wide variety of techniques including ocean tide gauges, satellite altimetry, Lunar Laser Ranging, and near-Earth satellite orbit modeling. Recent investigations of the more complex and less predictable non-tidal temporal variations in the gravity field have generally proceeded along two fronts: 1) the determination of long-wavelength variations in the gravity field through the changing perturbations seen in the orbits of near-Earth satellites, and 2) the prediction of temporal variations in gravity using geophysical, atmospheric, and oceanic models. A convergence of these efforts is sought to better understand the source of observed changes in the Earth's gravitational field.

Description: The terrestrial reference frame (TRF) is realized by a set of positions and velocities derived from a combination of the three space geodetic techniques, SLR, VLBI and GPS. The standard International TRF is constructed by the International Earth Rotation Service in such a way that it is stable with time and the addition of new data. An adopted model for overall plate motion, NUVEL-1 NNR, defines the conceptual reference frame in which all the plates are moving. In addition to the measurements made between reference points within the space geodetic instruments, it is essential to have accurate, documented eccentricity measurements from the instrument reference points to ground monuments. Proper local surveys between the set of ground monuments at a site are also critical for the use of the space geodetic results. Eccentricities and local surveys are, in fact, the most common and vexing sources of error in the use of the TRF for such activities as collocation and intercomparison.

Description: The Improved Stratospheric and Mesospheric Sounder (ISAMS) is producing the first global measurements of emission from the 1 yields 0 band of nitric oxide (NO). The emission from the lower thermosphere has been examined and is seen to increase dramatically at times corresponding to high solar activity. The temporal and geographical extent of the effect is reported, and possible mechanisms for the enhanced emission are discussed. The need for adequate representation of thermospheric NO emission in order to retrieve NO number densities at all heights from ISAMS data is discussed, as are prospects for science studies using such NO number density measurements.

Description: The Improved Stratospheric and Mesospheric (ISAMS) on board the Upper Atmosphere Research Satellite (UARS) incorporates a 12.1 micron window channel for the measurement of aerosol opacity. The retrieval scheme is discussed briefly and preliminary observations of the Mt. Pinatubo aerosol cloud are presented and compared with SAGE 2 observations at 1.02 microns. The effect of aerosol on other ISAMS channels and its spectral dependence is discussed.

Description: We present preliminary results of the validation of ozone measurements from the Improved Stratospheric and Mesospheric Sounder (ISAMS). The indications are that the ISAMS provides ozone data which generally agrees with other experiments and climatological values, except in regions of large thermal gradients or high aerosol loading. Corrections for these effects will be included in future reprocessing of the data.

Description: ISAMS is a limb sounding radiometer flying on the UARS, and designed to measure temperature, pressure, O3, CO, NO, NO2, N2O5, HNO3, CH4, H2O, N2O, and aerosol. Its capabilities are described, together with the present status of validation of its data products, and plans for future improvement.

Description: The quasi-biennial oscillations (QBO) in ozone and temperature vertical distributions are studied on the basis of ozonesonde data of 21 stations. Maximum QBO amplitudes in ozone are noted in the 16-20 kn layer over Resolute (75N), Aspendale (38S) and in the northern mid-latitude band, but in the 20-24 km layer in the northern subtropical band. In the upper layers the QBO effect is less evident. In the tropospheric layer it is difficult to note the QBO-related effect in all the groups of the data. In all the layers where the QBO effect is noted the positive deviations precede, but the negative deviations follow the time of maximum of the easterly equatorial wind at 50 mb level. No essential differences in phase or amplitude characteristics of the ozone QBO were noted for the Aspendale data compared with that for the Northern Hemisphere data. The QBO-effect is not noted in the temperature data in the mid-latitudes. Above Resolute and in subtropics the ozone and temperature effects are roughly in phase each with other, except in the 28-32 km layer over subtropics, where they are opposite each to other.

Description: We compare ground-based microwave observations of ozone in the upper stratosphere and mesosphere with daytime observations made from the SME (Solar Mesosphere Explorer) satellite, with nighttime data from the LIMS instrument, and with a diurnal photochemical model. The results suggest that the data are all in reasonable agreement and that the model-data discrepancy is much less than previously thought, particularly in the mesosphere. This appears to be due to the fact that the latest data are lower than earlier reports and the updated model predicts more ozone than older versions. The model and the data agree to within a factor of 1.5 at all altitudes and typically are within 20 percent.

Description: Time modulation of the flux of new Jupiter-dominated Oort cloud comets is the subject of interest here. The major perturbation of these comets during the present epoch is due to the tidal field of the relatively smooth distribution of matter in the galactic disk. A secondary source of the near-parabolic comet flux are stars penetrating the inner Oort cloud and providing impulses that create brief comet showers. Substantial stellar-induced showers occur approximately every 100 m.y. Less frequent (but stronger) impulses due to giant molecular clouds can also perturb comets from the inner cloud. These occur on timescales of approximately equal to 500 m.y. In contrast to these infrequent stochastic shower phenomena is the continuously varying tidal-induced flux due to the galaxy. As the Sun orbits the galactic center it undergoes quasiharmonic motion about the galactic midplane, which is superimposed on the small eccentricity, near-Keplerian motion in the plane having epicycle period approximately equal to 150 m.y. In the process the galactic tidal field on the Sun/cloud system will vary causing a modulation of the observable Oort cloud flux. We have created a model of the galactic matter distribution as it affects the solar motion over a time interval ranging from 300 m.y. in the past to 100 m.y. into the future. As constraints on the disk's compact dark matter component we require consistency with the following: (1) the observed galactic rotation curve, (2) today's flux distribution of new comets, (3) the studies of K-giant distributions, and (4) the periodicity found in the terrestrial cratering record. The adiabatically varying galactic tidal torque is then determined and used to predict the time dependence of the flux. We find that a model in which approximately half the disk matter is compact is consistent with these constraints. Under such circumstances the peak-to-trough flux variation will be approx. equal to 5:1 with a full width of 9 m.y. This variability will manifest in the terrestrial cratering record and is consistent with the observed cratering periodicity, if over half of the impacts on Earth are caused by comets or asteroids that originate in the outer Oort cloud.

