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This paper presents extensive validation analyses of ozone observations from the Atmospheric Chemistry Experiment (ACE) satellite instruments: the ACE Fourier Transform Spectrometer (ACE-FTS) and the Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation (ACE-MAESTRO) instrument. The ACE satellite instruments operate in the mid-infrared and ultraviolet-visible-near-infrared spectral regions using the solar occultation technique. In order to continue the long-standing record of solar occultation measurements from space, a detailed quality assessment is required to evaluate the ACE data and validate their use for scientific purposes. Here we compare the latest ozone data products from ACE-FTS and ACE-MAESTRO with coincident observations from satellite-borne, airborne, balloon-borne and ground-based instruments, by analysing volume mixing ratio profiles and partial column densities. The ACE-FTS version 2.2 Ozone Update product reports more ozone than most correlative measurements from the upper troposphere to the lower mesosphere. At altitude levels from 16 to 44 km, the mean differences range generally between 0 and +10% with a slight but systematic positive bias (typically +5%). At higher altitudes (45-60 km), the ACE-FTS ozone amounts are significantly larger than those of the comparison instruments by up to ~40% (typically +20%). For the ACE-MAESTRO version 1.2 ozone data product, agreement within ±10% (generally better than ±5%) is found between 18 and 40 km for the sunrise and sunset measurements. At higher altitudes (45-55 km), systematic biases of opposite sign are found between the ACE-MAESTRO sunrise and sunset observations. While ozone amounts derived from the ACE-MAESTRO sunrise occultation data are often smaller than the coincident observations (by as much as -10%), the sunset occultation profiles for ACE-MAESTRO show results that are qualitatively similar to ACE-FTS and indicate a large positive bias (+10 to +30%) in this altitude range. In contrast, there is no significant difference in bias found for the ACE-FTS sunrise and sunset measurements. These systematic effects in the ozone profiles retrieved from the measurements of ACE-FTS and ACE-MAESTRO are being investigated. This work shows that the ACE instruments provide reliable, high quality measurements from the tropopause to the upper stratosphere and can be used with confidence in this vertical domain

Hydrogen chloride (HCl) and hydrogen fluoride (HF) are respectively the main chlorine and fluorine reservoirs in the Earth's stratosphere. Their buildup resulted from the intensive use of man-made halogenated source gases, in particular CFC-11 (CCl3F) and CFC-12 (CCl2F2), during the second half of the 20th century. It is important to continue monitoring the evolution of these source gases and reservoirs, in support of the Montreal Protocol and also indirectly of the Kyoto Protocol. The Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) is a space-based instrument that has been performing regular solar occultation measurements of over 30 atmospheric gases since early 2004. In this validation paper, the HCl, HF, CFC-11 and CFC-12 version 2.2 profile data products retrieved from ACE-FTS measurements are evaluated. Volume mixing ratio profiles have been compared to observations made from space by MLS and HALOE, and from stratospheric balloons by SPIRALE, FIRS-2 and Mark-IV. Partial columns derived from the ACE-FTS data were also compared to column measurements from ground-based Fourier transform instruments operated at 12 sites. ACE-FTS data recorded from March 2004 to August 2007 have been used for the comparisons. These data are representative of a variety of atmospheric and chemical situations, with sounded air masses extending from the winter vortex to summer sub-tropical conditions. Typically, the ACE-FTS products are available in the 10–50 km altitude range for HCl and HF, and in the 7–20 and 7–25 km ranges for CFC-11 and -12, respectively. For both reservoirs, comparison results indicate an agreement generally better than 5–10% above 20 km altitude, when accounting for the known offset affecting HALOE measurements of HCl and HF. Larger positive differences are however found for comparisons with single profiles from FIRS-2 and SPIRALE. For CFCs, the few coincident measurements available suggest that the differences probably remain within ±20%.

The Atmospheric Chemistry Experiment (ACE), also known as SCISAT, was launched on 12 August 2003, carrying two instruments that measure vertical profiles of atmospheric constituents using the solar occultation technique. One of these instruments, the ACE Fourier Transform Spectrometer (ACE-FTS), is measuring volume mixing ratio (VMR) profiles of nitrous oxide (N 2 O) from the upper troposphere to the lower mesosphere at a vertical resolution of about 3–4 km. In this study, the quality of the ACE-FTS version 2.2 N 2 O data is assessed through comparisons with coincident measurements made by other satellite, balloon-borne, aircraft, and ground-based instruments. These consist of vertical profile comparisons with the SMR, MLS, and MIPAS satellite instruments, multiple aircraft flights of ASUR, and single balloon flights of SPIRALE and FIRS-2, and partial column comparisons with a network of ground-based Fourier Transform InfraRed spectrometers (FTIRs). Overall, the quality of the ACE-FTS version 2.2 N 2 O VMR profiles is good over the entire altitude range from 5 to 60 km. Between 6 and 30 km, the mean absolute differences for the satellite comparisons lie between -42 ppbv and +17 ppbv, with most within ±20 ppbv. This corresponds to relative deviations from the mean that are within ±15%, except for comparisons with MIPAS near 30 km, for which they are as large as 22.5%. Between 18 and 30 km, the mean absolute differences are generally within ±10 ppbv, again excluding the aircraft and balloon comparisons. From 30 to 60 km, the mean absolute differences are within ±4 ppbv, and are mostly between -2 and +1 ppbv. Given the small N 2 O VMR in this region, the relative deviations from the mean are therefore large at these altitudes, with most suggesting a negative bias in the ACE-FTS data between 30 and 50 km. In the comparisons with the FTIRs, the mean relative differences between the ACE-FTS and FTIR partial columns are within ±6.6% for eleven of the twelve contributing stations. This mean relative difference is negative at ten stations, suggesting a small negative bias in the ACE-FTS partial columns over the altitude regions compared. Excellent correlation ( R =0.964) is observed between the ACE-FTS and FTIR partial columns, with a slope of 1.01 and an intercept of -0.20 on the line fitted to the data.

