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A principal component analysis (PCA) is applied to the Southern Hemisphere (SH) total column ozone following the method established for analyzing the data in the Northern Hemisphere (NH) in a companion paper. The interannual variability (IAV) of extratropical O3 in the SH is characterized by four main modes, which account for 75% of the total variance. The first two leading modes are approximately zonally symmetric and relate to the Southern Hemisphere annular mode and the quasi-biennial oscillation. The third and fourth modes exhibit wavenumber-1 structures. Contrary to the Northern Hemisphere, the third and fourth modes are not related to stationary waves. Similar results are obtained for the 30–100-hPa geopotential thickness. The decreasing O3 trend in the SH is captured in the first mode. The largest trend is at the South Pole, with value ∼−2 Dobson Units (DU) yr−1. Both the spatial pattern and trends in the column ozone are captured by the Goddard Earth Observation System chemistry–climate model (GEOS-CCM) in the SH.

The prolific activity and presence of a plume on Saturn's tiny moon Enceladus offers us a unique opportunity to sample the interior composition of an icy satellite, and to look for interesting chemistry and possible signs of life. Based on studies of the potential habitability of Jupiter's moon Europa, icy satellite oceans can be habitable if they are chemically mixed with the overlying ice shell on Myr time scales. We hypothesize that Enceladus' plume, tectonic processes, and possible liquid water ocean may create a complete and sustainable geochemical cycle that may allow it to support life. We discuss evidence for surface/ocean material exchange on Enceladus based on the amounts of silicate dust material present in the Enceladus' plume particles. Microphysical cloud modeling of Enceladus' plume shows that the particles originate from a region of Enceladus' near surface where the temperature exceeds 190 K. This could be consistent with a shear-heating origin of Enceladus' tiger stripes, which would indicate extremely high temperatures ( approximately 250-273 K) in the subsurface shear fault zone, leading to the generation of subsurface liquid water, chemical equilibration between surface and subsurface ices, and crustal recycling on a time scale of 1 to 5 Myr. Alternatively, if the tiger stripes form in a mid-ocean-ridge-type mechanism, a half-spreading rate of 1 m/year is consistent with the observed regional heat flux of 250 mW m(-2) and recycling of south polar terrain crust on a 1 to 5 Myr time scale as well.

We perform a retrieval based on optimal estimation theory to retrieve the vertical distribution of ozone from simulated spectra in the Huggins bands. The model atmosphere includes scattering by aerosol as well as Rayleigh scattering. The virtual instrument is ground-based and zenith-viewing. Using this algorithm, we show that it is possible to retrieve the ozone profile provided that the spectral resolution is at least 0.2 nm and the signal to noise ratio greater than 500. Our synthetic retrievals suggest that if we are able to measure the Stokes parameters Q, U and V with accuracy comparable to that of the intensity, the information contained in the measurements, and therefore the inversion, will improve. Furthermore, we find that the measurement of the full Stokes vector from the ground-based instrument will especially enhance the retrieval of tropospheric ozone. Utilizing concepts from information theory, our arguments are confirmed by increases in the degrees of freedom and the Shannon information content in the simulated measurements.

Sensitivity studies have been performed to evaluate the errors resulting from ignoring polarization in analyzing spectroscopic measurements of the O_2A band from space, using the Orbiting Carbon Observatory (OCO) as a test case. An 11-layer atmosphere, with both gas and aerosol loading, and bounded from below by a lambertian reflecting surface, was used for the study. The numerical computations were performed with a plane-parallel vectorized discrete ordinate radiative transfer code. Beam and viewing geometry, surface reflectance and aerosol loading were varied one at a time to evaluate and understand the individual errors. Different behavior was observed in the line cores and the continuum because of the different paths taken by the photons in the two cases. The errors were largest when the solar zenith angle was high, and the aerosol loading and surface reflectance low. To understand the effect of neglecting polarization on CO_2 column retrievals, a linear error analysis study was performed on simulated measurements from the OCO spectral regions, viz. the 1.61 and 2.06 μm CO_2 bands and the O_2A band. It was seen that neglecting polarization could introduce errors as high as 10 ppm, which is substantially larger than the required retrieval precision of ∼2 ppm. A variety of approaches, including orders of scattering, spectral binning and the use of lookup tables are being explored to reduce the errors.

We use the JPL/Caltech 1-D photochemical model to solve continuity diffusion equation for atmospheric constituent abundances and total number density as a function of radial distance from the planet Venus. Photochemistry of the Venus atmosphere from 58 to 112 km is modeled using an updated and expanded chemical scheme (Zhang et al., 2010 and Zhang et al., 2012), guided by the results of recent observations and we mainly follow these references in our choice of boundary conditions for 40 species. We model water between 10 and 35 ppm at our 58 km lower boundary using an SO_2 mixing ratio of 25 ppm as our nominal reference value. We then vary the SO_2 mixing ratio at the lower boundary between 5 and 75 ppm holding water mixing ratio of 18 ppm at the lower boundary and finding that it can control the water distribution at higher altitudes. SO_2 and H_2O can regulate each other via formation of H_2SO_4. In regions of high mixing ratios of SO_2 there exists a “runaway effect” such that SO_2 gets oxidized to SO_3, which quickly soaks up H_2O causing a major depletion of water between 70 and 100 km. Eddy diffusion sensitivity studies performed characterizing variability due to mixing that show less of an effect than varying the lower boundary mixing ratio value. However, calculations using our nominal eddy diffusion profile multiplied and divided by a factor of four can give an order of magnitude maximum difference in the SO_2 mixing ratio and a factor of a few difference in the H_2O mixing ratio when compared with the respective nominal mixing ratio for these two species. In addition to explaining some of the observed variability in SO_2 and H_2O on Venus, our work also sheds light on the observations of dark and bright contrasts at the Venus cloud tops observed in an ultraviolet spectrum. Our calculations produce results in agreement with the SOIR Venus Express results of 1 ppm at 70–90 km (Bertaux et al., 2007) by using an SO_2 mixing ratio of 25 ppm SO_2 and 18 ppm water as our nominal reference values. Timescales for a chemical bifurcation causing a collapse of water concentrations above the cloud tops (>64 km) are relatively short and on the order of a less than a few months, decreasing with altitude to less than a few days.

Warm Neptune- and sub-Neptune-sized exoplanets in orbits smaller than Mercury’s are thought to have experienced extensive atmospheric evolution. Here we propose that a potential outcome of this atmospheric evolution is the formation of helium-dominated atmospheres. The hydrodynamic escape rates of Neptune- and subNeptune-sized exoplanets are comparable to the diffusion-limited escape rate of hydrogen, and therefore the escape is heavily affected by diffusive separation between hydrogen and helium. A helium atmosphere can thus be formed —from a primordial hydrogen–helium atmosphere—via atmospheric hydrodynamic escape from the planet. The helium atmosphere has very different abundances of major carbon and oxygen species from those of a hydrogen atmosphere, leading to distinctive transmission and thermal emission spectral features. In particular, the hypothesis of a helium-dominated atmosphere can explain the thermal emission spectrum of GJ 436b, a warm Neptune-sized exoplanet, while also being consistent with the transmission spectrum. This model atmosphere contains trace amounts of hydrogen, carbon, and oxygen, with the predominance of CO over CH4 as the main form of carbon. With our atmospheric evolution model, we find that if the mass of the initial atmosphere envelope is 10 �3 planetary mass, hydrodynamic escape can reduce the hydrogen abundance in the atmosphere by several orders of magnitude in ∼10 billion years. Observations of exoplanet transits may thus detect signatures of helium atmospheres and probe the evolutionary history of small exoplanets.