Description: The global distribution of Maastrichtian inoceramids is now known in enough detail that the patterns of disappearance can be used to place first-order constraints on paleoceanographic changes that may have occurred during that age. The Inoceramidae is an excellent group to focus on in a study of Maastrichtian events for the following reasons: (1) they were globally distributed in the early Maastrichtian; (2) they did not survive the age (i.e., they undergo change during the interval); and (3) they have left a rich microfossil and macrofossil record. Some inoceramids grew to be very large; however, even the largest often passively disaggregated and are preserved as hundreds of millions of characteristic, columnar, polygonal prisms of calcite approximately 100 microns across. This taphonomic process has greatly increased the inoceramid fossil record and provides a means of objectively estimating changes in their standing population. In addition, because these prisms commonly occur in Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) cores, it is relatively easy to generate a truly global database. The existing macrofossil record of inoceramids has less temporal and spacial resolution but greater taxonomic resolution than the microfossil record. In concert the microfossil and macrofossil records of inoceramids demonstrate that important changes occurred during the Maastrichtian. These changes are distinct from the KT boundary catastrophe but are part of the larger KT transition.

Description: On an airless, slowly rotating planetary body like the Moon, ejecta particles from an impact follow simple ballistic trajectories. If gaseous interactions in the fireball are ignored, ejecta particles follow elliptical orbits with the center of the planetary body at one focus until they encounter the surface at the point of reimpact. The partial elliptical orbit of the ejecta particle lies in a plane in inertial (galactic) coordinates. Because of the slow rotation rate (for example, 360 degrees/28 days for the Moon), the intersection of the orbital plane and the surface remains nearly a great circle during the flight time of the ejecta. For this reason, lunar rays, representing concentrations of ejecta with the same azimuth but different velocities and/or ejecta angles, lie essentially along great circles. Ejecta from airless but more rapidly rotating bodies will follow more complicated, curving trajectories when plotted in the coordinate frame of the rotating planet or viewed as rays on the planetary surface. The curvature of trajectories of ejecta particles can be treated as a manifestation of the Coriolis effect, with the particles being accelerated by Coriolis pseudoforces. However, it is more straightforward to calculate the elliptical orbit in inertial space and then determine how far the planet rotates beneath the orbiting ejecta particle before reimpact. The Earth's eastward rotation affects ballistic ejecta in two ways: (1) the eastward velocity component increases the velocity of eastbound ejecta and reduces the velocity of westbound ejecta; and (2) the Earth turns underneath inflight ejecta, so that although the latitude of reimpact is not changed, the longitude is displaced westward, with the displacement increasing as a function of the time the ejecta remains aloft.

Description: Results of different routine measurements performed in Dumont d'Urville (66 deg S, 140 deg E) since 1988 are presented. They include the seasonal variation of total ozone and NO2 as measured by a SAOZ UV-Visible spectrometer, Polar Stratospheric Cloud observations by a backscatter lidar and more recently, vertical ozone profiles by ECC sondes and ozone and aerosols stratospheric profiles by a DIAL lidar. The particular results of 1991 in relation with the volcanic events of Mount Pinatubo and Mount Hudson, and the position of the polar vortex over Dumont d'Urville are discussed.

Description: Preliminary results are presented of observations obtained during the EASOE campaign, with an airborne backscatter lidar and a ground-based DIAL ozone lidar system. Although the main signature observed on the lidar signals was due to the Pinatubo cloud which erupted in June 1991, distinct PSC events were detected on several occasions by the airborne lidar often in relation with orographic wave activity over the norvegian mountains. The ozone profiles obtained in Sodankyla with the ground based lidar are locally perturbed by the presence of the volcanic cloud. After a first correction of the aerosols effect, they present however a reasonably good agreement with the ozone sondes profiles performed on the same site.

Description: The NOAA National Weather Service currently derives global stratospheric wind analyses via several procedures. The first is the operational data assimilation system that extends from the surface up to about 50 mb and is in process of being tested to about 10 mb. In addition, a balanced wind is determined from the available Climate Analysis Center stratospheric height analyses that encompass the 70-0.4 mb region. The High Resolution Doppler Imager (HRDI) recently launched as a member of the Upper Atmosphere Research Satellite (UARS) is the first satellite instrument designed to measure winds in this stratospheric region and, thus, provide a basic evaluation of the NMC derived products. The HRDI accomplishes this by utilizing a triple-etalon Fabry-Perot interferometer that allows one to measure the Doppler shift of O2 absorption and emission features of the atmosphere, from which the wind field can be determined.

Description: The Improved Stratospheric and Mesospheric Sounder (ISAMS) is a multichannel radiometer and forms part of the science payload of the Upper Atmosphere Research Satellite (UARS). ISAMS measures infrared emissions from the Earth's atmosphere in several wavelength bands. Three such bands include emission from nitric oxide, nitrogen dioxide, and dinitrogen pentoxide. In this paper, we briefly discuss how the ISAMS instrument measures NO, NO2, and N2O5. We also present preliminary data from these channels and describe preliminary validation work.

Description: Aircraft, ground-based, and satellite measurements indicate large concentrations of ClO in the lower stratosphere in and near the polar vortex. The amount of local ozone depletion caused by these large ClO concentrations will depend on the relative rates of ozone loss and ClO recovery. ClO recovery occurs when NO(x), from HNO3 photolysis, reacts with ClO to form ClONO2. We show that air parcels with large amounts of ClO will experience a subsequent ozone depletion that depends on the solar zenith angle. When the solar zenith angle is large in the middle of winter, the recovery of the ClO concentration in the parcel is slow relative to ozone depletion. In the spring, when the solar zenith angle is smaller, the ClO recovery is much faster. After ClO recovery, the chlorine chemistry has not returned to normal. The ClO has been converted to ClONO2. ClO production from further encounters with PSCs will be limited by the heterogeneous reaction of ClONO2 with water. Large ozone depletions, of the type seen in the Antarctic, occur only if there is significant irreversible denitrification in the air parcel.

Description: Shklovsky and others have suggested that some of the major extinctions in the geological record might have been triggered by explosions of nearby supernovae. The frequency of such extinction events will depend on the galactic supernova frequency and on the distance up to which a supernova explosion will produce lethal effects upon terrestrial life. In the present note it will be assumed that a killer supernova has to occur so close to Earth that it will be embedded in a young, active, supernova remnant. Such young remnants typically have radii approximately less than 3 pc (1 x 10(exp 19) cm). Larger (more pessimistic?) killer radii have been adopted by Ruderman, Romig, and by Ellis and Schramm. From observations of historical supernovae, van den Bergh finds that core-collapse (types Ib and II) supernovae occur within 4 kpc of the Sun at a rate of 0.2 plus or minus 0.1 per century. Adopting a layer thickness of 0.3 kpc for the galacitc disk, this corresponds to a rate of approximately 1.3 x 10(exp -4) supernovae pc(exp -3) g.y.(exp -1). Including supernovae of type Ia will increase the total supernovae rate to approximately 1.5 x 10(exp -4) supernovae pc(exp -3) g.y.(exp -1). For a lethal radius of R pc the rate of killer events will therefore be 1.7 (R/3)(exp 3) x 10(exp -2) supernovae per g.y. However, a frequency of a few extinctions per g.y. is required to account for the extinctions observed during the phanerozoic. With R (extinction) approximately 3 pc, the galactic supernova frequency is therefore too low by 2 orders of magnitude to account for the major extinctions in the geological record.