The Atmospheric Chemistry Experiment (ACE) satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO3, ClONO2, and N2O5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS). This paper describes the ACE-FTS version 2.2 data products, including the N2O5 update, for the three species and presents validation comparisons with available observations. We have compared volume mixing ratio (VMR) profiles of HNO3, ClONO2, and N2O5 with measurements by other satellite instruments (SMR, MLS, MIPAS), aircraft measurements (ASUR), and single balloon-flights (SPIRALE, FIRS-2). Partial columns of HNO3 and ClONO2 were also compared with measurements by ground-based Fourier Transform Infrared (FTIR) spectrometers. Overall the quality of the ACE-FTS v2.2 HNO3 VMR profiles is good from 18 to 35 km. For the statistical satellite comparisons, the mean absolute differences are generally within ±1 ppbv ±20%) from 18 to 35 km. For MIPAS and MLS comparisons only, mean relative differences lie within±10% between 10 and 36 km. ACE-FTS HNO3 partial columns (~15–30 km) show a slight negative bias of −1.3% relative to the ground-based FTIRs at latitudes ranging from 77.8° S–76.5° N. Good agreement between ACE-FTS ClONO2 and MIPAS, using the Institut für Meteorologie und Klimaforschung and Instituto de Astrofísica de Andalucía (IMK-IAA) data processor is seen. Mean absolute differences are typically within ±0.01 ppbv between 16 and 27 km and less than +0.09 ppbv between 27 and 34 km. The ClONO2 partial column comparisons show varying degrees of agreement, depending on the location and the quality of the FTIR measurements. Good agreement was found for the comparisons with the midlatitude Jungfraujoch partial columns for which the mean relative difference is 4.7%. ACE-FTS N2O5 has a low bias relative to MIPAS IMK-IAA, reaching −0.25 ppbv at the altitude of the N2O5 maximum (around 30 km). Mean absolute differences at lower altitudes (16–27 km) are typically −0.05 ppbv for MIPAS nighttime and ±0.02 ppbv for MIPAS daytime measurements.

Altitude profiles of ClONO2 retrieved with the IMK (Institut für Meteorologie und Klimaforschung) science-oriented data processor from MIPAS/Envisat (Michelson Interferometer for Passive Atmospheric Sounding on Envisat) mid-infrared limb emission measurements between July 2002 and March 2004 have been validated by comparison with balloon-borne (Mark IV, FIRS2, MIPAS-B), airborne (MIPAS-STR), ground-based (Spitsbergen, Thule, Kiruna, Harestua, Jungfraujoch, Izaña, Wollongong, Lauder), and spaceborne (ACE-FTS) observations. With few exceptions we found very good agreement between these instruments and MIPAS with no evidence for any bias in most cases and altitude regions. For balloon-borne measurements typical absolute mean differences are below 0.05 ppbv over the whole altitude range from 10 to 39 km. In case of ACE-FTS observations mean differences are below 0.03 ppbv for observations below 26 km. Above this altitude the comparison with ACE-FTS is affected by the photochemically induced diurnal variation of ClONO2. Correction for this by use of a chemical transport model led to an overcompensation of the photochemical effect by up to 0.1 ppbv at altitudes of 30–35 km in case of MIPAS-ACE-FTS comparisons while for the balloon-borne observations no such inconsistency has been detected. The comparison of MIPAS derived total column amounts with ground-based observations revealed no significant bias in the MIPAS data. Mean differences between MIPAS and FTIR column abundances are 0.11±0.12×1014 cm−2 (1.0±1.1%) and −0.09±0.19×1014 cm−2 (−0.8±1.7%), depending on the coincidence criterion applied. χ2 tests have been performed to assess the combined precision estimates of MIPAS and the related instruments. When no exact coincidences were available as in case of MIPAS – FTIR or MIPAS – ACE-FTS comparisons it has been necessary to take into consideration a coincidence error term to account for χ2 deviations. From the resulting χ2 profiles there is no evidence for a systematic over/underestimation of the MIPAS random error analysis.

To characterize the spectrum of Earth viewed as an extrasolar planet, we observed the spatially integrated near-infrared (0.7-2.4 μm) reflection spectrum of Earth via the dark side of the Moon (earthshine). After contributions from the Sun, Moon, and local atmosphere were removed, the resulting spectrum was fitted with a simple model of the reflectivity of Earth. The best model fit is dominated by the reflection spectrum of the atmosphere above medium-altitude water clouds, with lesser contributions from high-altitude ice clouds and from the ground. The spectral features seen are H2O (six strong band structures from 0.7 to 2.0 μm), CO2 (six moderate-strength features from 1.4 to 2.1 μm), O2 (two moderate-strength features at 0.76 and 1.26 μm), and several weak CH4 features. Interpreted as a spectrum of an extrasolar planet, we would confidently conclude that this is a habitable planet, based on the presence of strong water bands. Furthermore, the simultaneous presence of oxygen and methane is a strong indicator of biological activity. We might also conclude that the planet is geologically active, based on the presence of CO2, water, and a dynamic atmosphere (inferred from cirrus clouds, cumulus clouds, and clear-air fractions in our model fit). This suggests that it would be valuable for the Terrestrial Planet Finder-Coronagraph (TPF-C) mission to include near-infrared spectroscopy capability. On the basis of the present work, we suggest that future long-term monitoring of the earthshine would allow us to discern how the globally integrated spectrum changes with planet rotation, cloud cover, and seasons.

We present results of early validation studies using retrieved atmospheric profiles from the Earth Observing System Microwave Limb Sounder (MLS) instrument on the Aura satellite. "Global" results are presented for MLS measurements of atmospheric temperature, ozone, water vapor, hydrogen chloride, nitrous oxide, nitric acid, and carbon monoxide, with a focus on the January-March 2005 time period. These global comparisons are made using long-standing global satellites and meteorological datasets, as well as some measurements from more recently launched satellites. Comparisons of MLS data with measurements from the Ft. Sumner, NM, September 2004 balloon flights are also presented. Overall, good agreement is obtained, often within 5% to 10%, but we point out certain issues to resolve and some larger systematic differences; some artifacts in the first publicly released MLS (version 1.5) dataset are noted. We comment briefly on future plans for validation and software improvements.

This paper describes the status circa 2001, of the HITRAN compilation that comprises the public edition available through 2001. The HITRAN compilation consists of several components useful for radiative transfer calculation codes: high-resolution spectroscopic parameters of molecules in the gas phase, absorption cross-sections for molecules with very dense spectral features, aerosol refractive indices, ultraviolet line-by-line parameters and absorption cross-sections, and associated database management software. The line-by-line portion of the database contains spectroscopic parameters for 38 molecules and their isotopologues and isotopomers suitable for calculating atmospheric transmission and radiance properties. Many more molecular species are presented in the infrared cross-section data than in the previous edition, especially the chlorofluorocarbons and their replacement gases. There is now sufficient representation so that quasi-quantitative simulations can be obtained with the standard radiance codes. In addition to the description and justification of new or modified data that have been incorporated since the last edition of HITRAN (1996), future modifications are indicated for cases considered to have a significant impact on remote-sensing experiments. (C) 2003 Elsevier Ltd. All rights reserved.

We present a photochemical model describing the changes in the isotopic composition of stratospheric water vapor that result from methane oxidation and reactions with O(1D). We then compare model calculations with measurements made with the Smithsonian Astrophysical Observatory far-infrared spectrometer during seven balloon flights that took place between 1989 and 1997. The agreement between the model calculations and measurements establishes the validity of the model and the internal consistency of the data set. Finally, we use the model and measurements together to estimate the mixing ratio and isotopic composition of water vapor entering the stratosphere and find that the average over all flights of the water vapor mixing ratio, δD, δ18O, and δ17O are 3.48±0.15 parts per million by volume, −679±20‰, −128±31‰, and −84±31‰, respectively, where the errors indicate the estimated accuracy.