Midtropospheric CO2 data from the Atmospheric Infrared Sounder (AIRS) are used in this study to explore the variability of CO2 over the South Atlantic Ocean. It was found that the area-averaged CO2 over the South Atlantic Ocean is less than that over South America by about 1 ppm during December–March. This CO2 contrast is due to the large-scale vertical circulation over this region. During December–March, there is sinking motion over the South Atlantic Ocean. The sinking motion brings high-altitude air with a slightly lower concentration of CO2 to the midtroposphere. Meanwhile, air rising over South America brings near-surface air with a higher concentration of CO2 to the midtroposphere. As a result, the AIRS midtropospheric CO2 concentration is lower over the South Atlantic Ocean than over South America during December–March. The detrended AIRS midtropospheric CO2 difference correlates well with the inverted and detrended 400-hPa vertical pressure velocity difference between the South Atlantic and South America. Results obtained from this study demonstrate the strong impact of large-scale circulation on the vertical distribution of CO2 in the free troposphere and suggest that midtropospheric CO2 measurements can be used as an innovative observational constraint on the simulation of large-scale circulations in climate models.

Motivated by the recent detection of propene (C_3H_6) in the atmosphere of Titan, we use a one-dimensional Titan photochemical model with an updated eddy diffusion profile to systematically study the vertical profiles of the stable species in the C_3-hydrocarbon family. We find that the stratospheric volume mixing ratio of propene (C_3H_6) peaks at 150 km with a value of 5 × 10^(−9), which is in good agreement with recent observations by the Composite Infrared Spectrometer on the Cassini spacecraft. Another important species that is currently missing from the hydrocarbon family in Titan's stratosphere is allene (CH_2CCH_2), an isomer of methylacetylene (CH_3C_2H). We predict that its mixing ratio in the stratosphere is about 10^(−9), which is on the margin of the detection limit. CH_2CCH_2 and CH_3C_2H equilibrate at a constant ratio in the stratosphere by hydrogen-exchanging reactions. Thus, by precisely measuring the ratio of CH_2CCH_2 to CH_3C_2H, the abundance of atomic hydrogen in the atmosphere can be inferred. No direct yield for the production of cyclopropane (c-C_3H_6) is available. From the discharge experiments of Navarro-Gonzalez & Ramirez, the abundance of cyclopropane is estimated to be 100 times less than that of C_3H_6.

We investigate the chemical stability of CO2-dominated atmospheres of desiccated M dwarf terrestrial exoplanets using a 1-dimensional photochemical model. Around Sun-like stars, CO2 photolysis by Far-UV (FUV) radiation is balanced by recombination reactions that depend on water abundance. Planets orbiting M dwarf stars experience more FUV radiation, and could be depleted in water due to M dwarfs' prolonged, high-luminosity pre-main sequences (Luger & Barnes 2015). We show that, for water-depleted M dwarf terrestrial planets, a catalytic cycle relying on H2O2 photolysis can maintain a CO2 atmosphere. However, this cycle breaks down for atmospheric hydrogen mixing ratios, 39 pages, 9 figures, 2 tables, accepted for publication in Astrophysical Journal

In 2004, the first reports of methane (CH4) in Mars’ atmosphere, by both Mars Express and ground-based observations, stirred up excitement in the scientific community [1,2]. These detections (at 10 ppbv level) immediately raised questions regarding the origin of methane. On Mars, oxidants and UV radiation destroy atmospheric methane in approximately 300 yrs [3]. Therefore, the presence of atmospheric methane requires ongoing or recent methane emission. On Earth, methane is almost entirely of (live and fossil) biological origin, while abiotic sources, believed to be predominantly volcanic and/or hydrothermal, account for the rest (a few percent) of the total CH4 flux into the atmosphere

The climate of Mars likely evolved from a warmer, wetter early state to the cold, arid current state. However, no solutions for this evolution have previously been found to satisfy the observed geological features and isotopic measurements of the atmosphere. Here we show that a family of solutions exist, invoking no missing reservoirs or loss processes. Escape of carbon via CO photodissociation and sputtering enriches heavy carbon (13C) in the Martian atmosphere, partially compensated by moderate carbonate precipitation. The current atmospheric 13C/12C and rock and soil carbonate measurements indicate an early atmosphere with a surface pressure, Published 24 November 2015 on Nature Communications

The atmospheric moisture and temperature profiles from the Atmospheric Infrared Sounder (AIRS)/Advanced Microwave Sounding Unit on the NASA Aqua mission, in combination with the precipitation from the Tropical Rainfall Measuring Mission (TRMM), are employed to study the vertical moist thermodynamic structure and spatial–temporal evolution of the Madden–Julian oscillation (MJO). The AIRS data indicate that, in the Indian Ocean and western Pacific, the temperature anomaly exhibits a trimodal vertical structure: a warm (cold) anomaly in the free troposphere (800–250 hPa) and a cold (warm) anomaly near the tropopause (above 250 hPa) and in the lower troposphere (below 800 hPa) associated with enhanced (suppressed) convection. The AIRS moisture anomaly also shows markedly different vertical structures as a function of longitude and the strength of convection anomaly. Most significantly, the AIRS data demonstrate that, over the Indian Ocean and western Pacific, the enhanced (suppressed) convection is generally preceded in both time and space by a low-level warm and moist (cold and dry) anomaly and followed by a low-level cold and dry (warm and moist) anomaly. The MJO vertical moist thermodynamic structure from the AIRS data is in general agreement, particularly in the free troposphere, with previous studies based on global reanalysis and limited radiosonde data. However, major differences in the lower-troposphere moisture and temperature structure between the AIRS observations and the NCEP reanalysis are found over the Indian and Pacific Oceans, where there are very few conventional data to constrain the reanalysis. Specifically, the anomalous lower-troposphere temperature structure is much less well defined in NCEP than in AIRS for the western Pacific, and even has the opposite sign anomalies compared to AIRS relative to the wet/dry phase of the MJO in the Indian Ocean. Moreover, there are well-defined eastward-tilting variations of moisture with height in AIRS over the central and eastern Pacific that are less well defined, and in some cases absent, in NCEP. In addition, the correlation between MJO-related midtropospheric water vapor anomalies and TRMM precipitation anomalies is considerably more robust in AIRS than in NCEP, especially over the Indian Ocean. Overall, the AIRS results are quite consistent with those predicted by the frictional Kelvin–Rossby wave/conditional instability of the second kind (CISK) theory for the MJO.