Description: The end-Permian mass extinction was the most extensive in the history of life and remains one of the most complex. Understanding its causes is particularly important because it anchors the putative 26-m.y. pattern of periodic extinction. However, there is no good evidence for an impact and this extinction appears to be more complex than others, involving at least three phases. The first began with the onset of a marine regression during the Late Permian and resulting elimination of most marine basins, reduction in habitat area, and increased climatic instability; the first pulse of tetrapod extinctions occurred in South Africa at this time. The second phase involved increased regression in many areas (although apparently not in South China) and heightened climatic instability and environmental degradation. Release of gas hydrates, oxidation of marine carbon, and the eruption of the Siberian flood basalts occurred during this phase. The final phase of the extinction episode began with the earliest Triassic marine regression and destruction of nearshore continental habitats. Some evidence suggests oceanic anoxia may have developed during the final phase of the extinction, although it appears to have been insufficient to the sole cause of the extinction.

Description: The fragmentation of a small asteroid in the atmosphere greatly increases its cross sections for aerodynamic braking and energy dissipation. At a typical impact velocity of 22 km/s, the atmosphere absorbs more than half the kinetic energy of stony meteoroids with diameters, D(sub m), less than 220 m and iron meteoroids with D(sub m) less than 80 m. The corresponding diameter for comets with impact velocity 50 km/s is D(sub m) less than 1600 m. Most of the atmospheric energy dissipation occurs in a fraction of a scale height, so large meteors appear to 'explode' or 'flare' at the end of their visible paths. This dissipation of energy in the atmosphere protects the earth from direct impact damage (e.g., craters), but it produces a blast wave that can do considerable damage. The area of destruction around the impact point in which the over-pressure in the blast wave exceeds 4 lb/sq in = 2.8 x 10(exp 5) dynes/cu cm, which is enough to knock over trees and destroy buildings, increases rapidly from zero for chondritic meteoroids less than 56 m in diameter (15 megatons) to about 200 sq km for those 80 m in diameter (48 megatons); the probable diameter of the tunguska impactor of 1908 is about 80 m. Crater formation and earthquakes are not significant in land impacts by stony asteroids less than about 200 m in diameter because of the air protection. A tsunami is probably the most devastating type of damage for asteroids 200 m to 1 km in diameter. An impact by an asteroid this size anywhere in the Atlantic would devastate coastal areas on both sides of the ocean. An asteroid a few kilometers across would produce a tsunami that would reach the foothills of the Appalachian Mountains in the upper half of the East Coast of the United States. Most of Florida is protected from a tsunami by the gradual slope of the ocean off its coast, which causes most of the tsunami energy to be reflected back into the Atlantic. The atmosphere plume produced by asteroids with diameters exceeding about 120 m cannot be contained by the atmosphere, so this bubble of high-temperature gas forms a new layer on top of the atmosphere. The dust entrapped in this hot gas is likely to have optical depths exceeding tau = 10 for asteroids with diameters exceeding about 0.5 to 1 km. The optical flux from asteroids 60 m or more in diameter is enough to ignite pine forests. However, the blast wave from an impacting asteroid goes beyond the radius in which the fire starts. The blast wave tends to blow out the fire, so it is likely that the impact will char the forest, as at Tunguska, but the impact will not produce a sustained fire. Because comets dissipate their energy much higher in the atmosphere than asteroids, they illuminate a much larger region and their blast wave is weaker. So they are much more effective in producing large fires. This suggests that the KT impactor was a comet rather than an asteroid.

Description: The total column ozone response to 11-year solar ultraviolet (UV) variations is estimated here from the observed response to 27-day solar variations adjusted for the theoretical difference between the 27-day response and 11-year response. The estimate is tested by comparing two data sets where long-term drifts have been removed, the Nimbus 7 TOMS Version 6 total column ozone and the 280 nm core-to-wing ratio (a proxy for solar UV variations). The 365-day running means of data area-weighted between 40 deg N to 40 deg S latitude give a 1.9% ozone variation related to the 11-year solar cycle compared with the estimate of 1.8%. Estimates of linear trends were reduced by a factor of 2 by including solar effects. The standard deviation from the empirical model was reduced from 1.0 to 0.6 Dobson Units, by including the quasi-biennial oscillation (QBO), but the QBO did not significantly alter trend estimates. Both the ozone responses to 27-day and 11-year solar variations were considerably stronger than predicted by a 2-D theoretical model.

Description: We present a model of the steady-state transport assuming three reservoirs: a lower mantle (P) with a relatively undepleted inventory of U, Th, Pu, I, He, Ne, Xe, Ar; an upper mantle that has been extensively outgassed (D); and the atmosphere. There is mass transport at a rate M(sub PD) by plumes from the lower mantle, a fraction of which is outgassed directly into the atmosphere, while the remainder feeds matter and associated nuclei into D. D is well outgassed at spreading centers and has material containing atmospheric gases added to it by subduction. In the case of He, there is no subduction component. The approach follows the treatment of Kellogg and Wasserburg. A summary of the pertinent equations and constraints was reported earlier. The U, Th and Pu in P are estimated for Earth models from refractory element abundances in meteorites. In this model the inventory of rare gases in D is governed by the simple mixing of components from P (both radiogenic and original) with distinctive atmospheric components. In addition, alpha decay and spontaneous fission of U, and (alpha, n) reaction on oxygen from energetic alpha particles produce radiogenic/nuclear daughter products in D. These include (4)He, (136)Xe and (21)Ne. (40)K in D generates excess radiogenic (40)Ar.

Description: Wadsleyite (beta-Mg2SiO4) is believed to be the most abundant phase in the Earth between depths of 400 and about 525km. Because of the unusual crystal chemistry, Smyth suggested that this phase might be a significant host for hydrogen in the transition zone. Indeed, of the nominally anhydrous phases believed to make up the upper mantle and transition zone none has been reported with a greater H content than wadsleyite. Young et al, report the synthesis of hydrous, Fe-bearing wadsleyite with up to 60,000 H per 10(exp 6) Si. Using ionic constraints and maximal subgroup symmetry, a hypothetical, ordered model for hydrous wadsleyite has been created and examined. The model has formula Mg7Si4O14(OH)2, has space group Pmmb, has an ordered vacancy into one of two non-equivalent M2 sites, and contains two different H positions, one on each of the non-equivalent O1 sites. Electrostatic calculations indicate that hydration would relieve the underbonding of O1 as well as the overbonding of the bridging oxygen, O2, so that the hydrous phase may be more stable than the anhydrous phase. This model makes several predictions that may be of significance for the mechanisms and amounts of H that may be stored in the transition zone of the Earth, and by which the model may be tested experimentally.