We develop a series of models of transport in the upper tropical troposphere in order to explain the observed abundance and isotopic composition of stratospheric water vapor. We start with the Rayleigh fractionation process and add the effects of mixing and recirculation of stratospheric air through the upper troposphere. We compare our measurements with model calculations for a range of input parameters and find that the observations are best explained by a model that mixes vapor from roughly 11 km (carried aloft either as condensate or through radiative heating and uplift) with air that has been dehydrated (in a large convective system) to a mixing ratio substantially below the saturation mixing ratio of the mean tropical tropopause. The result is that while most of the moisture comes from convective outflow near 11 km, most of the air in the upper troposphere consists of dehydrated air from convective systems with cloud top temperatures below that of the mean tropical tropopause. We also find that the water vapor mixing ratio in the stratosphere is determined not only by the temperature of the tropical tropopause but also by the relative importance of radiative heating, recirculation of stratospheric air, and deep convection in supplying air to the upper troposphere. Our results show that water vapor isotope ratios are a powerful diagnostic tool for testing the results of general circulation models.

Using recently measured rates for isotopic variants of the ozone formation reaction O + O 2 + M, we derive expressions for the enrichment of symmetric and asymmetric 50 O 3 3 and 49 O 3 in stratospheric ozone and calculate total enrichments of 123‰ and 107‰ for 50 O 3 and 49 O 3 respectively We compare the calculations with measurements made with the Smithsonian Astrophysical Observatory far-infrared spectrometer during seven balloon flights which took place between 1989 and 1997. We find that the calculations are in reasonable agreement with the average observed enrichments of 102 ±43‰ and 73±60‰ for 50 O 3 and 49 O 3 , respectively, where the errors indicate the estimated accuracy; we also find that our measurements are in agreement with other recent stratospheric and tropospheric measurements. Using our measurements of the enrichment of the asymmetric and symmetric forms of 50 O 3 and 49 O 3 , we estimate branching ratios of 0.43±0.03 and 0.46 ± 0.06 for production of the symmetric isotopomer by the reaction of 16 O with 34 O 2 and 33 O 2 , respectively.

The Improved Limb Atmospheric Spectrometer (ILAS), a solar occultation infrared satellite sensor, was launched in August 1996. The ILAS validation balloon campaigns were carried out from Kiruna, Sweden (68°N, 21°E), in February and March 1997 and Fairbanks, Alaska (65°N, 148°W), in April and May 1997. During these campaigns, measurements of nitric acid (HNO3) were made using infrared emission spectrometers (Cold Atmospheric Emission Spectral Radiometer, Michelson Interferometer for Passive Atmospheric Sounding-Balloon-Borne version 2, and farinfrared spectrometer) and infrared solar occultation spectrometers (Limb Profile Monitor of the Atmosphere and Mark IV interferometer). An in situ experiment (Chemiluminescence Detector) measured total reactive nitrogen (NOy,), from which HNO3 mixing ratios in the lower stratosphere were calculated. In addition, an in situ NOy, measurement was also made at 12 km altitude from the Deutsche Luft-und Raumfahrt Falcon aircraft in January 1997. The ILAS version 3.10 HNO3 mixing ratios obtained at the nearest location and averaged ILAS mixing ratios obtained within certain criteria were compared with the balloon data. The precision of the ILAS measurements was estimated from the random differences to be 0.8 parts per billion by volume (ppbv), corresponding to about 35% at 15 km and 10–15% at 20–35 km. While the absolute accuracy estimated from the systematic differences was as good as 0.5 ppbv (5%) at 20 km, the ILAS HNO3 mixing ratios were systematically lower than the balloon values by 1 ppbv (15–20%) at 25–30 km. The error in the altitude registration in the ILAS retrieval algorithm is a possible cause for the negative bias at higher altitudes.

We present remote-sensing measurements of the abundance of nitric acid (HNO3) in the lower and middle stratosphere (between 16 and 40 km) covering the period 1989–1997. The measurements were made with the Smithsonian Astrophysical Observatory Far-Infrared Spectrometer (FIRS-2) under a wide range of aerosol surface area density. We compare our measurements with the results of a photochemical steady state model to test our understanding of the chemistry of HNO3 under a variety of conditions. We find that HNO3 is significantly overestimated by the model at altitudes above 22 km, with the difference increasing with increasing altitude and decreasing aerosol surface area density. The agreement between modeled and measured HNO3 can be improved by either decreasing the rate of OH + NO2 by 35% or by using newly measured rate constants for the reactions OH + NO2 and OH + HNO3, but significant differences remain. We discuss these observations in the context of possible uncertainties in the calculated photolysis rate of HNO3 at wavelengths near 200 nm, uncertainties in the observations, errors caused by the use of constrained steady state models, and possible missing sink reactions for HNO3.

The stratospheric age spectrum is useful both as a diagnostic for testing models of stratospheric transport and as a tool for calculating the response of the stratosphere to changes in tropospheric composition. Although the age spectrum of an individual air parcel is not an observable quantity, it is possible to estimate a zonal mean age spectrum from long-term observations of a conserved tracer with sufficient temporal variability. We have constructed a conserved tracer by combining satellite and balloon-borne observations of water vapor and methane from 1986 to 1998. After discussing the possible roles of tropical sea surface temperatures and the quasi-biennial oscillation in determining stratospheric humidity, we use the observations to estimate the zonal mean age spectrum in the tropics and northern midlatitudes. The estimated age spectrum peaks at progressively greater tag times as the altitude increases above the tropopause, in agreement with model calculations. The mean age of air calculated from the derived age spectrum in the lower stratosphere is in good agreement with ages calculated from measurements of SF 6 , but the satellite record is still too short to calculate reliable ages from the age spectrum in the middle and upper stratosphere.

Balloon-borne observations of concentrations of OH, HO2, H2O, and O3 in the middle and upper stratosphere are used to test our understanding of HOx photochemistry. Assuming our photochemical model is complete, the measured [OH] and [HO2] above 38 km (where HOx partitioning is no longer dependent on [NO]) are modeled best by calculations that use a 25% reduction in the ratio of the reaction rate constants for O+HO2 and O+OH as well as either a 25% reduction of the rate constant of OH+HO2 (the primary HOx sink) or a 25% increase in HOx production. All of these changes are consistent with the uncertainties in the recommended rate constants. The kinetic parameters required to explain our observations of [OH] and [HO2] do not lead to a resolution of the long-standing “ozone deficit problem” above 45 km.