Cross sections for photoabsorption of NH_3, NH_2D, NHD_2, and ND_3 in the spectral region 140-220 nm were determined at ~298 K using synchrotron radiation. Absorption spectra of NH_2D and NHD_2 were deduced from spectra of mixtures of NH_3 and ND_3, of which the equilibrium concentrations for all four isotopologues obey statistical distributions. Cross sections of NH_2D, NHD_2, and ND_3 are new. Oscillator strengths, an integration of absorption cross sections over the spectral lines, for both A ← X and B ← X systems of NH_3 agree satisfactorily with previous reports; values for NH_2D, NHD_2, and ND_3 agree with quantum chemical predictions. The photolysis of NH_3 provides a major source of reactive hydrogen in the lower stratosphere and upper troposphere of giant planets such as Jupiter. Incorporating the measured photoabsorption cross sections of NH_3 and NH_2D into the Caltech/JPL photochemical diffusive model for the atmosphere of Jupiter, we find that the photolysis efficiency of NH_2D is lower than that of NH_3 by as much as 30%. The D/H ratio in NH_2D/NH_3 for tracing the microphysics in the troposphere of Jupiter is also discussed.

We present a detailed study of the distribution of key deuterated species (viz., atomic D and HD) and the associated deuterium Lyman-α airglow in the jovian thermosphere. The reactions that appear to govern the abundances of these deuterated species are used in conjunction with C_2-chemistry in a 1-D photochemical-diffusion model. While the D abundance is mainly sensitive to H densities and the vibrational temperature profile, the D vertical distribution also depends on other parameters such as eddy mixing and the uncertain values of some of the reaction rate constants. We consider different scenarios by varying several parameters controlling the D distribution in the thermosphere. A radiative transfer model with coupling of the H and D Lyman-α lines is employed to obtain line profiles and total intensities at disk center for these scenarios. This allows a comparison of the impact of various parameters on the jovian D Lyman-α emission. A consequence of these chemical processes in the jovian thermosphere is the formation of CH_2D, CH_3D, and C_2H_5D, and other deuterated species. We also discuss the source of these deuterated hydrocarbons and their abundance. We find that HD vibrational chemistry impacts D in the thermosphere, CH_3D and C_2H_5D are vibrationally enhanced in the thermosphere, and variations in abundance of CH_3D and C_2H_5D in the thermosphere may reflect dynamical activity (i.e., K_h) in the jovian upper atmosphere. An observing program dedicated to providing such measurements of these testable phenomena would provide further insight into the synergistic coupling between chemistry, energetics and airglow in the jovian upper atmosphere.

We have explored the detectability of exovegetation on the surface of a terrestrial planet orbiting an M star. The exovegetation is responsible for producing a pigment-derived surface signature that is redshifted with respect to the Earth vegetation's red edge. The redshift was estimated using a model of leaf optical property spectra (Jacquemoud & Baret) combined with a 3 photon photosynthetic scheme calculated by Wolstencroft & Raven for a possible exovegetation growing on an M star planet. To study the detectability of this surface biosignature on an M star terrestrial planet, we have used the three-dimensional model developed by Tinetti et al. for the case of the Earth. This model can generate disk-averaged spectra and broadband integrated fluxes, which will be useful for future terrestrial planet exploration missions, such as the NASA Terrestrial Planet Finder Coronagraph. Input to this model were the atmospheric profiles and cloud distributions predicted by Joshi and coworkers for a synchronous planet orbiting an M dwarf and the distinctive surface reflectance of the exovegetation. While on Earth this pigment-derived surface feature would be almost completely masked by water absorption, even in a cloud-free atmosphere, we found that the strength of the edge feature on our simulated M star terrestrial planet can exceed that on Earth, given the right conditions. Obviously, the detectability of such biosignatures would be highly dependent on the extent of vegetation surface area, cloud cover, and viewing angle.

We investigate the connection between the equatorial Madden‐Julian Oscillation (MJO) and different types of the Northern Hemisphere mid‐winter major stratospheric sudden warmings (SSWs), i.e., vortex‐displacement and vortex‐split SSWs. The MJO‐SSW relationship for vortex‐split SSWs is stronger than that for vortex‐displacement SSWs, as a result of the stronger and more coherent eastward propagating MJOs before vortex‐split SSWs than those before vortex‐displacement SSWs. Composite analysis indicates that both the intensity and propagation features of MJO may influence the MJO‐related circulation pattern at high latitudes and the type of SSWs. A pronounced Quasi‐Biennial Oscillation (QBO) dependence is found for vortex‐displacement and vortex‐split SSWs, with vortex‐displacement (‐split) SSWs occurring preferentially in easterly (westerly) QBO phases. The lagged composites suggest that the MJO‐related anomalies in the Arctic are very likely initiated when the MJO‐related convection is active over the equatorial Indian Ocean (around the MJO phase 3). Further analysis suggests that the QBO may modulate the MJO‐related wave disturbances via its influence on the upper tropospheric subtropical jet. As a result, the MJO‐related circulation pattern in the Arctic tends to be wave number‐one/wave number‐two ~25–30 days following phase 3 (i.e., approximately phases 7–8, when the MJO‐related convection is active over the western Pacific) during easterly/westerly QBO phases, which resembles the circulation pattern associated with vortex‐displacement/vortex‐split SSWs.

Radiative transfer computation is the rate-limiting step in most high spectral resolution remote sensing retrieval applications. While several techniques have been proposed to speed up radiative transfer calculations, they all suffer from accuracy considerations. We propose a new method, based on a principal component analysis of the optical properties of the system, that addresses these concerns. Taking atmospheric transmission in the O_2A band as a test case, we reproduced the reflectance spectrum at the top of the atmosphere (TOA), obtained using the multiple scattering code DISORT, with an accuracy of 0.3%, while achieving an order of magnitude improvement in speed.

The existence of methane in the martian atmosphere may be an indicator of subsurface life. Biological processes are known to fractionate the common isotopologues of methane, and hence measuring these isotopic ratios may yield constraints on the nature of the methane source. Any measurement of the isotopic ratios of atmospheric methane must consider the additional fractionation due to photochemistry in order to quantify the isotopic ratios of the source. Using a one-dimensional photochemical model, we find that photochemistry has a small (4.5‰) contribution to δ^(13)C(CH_4) but has a large (114‰) contribution to δD(CH_4). Confirmation of these fractionation values will require additional laboratory data on key model inputs, particularly the ultraviolet absorption cross sections of ^(13)CH_4 and kinetic rate coefficients for the reactions of ^(13)CH_4 and CH_3D with OH and O(^1D) at pressures and temperatures relevant to the martian atmosphere.