Description: (3)He/(4)He compositions are presented for groundwater samples from the Ethiopian segment of the East-Afrikan Rift and from its northern extension, the adjacent Afar region (Djibuti). Helium isotope data are compared to those obtained previously from the Gregory Rift, south of Ethiopia. The distribution pattern of mantle-derived volatiles along the entire East-African-Rift (-from south Kenya to Djibuti-) is discussed and their sources are identified. Helium isotope ratios (R) for samples from the Ethiopian part of the Rift range from 6.3 to 16.0 times the atmospheric ratio (Ra=1.4 x 10(exp -6) and thus show together with a MOR component a considerable hotspot helium component. These mantle helium concentrations are comparable to those observed in groundwaters and volcanic rocks from the Afar plume region in Djibuti. Here R/Ra values range from 9 to 13 times the atmospheric composition, with mantle-derived helium concentrations being higher than at spreading ocean ridges. R/Ra values from Ethiopia and Djibuti are entirely different from those observed in groundwaters at the southerly extending Gregory Rift in Kenya, where R/Ra values scatter between 0.5 and 6. At the northernmost part of the Gregory Rift, close to Ethiopia mantle helium contents are slightly higher, with R/Ra-values varying between 6.5 and 8.0.

Description: High resolution tomographic images that have been obtained of the subduction zones in the west Pacific do not only show very low P wave velocities above the leading edge of the slab at shallow depth, but also below 300 km. The two zones are generally, but not always, separated by a zone of normal shear velocity near 200 km depth. These findings confirm some earlier inferences from local seismic data in Japan, and similar findings of low Vp and low Q zones beneath South America. Surprisingly, such deep seismic low velocity zones have recently also been discovered beneath the locations of ancient subduction zones. A study of upper mantle shear velocity in Central Europe shows a similar distribution of low velocity zones beneath the Tornquist-Teisseyre line, the former west coast of the old continent of Baltica, and the site of the subducting Tornquist ocean in the early Palezoic. Preliminary results from a Russian-French experiment shows low P velocities below 250 km under the Urals, while an older tomographic study shows such low P velocities beneath the northern Appalachians.

Description: Recent studies of low-Z molecular materials including hydrogen to multimegabar pressures (less than 300 GPa) have uncovered a range of phenomena relevant to understanding the nature of the interiors of the outer planets and their satellites. Synchrotron x ray diffraction measurements (to 42 GPa) have been used to determine the crystal structure of the solid (hexagonal-close packed) and equation of state. Sound velocities in fluid and solid hydrogen (to 24 GPa) have been inverted to obtain elastic constants and aggregate bulk and shear moduli. In addition, an improved intermolecular potential has been determined which fits both static and shock-wave data. Use of the new potential for the molecular envelope of Jupiter suggests the need for major revisions of existing Jovian models or a reanalysis of reported free oscillations for the planet. Studies at higher pressures (greater than 100 GPa) reveal a sequence of pressure-induced symmetry-breaking transitions in molecular hydrogen, giving rise to three high-pressure phases (1, 2, and 3). Phase 1 is the rotationally disordered hcp phase which persists from low pressure to well above 100 GPa at high temperature (e.g., 300 K). Phase 2 is a low-temperature, high-pressure phase (transition at 100 GPa and 77 K in H2) with spectral features indicative of partial rotational ordering and crystallographic distortion. The transition to Phase 3 at 150 GPa is accompanied by a weakening of the molecular bond, gradual changes in orientational ordering, strong enhancement of the infrared intramolecular vibrational absorption, and strong intermolecular interactions similar to those of ambient-pressure network solids. Studies of the phase diagram reveal a triple point near 130 K and 160 GPa. Higher pressure measurements of vibrational spectra place a lower bound of approximately 250 GPa on the predicted transition pressure for dissociation of molecular hydrogen to form a monatomic metal.

Description: The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

Description: A case can be made that accretion of the Earth was a high-temperature process and that the primordial Earth was dry. A radial zone-refining process during accretion may have excluded low-melting point and volatile material, including large-ion lithophile elements toward the surface, leaving a refractory and zoned interior. Water, sediments and altered hydrous oceanic crust are introduced back into the interior by subduction, a process that may be more efficient today than in the past. Seismic tomography strongly suggests that a large part of the uppermantle is above the solidus, and this implies wet melting. The mantle beneath Archean cratons has very fast seismic velocities and appears to be strong to 150 km or greater. This is consistent with very dry mantle. It is argued that recycling of substantial quantities of water occurs in the shallow mantle but only minor amounts recycle to depths greater than 200 km. Recycling also oxidizes that mantle; ocean island ('hotspot') basalts are intermediate in oxidation state to island-arc and midocean ridge basalts (MORB). This suggests a deep uncontaminated reservoir for MORB. Plate tectonics on a dry Earth is discussed in order to focus attention on inconsistencies in current geochemical models of terrestrial evolution and recycling.

Description: Previous shock experiments by Ahrens and his colleagues show that degassing of H2O and CO2 occurs at 8-65GPa from hydrous minerals such as serpentine. In early solar system, the impact degassing would have played an important part in the formation of primary-atmospheres of the terrestrial planets. However, degassing conditions of noble gases are not well-known because there are few experiments for them. We conducted some shock recovery experiments to investigate the degassing condition and to understand the degassing mechanisms of water and noble gases. We used natural richterites (Ri), amphibolites (Am), serpentines (Sep) and orthoclases (or) as target samples. These, except Sep, contain radiogenic noble gases such as (40)Ar. The samples were put in stainless steel containers, and were show by a rail gun at ISAS or single-stage powder guns at Nagoya or Tohoku University, Japan. We used two kinds of containers: 'open' type containers having a ventilating path for released volatiles for most of samples and 'closed' type ones for some samples for comparison. On Ri and Sep, we made shock experiments for pre-heated (at 400-500 C) and unheated targets, and for powdered and uncrushed samples. Water and noble gases were analyzed both for the recovered shocked samples and the unshocked original samples, and the fractions of the degassed volatiles were calculated by comparing them. Water content in the sample was analyzed by thermo-gravimetry. Noble gases were extracted by heating the samples under high vacuum and analyzed with a sector-type mass spectrometer.