Since its first publication in 1973, the HITRAN molecular spectroscopic database has been recognized as the international standard for providing the necessary fundamental spectroscopic parameters for diverse atmospheric and laboratory transmission and radiance calculations. There have been periodic editions of HITRAN over the past decades as the database has been expanded and improved with respect to the molecular species and spectral range covered, the number of parameters included, and the accuracy of this information. The 1996 edition not only includes the customary line-by-line transition parameters familiar to HITRAN users, but also cross-section data, aerosol indices of refraction, software to filter and manipulate the data, and documentation. This paper describes the data and features that have been added or replaced since the previous edition of HITRAN. We also cite instances of critical data that are forthcoming.

The first simultaneous measurements of HO(x), NO(x), and Cl(x) radicals in the middle stratosphere show that NO(x) catalytic cycles dominate loss of ozone (O3) for altitudes between 24 and 38 km; Cl(x) catalytic cycles are measured to be less effective than previously expected; and there is no 'ozone deficit' in the photochemically dominated altitude range from 31 and 38 km, contrary to some previous theoretical studies.

The Halogen Occultation Experiment (HALOE) on UARS uses the method of solar occultation limb sounding to measure the composition and structure of the stratosphere and mesosphere. One of the HALOE channels is spectrally centered at 3.4 μm to measure the vertical profile and global distribution of hydrogen chloride. The mean difference between HALOE and 14 balloon correlative underflight measurements ranges from 8% to 19% throughout most of the stratosphere. This difference is within the limits of error bar overlap for the two data sets. The mean differences between HALOE and HCl data from ATMOS flights on the space shuttle is of the order of 15 to 20% for the 1992 flight and 10% for the 1993 flight. Generally, HALOE results tend to be low in these comparisons. Also, comparisons with two-dimensional model calculations and HALOE data are in good qualitative agreement regarding vertical profile shapes and features in a pressure versus latitude cross section. HCl values increase from ∼0.3 parts per billion by volume (ppbv) to 1 ppbv in the lower stratosphere to 2.6 ppbv to 3.3 ppbv just above the stratopause which is the upper limit of HALOE single-profile measurements. There is a dependence of HCl results on the angle between the orbit plane and the Earth-Sun vector with HCl varying by ±9% in the upper stratosphere. This variation appears to be altitude dependent and it is not discernible in the data below about 10 mbar.

The cryogenic limb array etalon spectrometer (CLAES) aboard UARS made near-global measurements of HNO3 and 388 days from January 9, 1992, to April 25, 1993, have been processed to data version 7 (V7). Results from UARS instruments, including CLAES, the improved stratospheric and mesospheric sounder, and the microwave limb sounder, provide the first near-global documentation of the evolution of denitrification in the Antarctic 1992 winter and spring vortex. We provide a description of the CLAES HNO3 V7 quality that includes comparisons with correlative measurements to assess overall quality, accuracy, and precision. Correlative profiles of volume mixing ratio (vmr) included those obtained by the space shuttle deployed ATMOS in two missions, March–April 1992 and April 1993, data from a variety of balloon-borne instruments at midlatitude (11 profiles), and in high-latitude northern winter (six profiles), and LIMS data. In general, the CLAES V7 HNO3 maximum values of vmr were of the order of 6–15% less than correlative for CLAES values ≤8 parts per billion by volume (ppbv). However, when CLAES peak vmr values were 10 to 13 ppbv, then CLAES values exceeded correlative by 0–7%. The comparisons were within the combined instrumental error estimates, or observed measurement variability, for the large majority of comparisons. As discussed, the retrieval of future versions will utilize updated spectral parameters and will also correct for a small uncompensated drift in radiometric calibration that occurred in the latter part of the mission. This is expected to improve the comparisons in the ≤8 ppbv range, perhaps at the expense of those in the ≥8 ppbv range. The data obtained January 9 to April 15, 1992, in comparison with data obtained January 9 to April 15, 1993, reveal strikingly evident 1-year period deseasonalized trends on a global basis. These trends agree quantitatively with available correlative data suitable for trend analysis. These include ATMOS in the southern midlatitudes and published long-term time series of HNO3 column obtained at 45°S and 20°N. These trends reveal a large decrease in the southern hemisphere and small increases in the northern hemisphere, such that the global average is toward a decrease. The global average decrease we attribute to the diminishing influence of heterogeneous conversion of N2O5 to HNO3 as the Pinatubo aerosol settles out during this time period, and the HNO3 recovers toward pre-Pinatubo conditions. We establish plausibility that the small increases in the north are due to hemispherically asymmetric QBO-like effects that are strong in the northern hemisphere and weak in the southern hemisphere and are phased to produce an increase in HNO3 over the 1-year time period of just the right magnitude to more than offset decrease due to settling out of the Pinatubo aerosol. Based on this study, our range of confidence in the CLAES HNO3 V7 product is from 70 to 3 mbar, in comparison with correlative data, and the precision on this range is of the order of 0.3–1.0 ppbv. This precision was derived from data repeatability and agrees within a factor of 2 or better with estimates based on instrument characterization and with error estimates embedded within the V7 data.

We report simultaneous measurements of the stratospheric concentration profiles of OH, HO2, H2O2, H2O, O3, HNO3, NO2, N2O, HCl, HOCl, and ClO during a midlatitude balloon flight in 1989. Measurements were made over almost an entire diurnal cycle by the Smithsonian Astrophysical Observatory Far-Infrared Spectrometer (FIRS-2) and the Jet Propulsion Laboratory Balloon Microwave Limb Sounder (BMLS). We analyze these measurements using a photochemical model constrained by observations of long-lived gases. Measured HOx species (OH and HO2) and H2O2 show fair agreement with theory throughout the diurnal cycle. Measurements of HNO3 are higher than theory near the concentration peak, while the levels of NO2 are consistent with the model at most altitudes. Measurements of ClO and HOCl are less than predicted concentrations, suggesting a source of HCl in addition to the reaction of Cl with CH4. Possibilities for such a source include a minor HCl + O2 product channel for the reaction of ClO with OH and a minor HCl + O3 channel for the reaction of ClO with HO2.

We measured column abundances of HF, HCl, O3, HNO3, and H2O on the NASA DC-8 during the AASE II campaign, using thermal emission spectroscopy. We made multiple traversals of the Arctic vortex and surroundings. Using HF as a tracer, we remove the effects of subsidence from the measured column abundances; perturbations in the resulting column abundances are attributed to chemical processing. We find that by January 1992 the stratospheric column in the vortex had been chemically depleted by about (55+/-10)% in HCl and (35+/-10)% in O3, and enhanced by about (15+/-10)% in HNO3 and (0+/-10)% in H2O.