The Cassini Ultraviolet Imaging Spectrograph (UVIS) is part of the remote sensing payload of the Cassini orbiter spacecraft. UVIS has two spectrographic channels that provide images and spectra covering the ranges from 56 to 118 nm and 110 to 190 nm. A third optical path with a solar blind CsI photocathode is used for high signal-to-noise-ratio stellar occultations by rings and atmospheres. A separate Hydrogen Deuterium Absorption Cell measures the relative abundance of deuterium and hydrogen from their Lyman-α emission. The UVIS science objectives include investigation of the chemistry, aerosols, clouds, and energy balance of the Titan and Saturn atmospheres; neutrals in the Saturn magnetosphere; the deuterium-to-hydrogen (D/H) ratio for Titan and Saturn; icy satellite surface properties; and the structure and evolution of Saturn’s rings.

The close-in extrasolar giant planets (CEGPs) reside in irradiated environments much more intense than that of the giant planets in our solar system. The high UV irradiance strongly influences their photochemistry and the general current view believed that this high UV flux will greatly enhance photochemical production of hydrocarbon aerosols. In this letter, we investigate hydrocarbon aerosol formation in the atmospheres of CEGPs. We find that the abundances of hydrocarbons in the atmospheres of CEGPs are significantly less than that of Jupiter except for models in which the CH$_4$ abundance is unreasonably high (as high as CO) for the hot (effective temperatures $\gtrsim 1000$ K) atmospheres. Moreover, the hydrocarbons will be condensed out to form aerosols only when the temperature-pressure profiles of the species intersect with the saturation profiles--a case almost certainly not realized in the hot CEGPs atmospheres. Hence our models show that photochemical hydrocarbon aerosols are insignificant in the atmospheres of CEGPs. In contrast, Jupiter and Saturn have a much higher abundance of hydrocarbon aerosols in their atmospheres which are responsible for strong absorption shortward of 600 nm. Thus the insignificance of photochemical hydrocarbon aerosols in the atmospheres of CEGPs rules out one class of models with low albedos and featureless spectra shortward of 600 nm., ApJL accepted

Light reflected or transmitted by a planetary atmosphere contains information about particles and molecules in the atmosphere. Therefore, accurate modeling of the radiation field may be used to retrieve information on atmospheric composition. In this paper, a multi-layer model for a vertically inhomogeneous atmosphere is implemented by using the doubling-adding method for a plane-parallel atmosphere. By studying the degree of linear polarization of the transmitted and reflected solar light in the Huggins bands, we find significant differences between tropospheric ozone and stratospheric ozone. The effects of tropospheric ozone change on the linear polarization are 10 times more than that of the same amount of stratospheric ozone change. We also show the aerosol effect on the linear polarization, but this effect is wavelength independent as compared to that caused by the tropospheric ozone change. The results provide a theoretical basis for the retrieval of tropospheric ozone from measurement of linear polarization of the scattered sunlight both from the ground and from a satellite.

We introduce two new techniques in analyzing martian spectrally resolved radiance data obtained by the Thermal Emission Spectrometer (TES): spectral empirical orthogonal function (EOF) analysis and the tri-spectral algorithm. Spectral EOF analysis allows us to obtain the variability of spectra and associated temporal and spatial patterns. The case study with TES 20° S–20° N data shows that the first principal component (PC1) dominates the total variance and is associated with surface or near-surface brightness temperature variations. The PC2 is associated with atmospheric variability, and a negative correlation between dust and ice absorptions can be clearly seen over many regions. The annual cycle is a major component of the PC1 temporal patterns. The fingerprint of the dust storm can be clearly seen in the PC2 temporal patterns in most areas except the highlands. Spectral EOF can be used for validation of the variability of martian GCMs. The tri-spectral algorithm is based on the differences between three bands (dust, ice and a weak CO_2 absorption band) to distinguish spectra sampled in different situations: water ice cloud, dust, and surface anisothermality. We use a line-by-line radiative transfer model coupled with multiple scattering to investigate the sensitivity of this algorithm to dust and ice optical depth as well as surface emissivity. The comparisons between results of this algorithm and the TES team's retrieved dust and ice opacity are consistent over all studied periods except during the peak of the dust storm. Our algorithm is complementary to the more sophisticated TES retrieval and can be used to screen large amounts of data to get an overview.

▪ Abstract The anthropogenic production of greenhouse gases and their consequent effects on global climate have garnered international attention for years. A remaining challenge facing scientists is to unambiguously quantify both sources and sinks of targeted gases. Microbiological metabolism accounts for the largest source of nitrous oxide (N2O), mostly due to global conversion of land for agriculture and massive usage of nitrogen-based fertilizers. A most powerful method for characterizing the sources of N2O lies in its multi-isotope signature. This review summarizes mechanisms that lead to biological N2O production and how discriminate placement of15N into molecules of N2O occurs. Through direct measurements and atmospheric modeling, we can now place a constraint on the isotopic composition of biological sources of N2O and trace its fate in the atmosphere. This powerful interdisciplinary combination of biology and atmospheric chemistry is rapidly advancing the closure of the global N2O budget.

We present coupled chemical–microphysical models for the formation, growth, and physical properties of the jovian polar haze based on a gas-phase photochemical model for the auroral regions developed by A. S. Wong et al. (2000, Astrophys. J.534, L215–217). In this model, auroral particle precipitation provides an important energy source for enhanced decomposition of methane and production of benzene and polycyclic aromatic hydrocarbons (PAHs). We find that at high altitude, A_4 (pyrene, a hydrocarbon consisting of four fused aromatic rings) should homogeneously nucleate to form tiny primary particles. At lower altitudes, A_3 (phenanthrene) and A_2 (naphthalene) heterogeneously nucleate on the A4 nuclei. These particles subsequently grow by additional condensation of A_2 on the nucleated particles and by coagulation and eventually sediment out to the troposphere. We run different cases of the aerosol microphysical model for different assumptions regarding the fractal dimension of aggregate particles formed by the coagulation process. If coagulation is assumed to produce spherical particles (of dimensionality 3), then their mean radius at altitudes below the 20-mbar pressure level is computed to be approximately 0.1 μm. If coagulation produces fractal aggregates of dimension 2.1, then their equivalent mean radius below the 20-mbar level is much larger, of order 0.7 μm. Aggregates with fractal dimensions between 2.1 and 3 form with equivalent mean radii between 0.1 and 0.7 μm. In every case, mean particle radius is found to decrease with increasing altitude, as expected for a system approximately in sedimentation–coagulation equilibrium. The predicted range of altitudes where aerosol formation occurs and the mean size to which particles grow are found to be generally consistent with observations. However, our calculations cannot presently account for the large amount of total aerosol loading inferred by M. G. Tomasko et al. (1986, Icarus65, 218–243). We suggest that the primarily neutral chemical pathway to heavy hydrocarbon and PAH formation proposed by Wong et al. (2000) may proceed too slowly to produce a sufficient amount of condensible material. Inclusion of ion and ion–neutral reactions in the chemical scheme could potentially lead to the prediction of higher PAH production rates, higher nucleation rates, and greater aerosol loading, producing better agreement with the observations.