Description: The stabilities and properties of water- and carbon-bearing phases in the earth have been determined from phase equilibrium measurements, combined with new data on the equations of state of water, carbon dioxide, carbonates and hydrates. The data have then been used to predict the fate of calcite and hydrous phases in subducting oceanic lithosphere. From the compositions of MORB's one can estimate concentrations of water and carbon of around 200 ppm and 80 ppm respectively in the upper mantle. Lower mantle estimates are very uncertain, but 1900 ppm water and 2000 ppm C are plausible concentrations. Measurements of the density of supercritical water to 3 GPa demonstrate that this phase is less compressible than anticipated from the equations of state of Haar et al. or Saul and Wagner and is closer to predictions based on molecular dynamics simulations. Conversely, fugacity measurements on carbon dioxide to 7 GPa show that this fluid is more compressible than predicted from the MRK equation of state. The results imply that hydrates are relatively more stable and carbonates less stable at pressures greater than 5 GPa than would be predicted from simple extrapolation of the low pressure data. Nevertheless, carbonates remain extremely refractory phases within both the upper and lower mantle.

Description: Diamonds are unique samples for inferring ancient mantle conditions, because of their enormous stability, antiquity and also of mantle origin. However, as temperatures in the mantle where diamonds have existed are very high (greater than 1000 C) and residence time of some diamonds could be more than a few billion years, it is imperative to examine whether or not diamonds have retained their pristine characteristics, especially those of noble gases, under such extreme conditions. As discussed in a review article by Ozima, there are rather large variations in the diffusivity of helium in diamonds obtained in the early determinations. The data are also limited to temperatures higher than 1200 C. In the present study, we conducted more refined diffusion experiments for He using carbonado diamonds, which have large amounts of radiogenic (4)He approximately 10(exp -2) cu cm STP/g. On the basis of the experimentally estimated diffusion coefficients, we will discuss retentivity of He in diamonds in the mantle condition.

Description: It is well known that the solubility of noble gases in magmas decreases with increasing atomic weight. Xenon, the weightiest of the stable noble gases, is the least soluble atmospheric gas in magma. It is not unreasonable to suppose that the noble gases should have degassed from (or equilibrated with) a bubbling mantle in order of increasing solubility, such that xenon was the most rapidly degassed and helium the least. The apparent relative ages of the famous radiogenic noble gas isotopes agrees, at least qualitatively, with this premise. When atmospheric loss processes are assigned their proper place, several long-standing xenonological puzzles become added evidence for xenon's relative antiquity. Xenon being the afore-mentioned sense the oldest atmospheric gas, will have been most greatly subject to escape, be it impact-driven or EUV-driven. Nonradiogenic xenon's pronounced isotopic fractionation has already been attributed to escape; why it should be more fractionated than krypton would be assigned to xenon's greater atmospheric age. The small atmospheric inventory of xenon relative to the other nonradiogenic noblegases, known as the 'missing xenon' problem, could easily be explained by differential escape. The relatively tiny atmospheric inventories of the radiogenic daughter products of 129 Iodine and 244 Plutonium, both much smaller than would be expected from the inferred abundances of the parents in meteorites, offer a third and fourth data to support the hypothesis that Earth has lost most of its xenon.

Description: According to a widespread believe, Earth's water was either added in form of a late volatile-rich veneer or as we have argued repeatedly that of all the water which was added to the Earth only that portion remained which was added towards the end of accretion when the mean oxygen fugacity of the accreting material became so high that metallic iron could not exist any longer. Prior to this moment, all the water in the latter scenario would have been used up for the oxidation of iron. Fe + H2O yields FeO + H2. Huge quantities of hydrogen would continuously be produced in this scenario which escaped. In the same moment the hydrogen on its way to the surface would lead to an efficient degassing of the growing Earth's mantle. The fact that - assuming C1 abundances - the amount of iridium in the Earth's mantle agrees, within a factor of two with the total water inventory of the Earth's mantle and crust is taken as evidence for the validity of such a scenario. In both scenarios, the Earth's mantle would remain dry and devoid of other volatiles. Some species soluble in metallic iron like carbon and hydrogen will probably partly enter the core in some portions. It is generally assumed that today a considerable portion of the earth's total water inventory resides in the mantle. It is also clear that over the history of the Earth the water of the Earth's oceans has been recycled many times through the mantle. This is the consequence of plate subduction. In a similar way mantle convection was probably responsible to being water into the originally dry mantle. As a consequence, today the Earth is wet both inside and outside.

Description: Experiments with the laser-heated diamond cell show that H2O and CO2 can be stabilized within crystalline mineral structures of the lower-mantle, and hence can be present at relatively non-volatile components of the Earth's deep interior. Samples quenched from high pressures and temperatures document that the MgCO3-FeCO3 magnesite-siderite solid-solution is stable and coexists with (Mg,Fe)SiO3 perovskite at 30-40 GPa and approximately 1500-2000 K. In contrast, H2O combines with the silicate to form (Mg,Fe)SiH2O4 phase D, coexisting with (Mg,Fe)SiO3 perovskite at these conditions. If enough water is present, phase D can become the predominant phase in the MgSiO3-H2O system at lower-mantle conditions. Our work extends previous studies to Fe-bearing compositions and to the pressures of the mid-lower mantle. Thus, the results of high-pressure experiments suggest that both H2O and CO2 can be abundant in the Earth's lower mantle, being present in stable hydroxisilicate and carbonate phases.

Description: The subduction of water and other volatiles into the mantle from oceanic sediments and altered oceanic crust is the major source of volatile recycling in the mantle. Until now, the geotherms that have been used to estimate the amount of volatiles that are recycled at subduction zones have been produced using the hypothesis that the slab is rigid and undergoes no internal deformation. On the other hand, most fluid dynamical mantle flow calculations assume that the slab has no greater strength than the surrounding mantle. Both of these views are inconsistent with laboratory work on the deformation of mantle minerals at high pressures. We consider the effects of the strength of the slab using two-dimensional calculations of a slab-like thermal downwelling with an endothermic phase change. Because the rheology and composition of subducting slabs are uncertain, we consider a range of Clapeyron slopes which bound current laboratory estimates of the spinel to perovskite plus magnesiowustite phase transition and simple temperature-dependent rheologies based on an Arrhenius law diffusion mechanism. In uniform viscosity convection models, subducted material piles up above the phase change until the pile becomes gravitationally unstable and sinks into the lower mantle (the avalanche). Strong slabs moderate the 'catastrophic' effects of the instabilities seen in many constant-viscosity convection calculations; however, even in the strongest slabs we consider, there is some retardation of the slab descent due to the presence of the phase change.