Three Fourier transform infrared (FTIR) spectromenters were based on board the NASA DC-8 during the second Airborne Arctic Stratospheric Expedition (AASE II) in 1992. Two FTIRs used solar absorption and one used thermal emission. We compare over 2000 measurements from these 3 FTIRs, on 12 DC-8 flights, for closely coincident air masses and times, both inside and outside the polar vortex. In the majority of cases the offset biases are quite small, in the range 1-4%, and comparable to the absolute precisions expected. In most cases the rms scatter is in the range 4-11%; this scatter is unlikely to be geophysical, but rather is probably instrumental or analytical in origin.

The Smithsonian Astrophysical Observatory (SAO) maintains a molecular line database (the SAO line database) for analysis of atmospheric spectra in the far i.r. and longer-wave mid i.r., from 10-800 cm -1 . This database combines the best currently available line parameters, including the HITRAN 1.2 molecular database, the JPL submillimeter, millimeter, and microwave spectral line catalog 3 (JPLSMM), and other available measurements and calculations. The current version of the database contains 154.895 lines from H 2 O, CO 2 , O 3 , N 2 O, CO, CH 4 , O 2 (including the 1 Δ state), NO, SO 2 , NO 2 , NH 3 , HNO 3 , OH, HF, HCl, HBr, HI, ClO, OCS, H 2 CO, HOCl, HCN, H 2 O 2 , O( 3 P ), and HO 2 . The database is available in both HITRAN-type 80 character (SAO92) and 100 character (SAO92A) formats. 1. L.S. Rothman, R.R. Gamache, A. Goldman, L.R. Brown, R.A. Toth, H.M. Pickett, R.L. Poynter, J.-M. Flaud, C. Camy-Peyret, A. Barbe, N. Husson, C.P. Rinsland, and M.A.H. Smith, Appl. Opt. 26 , 4058 (1987). 2. L.S. Rothman, R.R. Gamache, R.H. Tipping, C.P. Rinsland, M.A.H. Smith, D. Chris Benner, V. Malathy Devi, J.-M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S.T. Massie, L.R. Brown, and R.A. Toth, JQSRT . 48 , 469 (1992). 3. R.L. Poynter and H.M. Pickett, Submillimeter millimeter and microwave spectral line catalog, Publ. 80-23, revision 2, Jet Propulsion Laboratory, Pasadena, CA (1984).

[1] The Tropical Composition, Cloud and Climate Coupling Experiment (TC4), was based in Costa Rica and Panama during July and August 2007. The NASA ER-2, DC-8, and WB-57F aircraft flew 26 science flights during TC4. The ER-2 employed 11 instruments as a remote sampling platform and satellite surrogate. The WB-57F used 25 instruments for in situ chemical and microphysical sampling in the tropical tropopause layer (TTL). The DC-8 used 25 instruments to sample boundary layer properties, as well as the radiation, chemistry, and microphysics of the TTL. TC4 also had numerous sonde launches, two ground-based radars, and a ground-based chemical and microphysical sampling site. The major goal of TC4 was to better understand the role that the TTL plays in the Earth's climate and atmospheric chemistry by combining in situ and remotely sensed data from the ground, balloons, and aircraft with data from NASA satellites. Significant progress was made in understanding the microphysical and radiative properties of anvils and thin cirrus. Numerous measurements were made of the humidity and chemistry of the tropical atmosphere from the boundary layer to the lower stratosphere. Insight was also gained into convective transport between the ground and the TTL, and into transport mechanisms across the TTL. New methods were refined and extended to all the NASA aircraft for real-time location relative to meteorological features. The ability to change flight patterns in response to aircraft observations relayed to the ground allowed the three aircraft to target phenomena of interest in an efficient, well-coordinated manner.

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An upper limit is measured for stratospheric HBr from three balloon flights. The observations were made with the FIRS-2 far-infrared Fourier transform spectrometer. The 1sigma upper limits from the 1988, 1989, and 1990 balloon flights are 13 pptv at 35 km, 7 pptv at 32 km, and 3 pptv at 31 km, respectively. Combining all 3 flights, the weighted average 1sigma upper limit for HBr is 4 pptv at 32 km. This value is significantly smaller than the only other previously published spectroscopic value of 20 +/- 7 pptv (2sigma), but is consistent with a theoretical estimate which predicts roughly 0.4 pptv at this altitude.

The first unequivocal measurement of hydrogen peroxide in the stratosphere have been made, a concentration profile obtained from a balloon platform using Fourier transform thermal emission spectroscopy in the far infrared. Measurements were made using the 112/cm R-Q5 branch of the rotational-torsional spectrum, with some confirmation from the 94/cm R-Q4 branch. The volume mixing ratio of H2O2 is 1.6 x 10 to the -10th at 38.4 km, decreasing to 0.6 x 10 to the -10th at 23.8 km, with uncertainties of about 16 percent. These measurements are compared to a recent stratospheric model calculation.

The magnetic dipole-allowed spin-rotation lines of O2 potentially can be used for pointing calibration and confirmation of float altitude for far infrared spectra of the stratosphere obtained from balloon platforms. We demonstrate that current deficiencies in the spectroscopic database, particularly the air pressure-broadening coefficients, severely limit the capability of deriving useful pointing calibrations, and that precise pressure-broadening measurements for the transitions actually used in calibration are needed to improve this capability.

The first seasonal and interannual validation of OH measurements from the Aura Microwave Limb Sounder (MLS) has been conducted using ground-based OH column measurements from the Fourier Transform Ultra-Violet Spectrometer (FTUVS) over the Jet Propulsion Laboratory's Table Mountain Facility (TMF) during 2004–2007. To compare with FTUVS total column measurements, MLS OH vertical profiles over TMF are integrated to obtain partial OH columns above 21.5 hPa, which covers nearly 90% of the total column. The tropospheric OH and the lower stratopheric OH not measured by MLS are estimated using GEOS (Goddard Earth Observing System)-Chem and a Harvard 2-D model implemented within GEOS-Chem, respectively. A number of field observations and calculations from a photochemical box model are compared to OH profiles from these models to estimate the variability in the lower atmospheric OH and thus the uncertainty in the combined total OH columns from MLS and models. In general, the combined total OH columns agree extremely well with TMF total OH columns, especially during seasons with high OH. In winter with low OH, the combined columns are often higher than TMF measurements. A slightly weaker seasonal variation is observed by MLS relative to TMF. OH columns from TMF and the combined total columns from MLS and models are highly correlated, resulting in a mean slope of 0.969 with a statistically insignificant intercept. This study therefore suggests that column abundances derived from MLS vertical profiles have been validated to within the mutual systematic uncertainties of the MLS and FTUVS measurements.