The early evolution of Titan's atmosphere is expected to produce enrichment in the heavy isotopomers of CO, ^(13)CO and C^(18)O, relative to ^(12)C^(16)O. However, the original isotopic signatures may be altered by photochemical reactions. This paper explains why there is no isotopic enrichment in C in Titan's atmosphere, despite significant enrichment of heavy H, N, and O isotopes. We show that there is a rapid exchange of C atoms between the CH_4 and CO reservoirs, mediated by the reaction ^1CH_2+^*CO→^(1*)CH_2+CO, where ^*C is ^(13)C. Based on recent laboratory measurements, we estimate the rate coefficient for this reaction to be 3.2×10^(−12) cm^3 s^(−1) at the temperature appropriate for the upper atmosphere of Titan. We investigate the isotopic dilution of CO using the Caltech/JPL one-dimensional photochemical model of Titan. Our model suggests that the time constant for isotopic exchange through the above reaction is about 800 Myr, which is significantly shorter than the age of Titan, and therefore any original isotopic enhancement of ^(13)C in CO may have been diluted by the exchange process. In addition, a plausible model for the evolution history of CO on Titan after the initial escape is proposed.

Using CO_2 data from the Atmospheric Infrared Sounder (AIRS), it is found for the first time that the mid-tropospheric CO_2 concentration is ~1 part per million by volume higher during dry years than wet years over the southwestern USA from June to September. The mid-tropospheric CO_2 differences between dry and wet years are related to circulation and CO_2 surface fluxes. During drought conditions, vertical pressure velocity from NCEP2 suggests that there is more rising air over most regions, which can help bring high surface concentrations of CO_2 to the mid-troposphere. In addition to the circulation, there is more CO_2 emitted from the biosphere to the atmosphere during droughts in some regions, which can contribute to higher concentrations of CO_2 in the atmosphere. Results obtained from this study demonstrate the significant impact of droughts on atmospheric CO_2 and therefore on a feedback cycle contributing to greenhouse gas warming. It can also help us better understand atmospheric CO_2, which plays a critical role in our climate system.

We use MERRA (Modern Era Retrospective-Analysis for Research Applications) temperature and water vapor data to estimate the sampling biases of climatologies derived from the AIRS/AMSU-A (Atmospheric Infrared Sounder/Advanced Microwave Sounding Unit-A) suite of instruments. We separate the total sampling bias into temporal and instrumental components. The temporal component is caused by the AIRS/AMSU-A orbit and swath that are not able to sample all of time and space. The instrumental component is caused by scenes that prevent successful retrievals. The temporal sampling biases are generally smaller than the instrumental sampling biases except in regions with large diurnal variations, such as the boundary layer, where the temporal sampling biases of temperature can be ± 2 K and water vapor can be 10% wet. The instrumental sampling biases are the main contributor to the total sampling biases and are mainly caused by clouds. They are up to 2 K cold and > 30% dry over midlatitude storm tracks and tropical deep convective cloudy regions and up to 20% wet over stratus regions. However, other factors such as surface emissivity and temperature can also influence the instrumental sampling bias over deserts where the biases can be up to 1 K cold and 10% wet. Some instrumental sampling biases can vary seasonally and/or diurnally. We also estimate the combined measurement uncertainties of temperature and water vapor from AIRS/AMSU-A and MERRA by comparing similarly sampled climatologies from both data sets. The measurement differences are often larger than the sampling biases and have longitudinal variations.

HOx radicals are produced in the martian atmosphere by the photolysis of water vapor and subsequently participate in catalytic cycles that recycle carbon dioxide (CO2) from its photolysis product carbon monoxide (CO), providing a qualitative explanation for the stability of its atmosphere. Balancing CO2 production and loss based on our current understanding of martian gas-phase chemistry has, however, proven to be difficult. The photolysis of O3 produces O(1D), while oxidation of CO produces HOCO radicals, a new member of the HOx family. The O(1D) quantum yield has recently been updated, which quantifies nonzero quantum yields in the Huggins bands. In Earth's atmosphere HOCO is considered to be unimportant since it is quickly removed by abundant oxygen molecules. The smaller amount of O2 in the Mars' atmosphere causes HOCO's lifetime to be longer in Mars' atmosphere than Earth's (3×10-5s to 1.2days from Mars's surface to 240km, respectively). Limited kinetic data on reactions involving HOCO prevented consideration of its reactions directly in atmospheric models. Therefore, the impact of HOCO reactions on martian chemistry is currently unknown. Here, we incorporate new literature rate constants for HOCO chemistry and an updated representation of the O(1D) quantum yield in the Caltech/JPL 1-D photochemical model for Mars' atmosphere. Our simulations exemplify perturbations to NOy, HOx, and COx species, ranging from 5% to 50%. The modified O(1D) quantum yield and new HOCO chemistry cause a 10% decrease and a 50% increase in OH and H2O2 total column abundances, respectively. At low altitudes, HOCO production contributes 5% towards CO2 production. Given recent experimentally-obtained branching ratios for the oxidation of CO, HOCO may contribute up to 70% toward the production of NOy, where HOx and NOy species are enhanced up to a factor 3, which has implications for rethinking the fundamental understanding of NOy, HOx, and CO/CO2 cycling on Mars. Two new reaction mechanisms for converting CO to CO2 using HOCO reactions are proposed, which reveal that H2O2 is more intimately coupled to COx chemistry. Our simulations are in good agreement with satellite/spacecraft measurements of CO and H2O2 on Mars. © 2014.

Cross sections for photoabsorption of HCl and DCl are determined in the spectral region of 135-232 nm using radiation from a synchrotron light source. At wavelengths near the onset of absorption (λ > 200 nm), cross sections of HCl are approximately 5-10 times larger than those of DCl. These data are used to calculate rates of photodissociation of HCl and DCl in the Venusian atmosphere. For the entire wavelength region measured, the rate of photodissociation of DCl is only 16% that of HCl. The difference in rates of photodissociation contributes to the exceptionally large [D]/[H] ratio of the Venusian atmosphere.

The dominant processes affecting the concentration of tropospheric methane on interannual timescales are the biospheric and anthropogenic sources and changes in the abundance of the hydroxyl radical caused by the changes in the UV flux which result from changes in stratospheric ozone abundance. We have carried out an empirical study of the sensitivity of the methane to fluctuations in ozone column abundance. This analysis was carried out using monthly mean surface methane concentrations measured by the National Oceanic and Atmospheric Administration – Climate Monitoring and Diagnostics Laboratory (NOAA-CMDL) Global Cooperative Air Sampling Network from 1983 to 1998 and ozone column abundances obtained by the Total Ozone Mapping Spectrometer (TOMS) and the EP TOMS instruments over the same time period. We focused on interannual variability with periods between 15 and 60 months, in which interval the dominant ozone fluctuation is the quasi-biennial oscillation (QBO), with a period of approximately 29 months. In order to isolate the response of methane to ozone from the effects of variability in the sources and transport of methane, we restricted our analysis to data at mid-latitudes in the southern hemisphere. A statistical study shows that the sensitivity factor α≡−d(ln[CH_4])/d(ln[O_3])=−0.038±0.009. The response of CH_4 lags approximately 6 months behind the forcing by O_3. A simple model was used to interpret the empirical results. Our results confirm that any mechanism that affects stratospheric ozone impacts the oxidizing potential of the troposphere. CH_4 fluctuations provide a quantitative measure of this important effect linking the upper and the lower atmosphere.