Description: The studies of the relations of carbon and primary isotopes of noble gases were carried out on the natural gases and on the mantle rocks from the mantle M-type sources, which represent the degassed mantle reservoir (MORB's). These works has the aim of estimation of the values of the C/3He ratios in the deep mantle fluids to determine the flux of the mantle CO2 on the basis of known flux of primary mantle 3He. It was found, that in the natural gases the values of the C/3He ratios fall into the range from 1 times E plus 6 to 1 times E plus 15, and in the fluids of MORB's are constant near 2 times E plus 9. We have studied the mantle rocks from the relatively undergassed mantle P minus type sources: continental; Baikal Rift (Siberia), Mongolia, Catalonia (Spain), Pannonia Depression (central Europe) and ocean; Spietzbergen isl., Hawaii isl., Canarian isl. It ws found, that in mantle xenolites and the host alkaline basalts from the continental rifts and ocean islands, the values of the C/3He ratios fall into the range from E plus 11 to E plus 15 (and this result needed to be explained; the higher carbon to helium ratios is relatively undergassed mantle reservoir compared with the degassed one, requires whether hilly compatibility of helium compared with carbon, whether additional flux of 3He to the degassed mantle reservoir). From the other hand it was found that in the mantle rocks from the sources of P minus and M minus types, continental carbonatites, the values of the C/36Ar ratios are constant in the range from E plus 9 to E plus 10, the close values have the MORB's also.

Description: Two different approaches to explaining how hydrogen might be stored in the mantle are illustrated by a number of papers published over the past 25-30 years, but there has been little attempt to provide objective comparisons of the two. One approach invokes the presence in the mantle of dense hydrous magnesium silicates (DHMS) stable at elevated pressures and temperatures. The other involves nominally anhydrous minerals (NAM) that contain hydrogen as a minor constituent on the ppm level. Experimental studies on DHMS indicate these phases may be stable to pressures and temperatures as high at 16 GPa and 1200 C. This temperature is lower than that indicated by a mantle geotherm at 16 GPa, but may be reasonable for a subducting slab. It is possible that other DHMS could be stable to even higher pressures, but little is known about maximum temperature limits. For NAM, small amounts of hydrogen (up to several hundred ppm) have been detected in olivine, orthopyroxene, clinopyroxene, and garnet recovered from xenoliths in kimberlites, eclogites, and alkali basalts; it has been demonstrated that synthetic wadsleyite and perovskite can accommodate significant amounts of hydrogen. A number of problems are associated with each possibility. For NAM originating in the mantle, one would like to assume that the hydrogen measured in samples recovered on Earth's surface was incorporated when the phase-crystallized at high temperatures and pressures, but it could have been introduced during transport to the surface. Major problems for the DHMS proponents are that none of these phases have been found as minerals and little is yet known about their stabilities in systems containing other cations such as Fe, Al, and Ca.

Description: Application of the (40)Ar-(39)Ar method and noble gas studies to diamonds has increased our understanding of their age relationships to the host kimberlite or lamproite, and of the source and composition of volatile-rich fluids in the upper mantle. The properties of diamond (inert, high mechanical strength and low gas diffusivities) means they are especially useful samples for studying gases trapped deep within the earth (less than 150 km) as they are unlikely to have undergone loss or exchange of entrapped material since formation. Volatile-rich fluids (H2O-CO2) are important agents for metasomatic processes in the upper mantle, and the noble gases and halogens preferentially partition into this phase leading to a strong geochemical coherence between these groups of elements. The abundances of the halogens in the major reservoirs of the Earth shows a marked progression from chlorine, concentrated in the oceans, through to iodine which, through its affinity to organic material, is concentrated mainly in sediments. Abundances in the upper mantle are low. This is particularly true for iodine which is of special interest in view of its potential significance as an indicator of sediment recycling and by way of its link to (129)Xe amomalies in the mantle through the low extinct isotope (129)I. Extensions of the (40)Ar-(39)Ar technique enable measurements of halogens and other elements (K, Ca, Ba, U) by production of noble gas isotopes from these species during neutron irradiation. Samples analyzed in this way include 15 coated stones from an unknown source in Zaire, 3 boarts from the Jwaneng and 1 boart from the Orapa kimberlites, both in Botswana.

Description: Recent experimental investigations under mantle conditions have identified a suite of dense hydrous magnesium silicate (DHMS) phases that could be conduits to transport water to at least the 660 km discontinuity via mature, relatively cold, subducting slabs. Water released from successive dehydration of these phases during subduction could be responsible for deep focus earthquakes, mantle metasomatism and a host of other physico-chemical processes central to our understanding of the earth's deep interior. In order to construct a thermodynamic data base that can delineate and predict the stability ranges for DHMS phases, reliable thermochemical and thermophysical data are required. One of the major obstacles in calorimetric studies of phases synthesized under high pressure conditions has been limitation due to the small (less than 5 mg) sample mass. Our refinement of calorimeter techniques now allow precise determination of enthalpies of solution of less than 5 mg samples of hydrous magnesium silicates. For example, high temperature solution calorimetry of natural talc (Mg(0.99) Fe(0.01)Si4O10(OH)2), periclase (MgO) and quartz (SiO2) yield enthalpies of drop solution at 1044 K to be 592.2 (2.2), 52.01 (0.12) and 45.76 (0.4) kJ/mol respectively. The corresponding enthalpy of formation from oxides at 298 K for talc is minus 5908.2 kJ/mol agreeing within 0.1 percent to literature values.

Description: The following points are emphasized: one of the most important ones is certainly the first set of experimental data on the solubility of noble gases in metal phases at intermediate pressures, since the core was certainly not formed at ultra high pressures, as emphasized by Ahrens and confirmed by trace elements systematics Wanke. The experimental data clearly show that the core can not be a major reservoir for terrestrial rare gases; the second point is a more elaborate reconsideration of the (40)K-(40)Ar budget of the Earth. This shows that (40)Ar contained in continental crust plus upper mantle plus atmosphere is at maximum half of the (40)Ar inventory of the whole earth. This implies the existence of a two layered mantle; the third point is the discovery by the Australian noble gases group of the existence of high (20)Ne/(22)Ne and low (21)Ne/(22)Ne isotopic ratios in Loihi seamount samples. This results which are different to the MORB ratios confirm the idea of a two layered model, but suggest the existence of a primordial solar type Ne reservoir. Several possibilities about the origin of this (20)Ne excess in the mantle will be discussed; The high (40)Ar/(36)Ar, (129)Xe/(130)Xe and (134) Xe/(130)Xe, (136)Xe/(130)Xe are confirmed by new data. The corresponding ratios for the lower mantle will be discussed. (40)Ar/(36)Ar ratios up to 6000 can be accepted and will not modify the general model of the mantle. They confirm the atmosphere chronology, about 85 percent of the atmosphere was formed in the first 50 My and 15 percent later on.