In January 2007, the National Research Council (NRC) released the first decadal survey addressing Earth science entitled "Earth Science and Applications from Space: National Imperatives for the Next Decade and Beyond". The study, initiated in 2004, conducted a decadal survey to generate consensus recommendations from the Earth and environmental science and applications communities regarding a systems approach to the space-based and ancillary observations encompassing the research programs of NASA, the related operational programs of the National Oceanic and Atmospheric Administration (NOAA), and associated programs, such as Landsat, a joint initiative of the U.S. Geological Survey (USGS) and NASA. Among its many recommendations, were that NOAA and NASA should undertake a set of 17 missions, phased over the next decade in three year groupings. Of these 17 missions, 15 were designated to NASA. The four NASA Phase 1 missions are currently in Pre-Phase A study at different levels of development with SMAP, a soil moisture monitoring mission, targeting a launch date of 2013 and ICESat-II, intended to continue the record initiated by ICESat-I to monitor ice sheet height changes for climate change diagnosis, targeting a launch date of 2015. The CLARREO solar and earth radiation monitoring mission and the DESDynI Earth surface and ice deformation monitoring mission are preparing to enter Pre-Phase A in 2009. The five NASA Phase 2 missions are: SWOT, a wide swath altimeter mission measuring ocean, lake, and river water levels; HyspIRI, a hyperspectral mission for measuring land surface composition for agriculture and mineral characterization and vegetation types for ecosystem health; ASCENDS, a day/night, all-latitude, all-season CO2 column measuring mission; ACE, an aerosol and cloud profiling mission for climate and water cycle research with an ocean color measuring capability for open ocean biogeochemistry; and GEO-CAPE, a geostationary mission for measuring atmospheric gas columns for air quality forecasts and ocean color for coastal ecosystem health and climate emissions. Risk reduction and concept maturity studies are underway for these Phase 2 missions with the goal to improve their understanding and scope to enable the Earth Science Division (ESD) to make programmatic decisions for FY10 and beyond. An overview of their science requirements, system concept, technology readiness, and study status will be provided.

We calculate the expected signal-to-noise ratio (SNR) for spectral features in the transit spectrum of an Earth-like exoplanet, for the case of the nearest likely transit of a G and an M star, for a 6-m telescope in space. We find that the SNR values for all important spectral features, in the visible and infrared, are in the range 0.2 to 1.1, making the detection of such features difficult.

The Earth Observing System (EOS) Microwave Limb Sounder (MLS) aboard the Aura satellite has provided daily global HCl profiles since August 2004. We provide a characterization of the resolution, random and systematic uncertainties, and known issues for the version 2.2 MLS HCl data. The MLS sampling allows for comparisons with many (similar to 1500 to more than 3000) closely matched profiles from the Halogen Occultation Experiment (HALOE) and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). These data sets provide HCl latitudinal distributions that are, overall, very similar to those from (coincident) MLS profiles, although there are some discrepancies in the upper stratosphere between the MLS and HALOE gradients. As found in previous work, MLS and ACE HCl profiles agree very well (within similar to 5%, on average), but the MLS HCl abundances are generally larger (by 10-20%) than HALOE HCl. The bias versus HALOE is unlikely to arise mostly from MLS, as a similar systematic bias (of order 15%) is not observed between average MLS and balloon-borne measurements of HCl, obtained over Fort Sumner, New Mexico, in 2004 and 2005. At the largest pressure (147 hPa) for MLS HCl, a high bias (similar to 0.2 ppbv) is apparent in analyses of low to midlatitude data versus in situ aircraft chemical ionization mass spectrometry (CIMS) HCl measurements from the Aura Validation Experiment (AVE) campaigns in 2004, 2005, and 2006; this bias is also observed in comparisons of MLS and aircraft HCl/O-3 correlations. Good agreement between MLS and CIMS HCl is obtained at 100 to 68 hPa. The recommended pressure range for MLS HCl is from 100 to 0.15 hPa.

[1] The Earth Observing System (EOS) Microwave Limb Sounder (MLS) aboard the Aura satellite has provided essentially daily global measurements of ozone (O3) profiles from the upper troposphere to the upper mesosphere since August of 2004. This paper focuses on validation of the MLS stratospheric standard ozone product and its uncertainties, as obtained from the 240 GHz radiometer measurements, with a few results concerning mesospheric ozone. We compare average differences and scatter from matched MLS version 2.2 profiles and coincident ozone profiles from other satellite instruments, as well as from aircraft lidar measurements taken during Aura Validation Experiment (AVE) campaigns. Ozone comparisons are also made between MLS and balloon-borne remote and in situ sensors. We provide a detailed characterization of random and systematic uncertainties for MLS ozone. We typically find better agreement in the comparisons using MLS version 2.2 ozone than the version 1.5 data. The agreement and the MLS uncertainty estimates in the stratosphere are often of the order of 5%, with values closer to 10% (and occasionally 20%) at the lowest stratospheric altitudes, where small positive MLS biases can be found. There is very good agreement in the latitudinal distributions obtained from MLS and from coincident profiles from other satellite instruments, as well as from aircraft lidar data along the MLS track.

The Atmospheric Chemistry Experiment (ACE) satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO3, ClONO2, and N2O5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS). This paper describes the ACE-FTS version 2.2 data products, including the N2O5 update, for the three species and presents validation comparisons with available observations. We have compared volume mixing ratio (VMR) profiles of HNO3, ClONO2, and N2O5 with measurements by other satellite instruments (SMR, MLS, MIPAS), aircraft measurements (ASUR), and single balloon-flights (SPIRALE, FIRS-2). Partial columns of HNO3 and ClONO2 were also compared with measurements by ground-based Fourier Transform Infrared (FTIR) spectrometers. Overall the quality of the ACE-FTS v2.2 HNO3 VMR profiles is good from 18 to 35 km. For the statistical satellite comparisons, the mean absolute differences are generally within ±1 ppbv (±20%) from 18 to 35 km. For MIPAS and MLS comparisons only, mean relative differences lie within ±10% between 10 and 36 km. ACE-FTS HNO3 partial columns (~15–30 km) show a slight negative bias of −1.3% relative to the ground-based FTIRs at latitudes ranging from 77.8° S–76.5° N. Good agreement between ACE-FTS ClONO2 and MIPAS, using the Institut für Meteorologie und Klimaforschung and Instituto de Astrofísica de Andalucía (IMK-IAA) data processor is seen. Mean absolute differences are typically within ±0.01 ppbv between 16 and 27 km and less than +0.09 ppbv between 27 and 34 km. The ClONO2 partial column comparisons show varying degrees of agreement, depending on the location and the quality of the FTIR measurements. Good agreement was found for the comparisons with the midlatitude Jungfraujoch partial columns for which the mean relative difference is 4.7%. ACE-FTS N2O5 has a low bias relative to MIPAS IMK-IAA, reaching −0.25 ppbv at the altitude of the N2O5 maximum (around 30 km). Mean absolute differences at lower altitudes (16–27 km) are typically −0.05 ppbv for MIPAS nighttime and ±0.02 ppbv for MIPAS daytime measurements.