Reducing climate drift in coupled atmosphere–ocean general circulation models (AOGCMs) usually requires 1000–2000 years of spinup, which has not been practical for every modeling group to do. For the purpose of evaluating the impact of climate drift, the authors have performed a multimillennium-long control run of the Goddard Institute for Space Studies model (GISS-EH) AOGCM and produced different twentieth-century historical simulations and subsequent twenty-first-century projections by branching off the control run at various stages of equilibration. The control run for this model is considered at quasi equilibration after a 1200-yr spinup from a cold start. The simulations that branched off different points after 1200 years are robust, in the sense that their ensemble means all produce the same future projection of warming, both in the global mean and in spatial detail. These robust projections differ from the one that was originally submitted to the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4), which branched off a not-yet-equilibrated control run. The authors test various common postprocessing schemes in removing climate drift caused by a not-yet-equilibrated ocean initial state and find them to be ineffective, judging by the fact that they differ from each other and from the robust results that branched off an equilibrated control. The authors' results suggest that robust twenty-first-century projections of the forced response can be achieved by running climate simulations from an equilibrated ocean state, because memory of the different initial ocean state is lost in about 40 years if the forced run is started from a quasi-equilibrated state.

This paper presents a systematic method for the analysis of photo-induced isotopic fractionation. The physical basis for this fractionation mechanism centers on the fact that isotopic substitution alters the energy levels, molecular symmetries, spin statistical weights and other fundamental molecular properties, producing spectroscopic signatures distinguishable from that of the parent isotopomer. These mass-dependent physical properties are identical to those invoked by Urey to explain stable isotope fractionation in chemical systems subject to thermodynamic equilibrium. Photo-induced isotopic fractionation is a completely general phenomenon and should be observable in virtually all gas phase photochemical systems. Water photo-induced isotopic fractionation has been examined in detail using experimental and theoretical data. These results illustrate the salient features of this fractionation mechanism for molecules possessing continuous UV absorption spectra and unit photodissociation quantum yields. Using the photo-induced isotopic fractionation methodology in conjunction with standard photochemical models, we predict substantial deuterium enrichment of water vapor in the planetary atmospheres of Earth and Mars.

Using reflectivity measurements from the Total Ozone Mapping Spectrometer (TOMS), we show that over the months when stratocumulus clouds are prominent off the Peru Coast, the ultraviolet (UV) reflectance of two marine sites is consistently higher than that of the surroundings. The regions of reflectivity enhancement coincide with large anthropogenic sulfate aerosol emission sources, and the magnitude of the enhancement has a strong seasonal dependence that is related to the seasonal cloud movement. We propose the indirect aerosol effect as a plausible explanation for the reflectivity observations.

This paper shows that N_2O isotopic fractionation in the stratosphere may be understood within the limits of the standard photochemical models if mass-dependent photodissociation rates for the various N_2O isotopomers are incorporated. Thus, we conclude that there is no demonstrable reason to invoke a significant chemical source of N_2O in the middle atmosphere. This paper presents a general theory for isotopomer dependent photodissociation rates that accounts for the isotopic fractionation observed in stratospheric N_2O and how photodissociations appear to be both a source and a sink of N_2O in the middle atmosphere. Photo-induced isotopic fractionation effects (PHIFE), explain the distinct fractionation signatures found for ^(15)N/^(14)N and ^(18)O/^(16)O ratios in both laboratory and remote sensing measurements. Furthermore, PHIFE predicts substantially different isotopic fractionations in the stratosphere for the isotopomers ^(15)N^(14)N^(16)O and ^(14)N^(15)N^(16)O, which have identical molecular weights but different isotopic substitution sites. Modeling results based on this theory suggest that there is no demonstrable reason to invoke a significant chemical source of N_2O in the middle atmosphere and that N_2O multi-isotope correlations should prove a useful measure of stratospheric air parcel history.

We analyze recently published nitrogen and hydrogen isotopic data to constrain the initial volatile abundances on Saturn's giant moon Titan. The nitrogen data are interpreted in terms of a model of non-thermal escape processes that lead to enhancement in the heavier isotope. We show that these data do not, in fact, strongly constrain the abundance of nitrogen present in Titan's early atmosphere, and that a wide range of initial atmospheric masses (all larger than the present value) can yield the measured enhancement. The enrichment in deuterated methane is now much better determined than it was when Pinto et al. (1986. Nature 319, 388-390) first proposed a photochemical mechanism to preferentially retain the deuterium. We develop a simple linear theory to provide a more reliable estimate of the relative dissociation rates of normal and deuterated methane. We utilize the improved data and models to compute initial methane reservoirs consistent with the observed enhancement. The result of this analysis agrees with an independent estimate for the initial methane abundance based solely on the present-day rate of photolysis and an assumption of steady state. This consistency in reservoir size is necessary but not sufficient to infer that methane photolysis has proceeded steadily over the age of the solar system to produce large quantities of less volatile organics. Our analysis indicates an epoch of early atmospheric escape of nitrogen, followed by a later addition of methane by outgassing from the interior. The results also suggest that Titan's volatile inventory came in part or largely from a circum-Saturnian disk of material more reducing than the surrounding solar nebula. Many of the ambiguities inherent in the present analysis can be resolved through Cassini-Huygens data and a program of laboratory studies on isotopic and molecular exchange processes. The value of, and interest in, the Cassini-Huygens data can be greatly enhanced if such a program were undertaken prior to the prime phase of the mission.

In situ measurements of CO were made in the upper troposphere and lower stratosphere (7–21 km altitude) with the Jet Propulsion Laboratory (JPL) Aircraft Laser Infrared Absorption Spectrometer (ALIAS) on 58 flights of the NASA ER-2 aircraft from October 1995 through September 1997, between 90°N and 3°S latitude. Measured upper tropospheric CO was variable and typically ranged between 55 and 115 ppb, except for higher values over Alaska during summer 1997. Tropical stratospheric CO ranged from 58 ± 5 ppb at the tropopause to 12 ± 2 ppb above 20 km, having similar profiles in all seasons of the year. The tropical profile is reproduced by a simple Lagrangian box model of tropical ascent using measured CH4 and OH concentrations, Cl and O(^1D) concentrations from a photochemical model, and diabatic heating rates from a radiative heating model. From measured CO, quasi-horizontal mixing between the tropical and mid-latitude lower stratosphere is inferred to be rapid in the region between 400 K and 450 K potential temperature (altitudes less than 20 km).