Description: In the summer of 1991, a major scientific campaign (NLC-91) involving 31 rocket flights was conducted from ESRANGE, Kiruna, Sweden and from Heiss Island, Russia to investigate the chemical, dynamical, and electrodynamical properties of the polar summer mesosphere. The rocket flights were also coordinated with two coherent radar facilities, EISCAT (European Incoherent Scatter Scientific Association) and CUPRI (Cornell University Portable Radar Instrument), as well as other ground facilities, to provide continual monitoring of the mesosphere by remote sensing techniques. The primary objectives of the campaign were to study noctilucent clouds (NLC's) and polar mesospheric summer echoes (PMSE's), including their possible relationship to local aerosols and/or small scale turbulence. The program involved scientific participation from eight countries, and promises to produce many results during the next few years. This overview considers the scientific campaign and briefly discusses preliminary results. These results are provided in more detail in papers following this overview.

Description: Subduction zones are presently the dominant sites on Earth for recycling and mass transfer between the crust and mantle; they feed hydrated basaltic oceanic crust into the upper mantle, where dehydration reactions release aqueous fluids and/or hydrous melts. The loci for fluid and/or melt generation will be determined by the intersection of dehydration reaction boundaries of primary hydrous minerals within the subducted lithosphere with slab geotherms. For metabasalt of the oceanic crust, amphibole is the dominant hydrous mineral. The dehydration melting solidus, vapor-absent melting phase relationships; and amphibole-out phase boundary for a number of natural metabasalts have been determined experimentally, and the pressure-temperature conditions of each of these appear to be dependent on bulk composition. Whether or not the dehydration of amphibole is a fluid-generating or partial melting reaction depends on a number of factors specific to a given subduction zone, such as age and thickness of the subducting oceanic lithosphere, the rate of convergence, and the maturity of the subduction zone. In general, subduction of young, hot oceanic lithosphere will result in partial melting of metabasalt of the oceanic crust within the garnet stability field; these melts are characteristically high-Al2O3 trondhjemites, tonalites and dacites. The presence of residual garnet during partial melting imparts a distinctive trace element signature (e.g., high La/Yb, high Sr/Y and Cr/Y combined with low Cr and Y contents relative to demonstrably mantle-derived arc magmas). Water in eclogitized, subducted basalt of the oceanic crust is therefore strongly partitioned into melts generated below about 3.5 GPa in 'hot' subduction zones. Although phase equilibria experiments relevant to 'cold' subduction of hydrated natural basalts are underway in a number of high-pressure laboratories, little is known with respect to the stability of more exotic hydrous minerals (e.g., ellenbergite) and the potential for oceanic crust (including metasediments) to transport water deeper into the mantle.

Description: The degassing of the Earth during accretion is constrained by Pu-U-I-Xe systematics. Degassing was much more efficient during the first 100-200 Ma than subsequently, and it was more complete for Xe than for the lighter gases. More than 90 percent of the degassed Xe escaped from the atmosphere during this period. The combination of fractional degassing of melts and rare gas escape from the atmosphere is able to explain the deficit of terrestrial Xe as a simple consequence of this early degassing history. By the time Xe was quantitatively retained in the atmosphere, the abundances of Kr and the lighter gases in the Earth's interior were similar to or higher than the present-day atmospheric abundances. Subsequent transfer of these lighter rare gases into the atmosphere requires a high rate of post-accretion degassing and melt production. Considerations of Pu-U-Xe systematics suggest that relatively rapid post-accretion degassing was continued to ca. 4.1-4.2 Ga. The present-day degassing history of the Earth is investigated through consideration of rare gas isotope abundances. Although the Earth is a highly degassed body, depleted in rare gases by many orders of magnitude relative to their solar abundances, it is at the present-day losing primordial rare gases which were trapped at the time of accretion.

Description: Nitrogen and noble gases are important tracers in geochemistry and chosmochemistry. Compared to noble gases, however, physicochemical properties of nitrogen, such as solubility in melt or melt/silicate partition, are not well known. Solubility of nitrogen in basalt melt depends on redox condition of the atmosphere. For example, solubility of nitrogen in E chondrite melt under reducing conditions is as high as 2 mol percent at 1500 C, suggesting that nitrogen is chemically dissolved in silicate melts, i.e., being dissolved as free anions or replacing oxygen sites in silicate network. However, the solubility and the dissolution mechanism of nitrogen under oxidizing conditions are not well investigated. To obtain nitrogen solubility in silicate melts under various redox conditions and to understand its mechanism, we are conducting experiments by using (15)N(15)N-labeled nitrogen gas. This makes it easy to distinguish dissolved nitrogen from later contamination of atmospheric nitrogen, and hence enables us to measure the nitrogen solubility accurately. As a preliminary experiment, we have measured solubility of nitrogen in basalt melt under the atmospheric oxygen pressure.

Description: A model for He and Xe was presented previously which incorporates mass transfer of rare gases from an undegassed lower mantle (P) and the atmosphere into a degassed upper mantle (D). We extend the model to include Ne and Ar. Model constraints on rare gas relative abundances within P are derived. Discussions of terrestrial volatile acquisition have focused on the rare gas abundance pattern of the atmosphere relative to meteoritic components, and the pattern of rare gases still trapped in the Ear,th is important in identifying volatile capture and loss processes operating during Earth formation. The assumptions and principles of the model are discussed in Wasserburg and Porcelli (this volume). For P, the concentrations in P of the decay/nuclear products 4 He, 21 Ne, 40 Ar, and 136 Xe can be calculated from the concentrations of the parent elements U, Th, K, and Pu. The total concentration of the daughter element in P is proportional to the isotopic shifts in P. For Ar, ((40)Ar/(36)Ar)p - ((40)Ar/(36)Ar)o =Delta (exp 40) p= 40 Cp/(exp 36)C where(i)C(sub j) the concentration of isotope i in j. In D, isotope compositions are the result of mixing rare gases from P, decay/nuclear products generated in the upper mantle, and subducted rare gases (for Ar and Xe).