Validation of stratospheric BrO vertical profiles obtained by the Microwave Limb Sounder (MLS) on the Aura satellite is discussed. MLS BrO measurements are compared with expectations of its latitudinal and seasonal dependence, as well as with more localized balloon-borne measurements of BrO. We describe the expected precision and systematic errors of the version 2.2 retrieval and show that scientific studies using MLS BrO vertical profiles require extensive averaging to increase the signal-to-noise ratio to useful values. A monthly zonal mean over a 10° latitude bin (about 3,000 individual profiles) results in a precision of approximately ±4 ppt (〜25% of a typical daytime signal). Moreover, it is necessary to take day/night differences to remove large biases. The pressure range over which the data are considered useful is 10 to 3.2 hPa. Over this range, the estimated accuracy in the day/night difference is about ±20%. The vertical resolution is 5.5 km for 10 to 3.2 hPa. Day/night differences are a good measure of daytime BrO from 10 to 4.6 hPa; for 3.2 hPa the nonnegligible nighttime BrO needs to be accounted for. We infer total inorganic bromine (Bry) to be 22.1 ± 5.5 ppt on the basis of analysis of MLS measurements of BrO, which implies a contribution of 6.5 ± 5.5 ppt to stratospheric bromine from sources other than long-lived CH3Br and halons

[1] The quality of the version 2.2 (v2.2) middle atmosphere water vapor and nitrous oxide measurements from the Microwave Limb Sounder (MLS) on the Earth Observing System (EOS) Aura satellite is assessed. The impacts of the various sources of systematic error are estimated by a comprehensive set of retrieval simulations. Comparisons with correlative data sets from ground-based, balloon and satellite platforms operating in the UV/visible, infrared and microwave regions of the spectrum are performed. Precision estimates are also validated, and recommendations are given on the data usage. The v2.2 H2O data have been improved over v1.5 by providing higher vertical resolution in the lower stratosphere and better precision above the stratopause. The single-profile precision is � 0.2–0.3 ppmv (4–9%), and the vertical resolution is � 3–4 km in the stratosphere. The precision and vertical resolution become worse with increasing height above the stratopause. Over the pressure range 0.1–0.01 hPa the precision degrades from 0.4 to 1.1 ppmv (6–34%), and the vertical resolution degrades to � 12–16 km. The accuracy is estimated to be 0.2–0.5 ppmv (4–11%) for the pressure range 68–0.01 hPa. The scientifically useful range of the H2O data is from 316 to 0.002 hPa, although only the 82–0.002 hPa pressure range is validated here. Substantial improvement has been achieved in the v2.2 N2O data over v1.5 by reducing a significant low bias in the stratosphere and eliminating unrealistically high biased mixing ratios in the polar regions. The single-profile precision is � 13–25 ppbv (7–38%), the vertical resolution is � 4–6 km and the accuracy is estimated to be 3–70 ppbv (9–25%) for the pressure range 100–4.6 hPa. The scientifically useful range of the N2O data is from 100 to 1 hPa.

Vertical profiles of stratospheric HOCl calculated with a diurnal steady-state photochemical model that uses currently recommended reaction rates and photolysis cross sections underestimate observed profiles of HOCl obtained by two balloon-borne instruments, FIRS-2 (a far-infrared emission spectrometer) and MkIV (a mid-infrared, solar absorption spectrometer). Considerable uncertainty (a factor of two) persists in laboratory measurements of the rate constant (k(sub 1)) for the reaction ClO + HO2 yields HOCl + O2. Agreement between modeled and measured HOCl can be attained using a value of k(sub 1) from Stimpfle et al. (1979) that is about a factor-of-two faster than the currently recommended rate constant. Comparison of modeled and measured HOCl suggests that models using the currently recommended value for k(sub 1) may underestimate the role of the HOCl catalytic cycle for ozone depletion, important in the midlatitude lower stratosphere.

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), on-board the European ENVIronmental SATellite (ENVISAT) launched on 1 March 2002, is a middle infrared Fourier Transform spectrometer measuring the atmospheric emission spectrum in limb sounding geometry. The instrument is capable to retrieve the vertical distribution of temperature and trace gases, aiming at the study of climate and atmospheric chemistry and dynamics, and at applications to data assimilation and weather forecasting. MIPAS operated in its standard observation mode for approximately two years, from July 2002 to March 2004, with scans performed at nominal spectral resolution of 0.025 cm−1 and covering the altitude range from the mesosphere to the upper troposphere with relatively high vertical resolution (about 3 km in the stratosphere). Only reduced spectral resolution measurements have been performed subsequently. MIPAS data were re-processed by ESA using updated versions of the Instrument Processing Facility (IPF v4.61 and v4.62) and provided a complete set of level-2 operational products (geo-located vertical profiles of temperature and volume mixing ratio of H2O, O3, HNO3, CH4, N2O and NO2) with quasi continuous and global coverage in the period of MIPAS full spectral resolution mission. In this paper, we report a detailed description of the validation of MIPAS-ENVISAT operational ozone data, that was based on the comparison between MIPAS v4.61 (and, to a lesser extent, v4.62) O3 VMR profiles and a comprehensive set of correlative data, including observations from ozone sondes, ground-based lidar, FTIR and microwave radiometers, remote-sensing and in situ instruments on-board stratospheric aircraft and balloons, concurrent satellite sensors and ozone fields assimilated by the European Center for Medium-range Weather Forecasting. A coordinated effort was carried out, using common criteria for the selection of individual validation data sets, and similar methods for the comparisons. This enabled merging the individual results from a variety of independent reference measurements of proven quality (i.e. well characterized error budget) into an overall evaluation of MIPAS O3 data quality, having both statistical strength and the widest spatial and temporal coverage. Collocated measurements from ozone sondes and ground-based lidar and microwave radiometers of the Network for the Detection Atmospheric Composition Change (NDACC) were selected to carry out comparisons with time series of MIPAS O3 partial columns and to identify groups of stations and time periods with a uniform pattern of ozone differences, that were subsequently used for a vertically resolved statistical analysis. The results of the comparison are classified according to synoptic and regional systems and to altitude intervals, showing a generally good agreement within the comparison error bars in the upper and middle stratosphere. Significant differences emerge in the lower stratosphere and are only partly explained by the larger contributions of horizontal and vertical smoothing differences and of collocation errors to the total uncertainty. Further results obtained from a purely statistical analysis of the same data set from NDACC ground-based lidar stations, as well as from additional ozone soundings at middle latitudes and from NDACC ground-based FTIR measurements, confirm the validity of MIPAS O3 profiles down to the lower stratosphere, with evidence of larger discrepancies at the lowest altitudes. The validation against O3 VMR profiles using collocated observations performed by other satellite sensors (SAGE II, POAM III, ODIN-SMR, ACE-FTS, HALOE, GOME) and ECMWF assimilated ozone fields leads to consistent results, that are to a great extent compatible with those obtained from the comparison with ground-based measurements. Excellent agreement in the full vertical range of the comparison is shown with respect to collocated ozone data from stratospheric aircraft and balloon instruments, that was mostly obtained in very good spatial and temporal coincidence with MIPAS scans. This might suggest that the larger differences observed in the upper troposphere and lowermost stratosphere with respect to collocated ground-based and satellite O3 data are only partly due to a degradation of MIPAS data quality. They should be rather largely ascribed to the natural variability of these altitude regions and to other components of the comparison errors. By combining the results of this large number of validation data sets we derived a general assessment of MIPAS v4.61 and v4.62 ozone data quality. A clear indication of the validity of MIPAS O3 vertical profiles is obtained for most of the stratosphere, where the mean relative difference with the individual correlative data sets is always lower than ±10%. Furthermore, these differences always fall within the combined systematic error (from 1 hPa to 50 hPa) and the standard deviation is fully consistent with the random error of the comparison (from 1 hPa to ~30–40 hPa). A degradation in the quality of the agreement is generally observed in the lower stratosphere and upper troposphere, with biases up to 25% at 100 hPa and standard deviation of the global mean differences up to three times larger than the combined random error in the range 50–100 hPa. The larger differences observed at the bottom end of MIPAS retrieved profiles can be associated, as already noticed, to the effects of stronger atmospheric gradients in the UTLS that are perceived differently by the various measurement techniques. However, further components that may degrade the results of the comparison at lower altitudes can be identified as potentially including cloud contamination, which is likely not to have been fully filtered using the current settings of the MIPAS cloud detection algorithm, and in the linear approximation of the forward model that was used for the a priori estimate of systematic error components. The latter, when affecting systematic contributions with a random variability over the spatial and temporal scales of global averages, might result in an underestimation of the random error of the comparison and add up to other error sources, such as the possible underestimates of the p and T error propagation based on the assumption of a 1 K and 2% uncertainties, respectively, on MIPAS temperature and pressure retrievals. At pressure lower than 1 hPa, only a small fraction of the selected validation data set provides correlative ozone data of adequate quality and it is difficult to derive quantitative conclusions about the performance of MIPAS O3 retrieval for the topmost layers.