To investigate secular changes in CO and CH_4, we examined monthly means of tropospheric measurements made from samples collected at 19 fixed sites in the National Oceanic and Atmospheric Administration (NOAA) Climate Monitoring and Diagnostics Laboratory (CMDL) global cooperative flask sampling network. The CH_4 data are available for the period 1984–1995. A somewhat shorter time series is available for CO (1989–1995). The data were analyzed to extract a consistent pattern of change in time and in latitude. The most important preliminary finding is that the patterns of CO and CH_4 change appear to resemble that of biomass burning. That is, there is maximum change during local spring in both northern and southern hemispheres. If we attribute a significant part of the change in CH_4 trend (3–6 ppb/yr) to biomass burning, the corresponding change in CO is approximately 2–5 ppb/yr. This would explain the bulk of the observed change in CO (4–7 ppb/yr).

Water is predicted to be among, if not the most abundant molecular species after hydrogen in the atmospheres of close-in extrasolar giant planets (hot-Jupiters) Several attempts have been made to detect water on an exoplanet, but have failed to find compelling evidence for it or led to claims that should be taken with caution. Here we report an analysis of recent observations of the hot-Jupiter HD189733b taken during the transit, where the planet passed in front of its parent star. We find that absorption by water vapour is the most likely cause of the wavelength-dependent variations in the effective radius of the planet at the infrared wavelengths 3.6, 5.8 and 8 microns. The larger effective radius observed at visible wavelengths may be due to either star variability or the presence of clouds/hazes. We explain the most recent thermal infrared observations of the planet during secondary transit behind the star, reporting a non-detection of water on HD189733b, as being a consequence of the nearly isothermal vertical profile of the planet.s atmosphere. Our results show that water is detectable on extrasolar planets using the primary transit technique and that the infrared should be a better wavelength region than the visible, for such searches.

Simultaneous in situ measurements of N_2O and CH_4 were made with a tunable diode laser spectrometer (ALIAS II) aboard the Observations from the Middle Stratosphere (OMS) balloon platform from New Mexico, Alaska, and Brazil during 1996 and 1997. We find different compact relationships of CH_4 with N_2O in the tropics and extra-tropics because mixing is slow between these regions. Transport into the extra-tropics from the tropics or the polar vortex leads to deviations from the normal compact relationship. We use measured N_2O and CH_4 and a simple model to quantify entrainment of mid-latitude stratospheric air into the tropics. The entrainment time scale is estimated to be 16 (+17, −8) months for altitudes between 20 and 28 km. The fraction of tropical air entrained from the extra-tropical stratosphere is 50% (+18%, −30%) at 20 km, increasing to 78% (+11%, −19%) at 28 km.

Simultaneous in situ measurements of HCl and ClO have been made for the first time in the southern hemisphere, allowing a systematic study of the processes governing chlorine activation between 15 and 20 km in the 1994 Antarctic winter. Data for several other gases (O_3, NO, NO_y, OH, HO_2, N_(2)O, CH_4, CO, H_(2)O, CFCs), particulates, and meteorological parameters were collected from the ER-2 aircraft out of New Zealand as part of the 1994 Airborne Southern Hemisphere Ozone Experiment/Measurements of Atmospheric Effects of Stratospheric Aircraft (ASHOE/MAESA) campaign. Observations from the ER-2 in the fall (April–May), prior to polar night, show that chlorine activation begins with 60–75% of inorganic chlorine as HCl. By midwinter (July–August), near-total removal of HCl is observed. The wintertime loss of HCl in air recently exposed to extreme temperatures is found to be correlated with high levels of reactive chlorine (ClO and its dimer, Cl_(2)O_2) in the linear fashion expected from the stoichiometry of the heterogeneous reaction of hydrochloric acid with chlorine nitrate on polar stratospheric clouds (PSCs): HCl + ClONO_2 → Cl_2 + HNO_3. To constrain the role of different heterogeneous reactions and PSC types, we have used a photochemical trajectory model which includes heterogeneous sulfate and PSC chemistry. Model calculations of the evolution of reactive gases are compared with the in situ observations. In addition, simultaneous measurements of OH and HO_2 are used as a diagnostic for the occurrence of the heterogeneous reaction HOCl + HCl → Cl_2 + H_(2)O, which contributes to suppressed levels of HO_x inside the vortex. It is shown that the amount of chlorine activation is not strongly dependent on the composition of PSCs. However, HO_x levels exhibit different signatures depending on the type of heterogeneous surfaces that affected chlorine activation. Furthermore, this analysis implies that in the edge region of the Antarctic vortex, the observed near-total removal of HCl can result from latitudinal excursions of air parcels in and out of sunlight during the winter, which photochemically resupply HOCl and ClONO_2 as oxidation partners for HCl.

Due to larger multiple scattering effects in the troposphere compared to that in the stratosphere, the optical path of tropospheric ozone is markedly enhanced (as compared with that of stratospheric ozone) in the Huggins bands from 310 to 345 nm. Model study of the direct and diffuse solar fluxes on the ground shows differences between tropospheric and stratospheric ozone. The characteristic signature of tropospheric ozone enables us to distinguish a change in troposheric ozone from that of stratospheric ozone. A simple retrieval algorithm is used to recover the tropospheric column ozone from simulated data.

A calculation of the A2 sigma --> X2 pi (0, 0) band emission rate factors and line center absorption cross sections of OH applicable to its measurement using solar resonant fluorescence in the terrestrial atmosphere is presented in this paper. The most accurate available line parameters have been used. Special consideration has been given to the solar input flux because of its highly structured Fraunhofer spectrum. The calculation for the OH atmospheric emission rate factor in the solar resonant fluorescent case is described in detail with examples and intermediate results. Results of this calculation of OH emission rate factors for individual rotational lines are on average 30% lower than the values obtained in an earlier work.

Spectra of exoplanet atmospheres provide us the opportunity to improve our understanding of these objects just as remote sensing in our own solar system has increased our understanding of the solar system bodies. The challenge is to quantitatively determine the range of temperatures and species abundances allowed by the data. This challenge is often difficult given the low information content of most exoplanet spectra which commonly leads to degeneracies in the interpretation. A variety of temperature and abundance retrieval approaches have been applied to exoplanet spectra, but no previous investigations have sought to compare these approaches. In this investigation we compare three different retrieval methods: Optimal Estimation, Differential Evolution Markov Chain Monte Carlo, and Bootstrap Monte Carlo. We call our suite of retrieval algorithms the Caltech Inverse Modeling and Retrieval Algorithms (CHIMERA). We discuss what we can expect in terms of uncertainties in abundances and temperatures given current observations as well as potential future observations and what conclusions can be drawn given those uncertainties. In general we find that the three approaches agree for high quality spectra expected to come from potential future spaceborne missions, but disagree for low quality spectra representative of current observations. We also show that the Gaussian posterior probability distribution assumption made in the Optimal Estimation approach is valid for high quality spectral data. We also discuss the implications of our models for the inferred C to O ratios of exoplanetary atmospheres, which of course are important for understanding formation environments. More specifically we show that in the observational limit of a few photometric points, the retrieved C/O is biased towards values near solar and near one simply due to the assumption of uninformative priors., 27 pages, 13 figures