Description: The depletion of Na, K, Rb, and Cs in the Earth's upper mantle and crust relative to their abundances in chondrites is a long standing problem in geochemistry. Here we consider two commonly invoked mechanisms, namely core formation, and vaporization, for producing the observed depletions. Our models predict that a significant percentage of the Earth's bulk alkali element inventory is in the core (30 percent for Na, 52 percent for K, 74 percent for Rb, and 92 percent for Cs). These predictions agree with independent estimates from nebular volatility trends and (for K) from terrestrial heat flow data. Our models also predict that vaporization and thermal escape during planetary accretion are unlikely to produce the observed alkali element depletion pattern. However, loss during the putative giant impact which formed the Moon cannot be ruled out. Experimental, observational, and theoretical tests of our predictions are also described. Alkali element partitioning into the Earth's core was modeled by assuming that alkali element partitioning during core formation on the aubrite parent body (APB) is analogous to that on the early Earth. The analogy is reasonable for three reasons. First, the enstatite meteorites are the only known meteorites with the same oxygen isotope systematics as the Earth-Moon system. Second, the large core size of the Earth and the V depletion in the mantle requires accretion from planetesimals as reduced as the enstatite chondrites. Third, experimental studies of K partitioning between silicate and metal plus sulfide show that more K goes into the metal plus sulfide at higher pressures than at one atmosphere pressure. Thus partitioning in the relatively low pressure natural laboratory of the APB is a good guide to alkali elemental partitioning during the growth of the Earth.

Description: The stability of hydrous phases in a natural upper mantle system has been investigated at 9.3 GPa using a gel of KLB-1 peridotite composition with brucite which contains 14 wt. percent (30 atom. percent) water. No hydrous mineral was found at 950 (+150 -50) degree C. At 800 degree C, an assemblage of phase A, phase E, enstatite, clinohumite, and garnet is obtained. Although there is a significant thermal gradient over the sample, phase E is found to be surrounded by phase A in the lower temperature part. Electron probe analyses show that phase E has 35.5 SiO2, 4.4 Al2O3, 41.1 MgO and 8.5 wt. percent FeO* (Mg value is 90) with an oxide sum of 89.7 wt. percent, and possesses a stoichiometry similar to that proposed by Kanzaki. CaO and TiO2 are both less than 0.1 wt. percent. Coexisting phase A has 0.5 wt. percent CaO but only 0.4 wt. percent Al2O3 concentration. Phase A coexists with only enstatite in the water-saturated MgO-FeO-SiO2 system at 800 degree C and 9.3 GPa as well as the results in the water-saturated MgO-SiO2 system. Therefore it is suggested that the addition of Al2O3 expands the stability field of phase E to lower than 13 - 17 GPa in the water-saturated MgO-SiO2 system.

Description: Neon isotopic compositions in mantle-derived samples commonly are enriched in (20)Ne and (21)Ne relative to (22)Ne compared with atmospheric neon ((20)Ne/(22)Ne and (21)Ne/(22)Ne ratios in atmospheric neon are 9.8 and 0.029, respectively), together with significant primordial (3)He. Such results have been obtained on MORB's, intraplate plume-related oceanic island basalts, backarc basin basalts, mantle xenoliths, ancient diamonds and CO2 well gases (e.g., 1 - 8). The highest (20)Ne/(22)Ne ratio observed in MORB glasses (= 13.6 plus or minus 1.3 is close to the solar value (= 13.6, as observed in solar wind). In order to explain the enrichment of (20)Ne and (21)Ne relative to atmospheric neon for samples derived from the mantle, it is necessary to postulate the presence of at least two distinct non-atmospheric components. The two most likely candidates are solar and nucleogenic ((20)Ne/(22)Ne solar = 13.6 (21)Ne/(22)Ne solar = 0.032, (20)Ne/(22)Ne nucleogenic = 2.5 and (21)Ne/(22)Ne nucleogenic = 32). This is because solar neon is the only known component with a (20)Ne/(22)Ne ratio greater than both the atmospheric value and that observed in samples derived from the mantle. Nucleogenic neon is well known to elevate (21)Ne/(22)Ne ratios. Neon isotopic signatures observed in mantle-derived samples can be accounted for by mixing of the three neon end members: solar, nucleogenic and atmospheric.

Description: There is general agreement that primary carbon and redox state of mantle play an important role in the formation of carbon species in the terrestrial basalts as well as in the composition of gases, evacuated by these liquids to the upper layers of the Earth. It is expected, that interaction between native carbon and production of partial melting of the upper mantle : C(graphite,diamond) + O2(-) (melt) + O2 = CO3(2-) (melt) (1) leads to the formation of CO3(2-) (carbonate ion) in melt. Next mechanism, that may control the presence of free carbon and the formation of C-bearing components in magmas, is the carbon solubility in minerals under mantle conditions by participating in point defect equilibria.

Description: Published data on Xe isotope compositions in primitive carbonaceous meteorites are examined using multidimensional correlation analysis. Distribution of the Xe data in multidimensional data space, except for (129)Xe, can be characterized by a single component, whose isotope composition is identical to 'H plus L minus Xe'. Additional small contributions to the data variations, less than 1 percent of total variations, can be attributed to 'S minus Xe' as well as atmospheric contamination. Isotopic composition of primitive Xe common to the Earth's atmosphere and carbonaceous meteorites are determined with the same assumption as adopted by Pepin and Phinney: primitive Xe is precisely related to fission-free Xe in the Earth's atmosphere by mass fractionation. The determined isotopic composition of primitive Xe is closer to Solar-type Xe, rather than U-Xe (and the primitive Xe estimated from chondrite-achondrite correlation. Hence, the present published data on Xe isotope compositions in meteorites do not seem to require any special component for the primitive Xe common to the Earth's atmosphere and carbonaceous meteorites. Thus Earth's accreting planetesimals would have trapped Xe from the surrounding nebula gases where Xe isotope composition is identical to Solar-type Xe. The trapped Xe was subsequently subject to isotopic fractionation due to gravitational separation as planetesimals grew. Finally fissiogenic Xe from (244)Pu was added to form the present Xe isotope composition of the Earth's atmosphere. The amount of fissiogenic (136)Xe is estimated to be 2.6 percent of the total amount of (136)Xe in the atmosphere, which is about a half of that estimated by Pepin and Phinney (4.65 percent).

Description: The results of the diffusion experiment for solar He and Ne in IDP's in a magnetic separate from Pacific Ocean sediment suggest that solar He and Ne would be easily released from IDP grains and hence lost from subducting slabs at shallow depths. However, since the diffusion experiments was conducted under high vacuum, there may be a possibility that magnetite grains, which are supposedly the main constituent of the magnetic fraction, might be partly reduced to form a metal phase due to low oxygen fugacity in the experimental condition. If this is the case, such a phase change might affect the gas release and hence the results of the diffusion coefficients. In order to examine whether or not such a phase change really occurred in the condition of the diffusion experiment, I conducted a heating experiment for a magnetic separate from Pacific Ocean sediment. In the same condition as in the diffusion experiment, and the run products were examined with an x ray diffraction method. Three samples were prepared: they were wrapped with platinum foil, put in a vacuum line, and heated in a molybdenum crucible for two hours at 500 C, 800 C,and 950 C, respectively. After cooling the furnace, the samples were taken out from the crucible and analyzed with an x ray diffraction method.