The FIRST project shows the capabilities of an imaging FTS that covers the important long wavelength portion of the OLR. Here we describe the motivation behind the project, the prototype initial instrument, and results.

simultaneouslyboth in day and night [Waters et al., submitted]. Furtherdetails on the THz module and the OH measurementand calibration are given in Pickett [submitted]. Earlyvalidation of other molecules measured by MLS are givenin Froidevaux et al. [submitted]. The retrieval softwareversion used in this paper is 1.51.The BOH and FIRS-2 instruments were launched on acommon balloon gondola on September 23, 2004, from Ft.Sumner, NM (latitude = 34.5

We present first light spectra from the new Far-Infrared Spectroscopy of the Troposphere (FIRST) instrument. FIRST is a Fourier Transform Spectrometer developed to measure accurately the far-infrared (15 to 100 micrometers; 650 to 100 wavenumbers) emission spectrum of the Earth and its atmosphere. The observations presented here were obtained during a high altitude balloon flight from Ft. Sumner, New Mexico on 7 June 2005. The flight data demonstrate the instrument's ability to observe the entire energetically significant infrared emission spectrum (50 to 2000 wavenumbers) at high spectral and spatial resolution on a single focal plane in an instrument with one broad spectral bandpass beamsplitter. Comparisons with radiative transfer calculations demonstrate that FIRST accurately observes the very fine spectral structure in the far-infrared. Comparisons of the atmospheric window radiances measured by FIRST and by instruments on the NASA Aqua satellite that overflew FIRST are in excellent agreement. FIRST opens a new window on the spectrum that can be used for studying atmospheric radiation and climate, cirrus clouds, and water vapor in the upper troposphere.

The radiative balance of the troposphere, and hence global climate, is dominated by the infrared absorption and emission of water vapor, particularly at far-infrared (far-IR) wavelengths from 15-50 μm. Current and planned satellites observe the infrared region to about 15.4 μm, ignoring spectral measurement of the far-IR region from 15 to 100μm. The far-infrared spectroscopy of the troposphere (FIRST) project, flown in June 2005, provided a balloon-based demonstration of the two key technologies required for a space-based far-IR spectral sensor. We discuss the FIRST Fourier transform spectrometer system (0.6 cm -1 unapodized resolution), its radiometric calibration in the spectral range from 10 to 100 μm, and its performance and science data from the flight. Two primary and two secondary goals are given and data presented to show the goals were achieved by the FIRST flight.

[1] Observations of OH and HO2 from Aura MLS for four seasons and diurnal profiles from the FIRS-2 balloon instrument for Fall 2004 are compared with photochemical model simulations testing three sets of kinetics parameters. MLS and FIRS-2 OH profiles, between 25–60 km, are lower than model results using standard kinetics. Use of a faster, previously published rate constant for O+OH leads to better agreement with MLS and FIRS-2 profiles of OH. A 20% increase in the rate of HO2+OH and the faster rate for O+OH results in improved overall agreement with observations of OH, HO2, HOx, and HO2/OH. Since the MLS and FIRS-2 observations of HOx are reasonably well described by these models, they are therefore not consistent with the previously reported HOx dilemma. However, all models considered here result in calculated odd oxygen loss exceeding production, consistent with the long standing ozone deficit problem.

We have developed a characterization of the geological evolution of the Earths atmosphere and surface in order to model the observable spectra of an Earth-like planet through its geological history. These calculations are designed to guide the interpretation of an observed spectrum of such a planet by future instruments that will characterize exoplanets. Our models focus on spectral features that either imply habitability or are required for habitability. These features are generated by H2O, CO2, CH4, O2, O3, N2O, and vegetation-like surface albedos. We chose six geological epochs to characterize. These epochs exhibit a wide range in abundance for these molecules, ranging from a CO2 rich early atmosphere, to a CO2/CH4-rich atmosphere around 2 billion years ago to a present-day atmosphere. We analyzed the spectra to quantify the strength of each important spectral feature in both the visible and thermal infrared spectral regions, and the resolutions required to unambiguously observe the features for each epoch. We find a wide range of spectral resolutions required for observing the different features. For example, H2O and O3 can be observed with relatively low resolution, while O2 and N2O require higher resolution. We also find that the inclusion of clouds in our models significantly affects both the strengths and resolutions required to observe all spectral features., Comment: 34 pages, 24 fig, pdf, ApJ, TBP