The equilibrium climate sensitivity (ECS) has a large uncertainty range among models participating in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4) and has recently been presented as “inherently unpredictable.” One way to circumvent this problem is to consider the transient climate response (TCR). However, the TCR among AR4 models also differs by more than a factor of 2. The authors argue that the situation may not necessarily be so pessimistic, because much of the intermodel difference may be due to the fact that the models were run with their oceans at various stages of flux adjustment with their atmosphere. This is shown by comparing multimillennium-long runs of the Goddard Institute for Space Studies model, version E, coupled with the Hybrid Coordinate Ocean Model (GISS-EH) and the Community Climate System Model, version 4 (CCSM4) with what were reported to AR4. The long model runs here reveal the range of variability (~30%) in their TCR within the same model with the same ECS. The commonly adopted remedy of subtracting the “climate drift” is ineffective and adds to the variability. The culprit is the natural variability of the control runs, which exists even at quasi equilibration. Fortunately, for simulations with multidecadal time horizon, robust solutions can be obtained by branching off thousand-year-long control runs that reach “quasi equilibration” using a new protocol, which takes advantage of the fact that forced solutions to radiative forcing forget their initial condition after 30–40 yr and instead depend mostly on the trajectory of the radiative forcing.

The hydroxyl radical (OH) plays an important role in middle atmospheric photochemistry, particularly in ozone (O 3 ) chemistry. Because it is mainly produced through photolysis and has a short chemical lifetime, OH is expected to show rapid responses to solar forcing [e.g., the 11-y solar cycle (SC)], resulting in variabilities in related middle atmospheric O 3 chemistry. Here, we present an effort to investigate such OH variability using long-term observations (from space and the surface) and model simulations. Ground-based measurements and data from the Microwave Limb Sounder on the National Aeronautics and Space Administration’s Aura satellite suggest an ∼7–10% decrease in OH column abundance from solar maximum to solar minimum that is highly correlated with changes in total solar irradiance, solar Mg-II index, and Lyman-α index during SC 23. However, model simulations using a commonly accepted solar UV variability parameterization give much smaller OH variability (∼3%). Although this discrepancy could result partially from the limitations in our current understanding of middle atmospheric chemistry, recently published solar spectral irradiance data from the Solar Radiation and Climate Experiment suggest a solar UV variability that is much larger than previously believed. With a solar forcing derived from the Solar Radiation and Climate Experiment data, modeled OH variability (∼6–7%) agrees much better with observations. Model simulations reveal the detailed chemical mechanisms, suggesting that such OH variability and the corresponding catalytic chemistry may dominate the O 3 SC signal in the upper stratosphere. Continuing measurements through SC 24 are required to understand this OH variability and its impacts on O 3 further.

The upper haze (UH) of Venus is variable on the order of days and it is populated by two particle modes. We use a 1D microphysics and vertical transport model based on the Community Aerosol and Radiation Model for Atmospheres to evaluate whether interaction of upwelled cloud particles and sulfuric acid particles nucleated in situ on meteoric dust are able to generate the two size modes and whether their observed variability are due to cloud top vertical transient winds. Nucleation of photochemically produced sulfuric acid onto polysulfur condensation nuclei generates mode 1 cloud droplets that then diffuse upwards into the UH. Droplets generated in the UH from nucleation of sulfuric acid onto meteoric dust coagulate with the upwelled cloud particles and cannot reproduce the observed bimodal size distribution. The mass transport enabled by cloud top transient winds are able to generate a bimodal size distribution in a time scale consistent with observations. Sedimentation and convection in the middle and lower clouds causes the formation of large mode 2 and mode 3 particles. Evaporation of these particles below the clouds creates a local sulfuric acid vapor maximum that causes upwelling of sulfuric acid back into the clouds. If the polysulfur condensation nuclei are small and their production rate is high, coagulation of small droplets onto larger droplets in the middle cloud may result in sulfuric acid "rain" below the clouds once every few Earth months. Reduction of the polysulfur condensation nuclei production rate destroys this oscillation and reduces the mode 1 particle abundance in the middle cloud by two orders of magnitude, though it better reproduces the sulfur-to-sulfuric-acid mass ratio in the cloud and haze droplets. In general we find satisfactory agreement between our results and observations, though improvements could be made by incorporating sulfur microphysics., Comment: 62 pages, 18 figures, 1 table. Accepted for publication in Icarus

Vertical enrichment profiles of stratospheric ^(16)O^(16)O^(18)O and ^(16)O^(18)O^(16)O (hereafter referred to as ^(668)O_3 and ^(686)O_3 respectively) have been derived from space-based solar occultation spectra recorded at 0.01 cm^(−1) resolution by the ATMOS (Atmospheric Trace MOlecule Spectroscopy) Fourier-transform infrared (FTIR) spectrometer. The observations, made during the Spacelab 3 and ATLAS-1, -2, and -3 shuttle missions, cover polar, mid-latitude and tropical regions between 26 to 2.6 mb inclusive (≈ 25 to 41 km). Average enrichments, weighted by molecular ^(48)O_3 density, of (15±6)% were found for ^(668)O_3 and (10±7)% for ^(686)O_3. Defining the mixing ratio of ^(50)O_3 as the sum of those for ^(668)O_3 and ^(686)O_3, an enrichment of (13±5)% was found for ^(50)O_3 (1σ standard deviation). No latitudinal or vertical gradients were found outside this standard deviation. From a series of ground-based measurements by the ATMOS instrument at Table Mountain, California (34.4°N), an average total column ^(668)O_3 enrichment of (17±4)% (1σ standard deviation) was determined, with no significant seasonal variation discernable. Possible biases in the spectral intensities that affect the determination of absolute enrichments are discussed.

Stratospheric mixing ratios of CH_3D from 100 mb to 17 mb (≈ 15 to 28 km) and HDO from 100 mb to 10 mb (≈ 15 to 32 km) have been inferred from high resolution solar occultation infrared spectra from the Atmospheric Trace MOlecule Spectroscopy (ATMOS) Fourier-transform interferometer. The spectra, taken on board the Space Shuttle during the Spacelab 3 and ATLAS-1, -2, and -3 missions, extend in latitude from 70°S to 65°N. We find CH_3D entering the stratosphere at an average mixing ratio of (9.9±0.8) × 10^(−10) with a D/H ratio in methane (7.1±7.4)% less than that in Standard Mean Ocean Water (SMOW) (1σ combined precision and systematic error). In the mid to lower stratosphere, the average lifetime of CH_3D is found to be (1.19±0.02) times that of CH_4, resulting in an increasing D/H ratio in methane as air “ages” and the methane mixing ratio decreases. We find an average of (1.0±0.1) molecules of stratospheric HDO are produced for each CH_3D destroyed (1σ combined precision and systematic error), indicating that the rate of HDO production is approximately equal to the rate of CH_3D destruction. Assuming negligible amounts of deuterium in species other than HDO, CH_3D and HD, this limits the possible change in the stratospheric HD mixing ratio below about 10 mb to be ±0.1 molecules HD created per molecule CH_3D destroyed.