Aaron Goldman

The HITRAN molecular spectroscopic database: edition of 2000 including updates through 2001

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

The HITRAN molecular spectroscopic database and HAWKS (HITRAN atmospheric workstation)

Nineteen ninety-eight marks the 25th anniversary of the release of the first HITRAN database. HITRAN is recognized as the international standard of the 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 is forthcoming. A new release is planned for 1998.

Spectral line parameters for the A2∑-X2Π(0,0) band of OH for atmospheric and high temperatures

Abstract Individual spectral line parameters including line positions, strengths, and intensities, have been generated for the A 2 ∑- X 2 Π(0,0) band of OH, applicable to atmospheric and high temperatures. Energy levels and transition frequencies are calculated by numerically diagonalizing the Hamiltonian. Line strengths are calculated using the dipole matrix and eigenvectors derived from energy matrix diagonalization. The line strengths are compared to those calculated from previously published algebraic line strength formulas. Tables of line parameters are presented for 240 and 4600°K.

Atmospheric sulfur hexafluoride: Sources, sinks and greenhouse warming

Model calculations using estimated reaction rates of sulfur hexafluoride (SF6) with OH and O(1D) indicate that the atmospheric lifetime due to these processes may be very long (25,000 years). An upper limit for the UV cross section would suggest a photolysis lifetime much longer than 1000 years. The possibility of other removal mechanisms are discussed. The estimated lifetimes are consistent with other estimated values based on recent laboratory measurements. There appears to be no known natural source of SF6. An estimate of the current production rate of SF6 is about 5 kt/yr. Based on historical emission rates, we calculated a present-day atmospheric concentrations for SF6 of about 2.5 parts per trillion by volume (pptv) and compared the results with available atmospheric measurements. It is difficult to estimate the atmospheric lifetime of SF6 based on mass balance of the emission rate and observed abundance. There are large uncertainties concerning what portion of the SF6 is released to the atmosphere. Even if the emission rate were precisely known, it would be difficult to distinguish among lifetimes longer than 100 years since the current abundance of SF6 is due to emission in the past three decades. More information on the measured trends over the past decade and observed vertical and latitudinal distributions of SF6 in the lower stratosphere will help to narrow the uncertainty in the lifetime. Based on laboratory-measured IR absorption cross section for SF6, we showed that SF6 is about 3 times more effective as a greenhouse gas compared to CFC 11 on a per molecule basis. However, its effect on atmospheric warming will be minimal because of its very small concentration. We estimated the future concentration of SF6 at 2010 to be 8 and 10 pptv based on two projected emission scenarios. The corresponding equilibrium warming of 0.0035°C and 0.0043°C is to be compared with the estimated warming due to CO2 increase of about 0.8°C in the same period.

Comparison of carbon monoxide measurements by TES and MOPITT: Influence of a priori data and instrument characteristics on nadir atmospheric species retrievals

[1] Comparisons of tropospheric carbon monoxide (CO) volume mixing ratio profiles and total columns are presented from nadir-viewing measurements made by the Tropospheric Emission Spectrometer (TES) on the NASA Aura satellite and by the Measurements of Pollution in the Troposphere (MOPITT) instrument on the NASA Terra satellite. In this paper, we first explore the factors that relate the retrieved and the true species profiles. We demonstrate that at a given location and time the retrieved species profiles reported by different satellite instrument teams can be very different from each other. We demonstrate the influence of the a priori data and instrument characteristics on the CO products from TES and MOPITT and on their comparisons. Direct comparison of TES and MOPITT retrieved CO profiles and columns show significant differences in the lower and upper troposphere. To perform a more proper and rigorous comparison between the two instrument observations we allow for different a priori profiles and averaging kernels. We compare (1) TES retrieved CO profiles adjusted to the MOPITT a priori with the MOPITT retrievals and (2) the above adjusted TES CO profiles with the MOPITT profiles vertically smoothed by the TES averaging kernels. These two steps greatly improve the agreement between the CO profiles and the columns from the two instruments. No systematic differences are found as a function of latitude in the final comparisons. These results show that knowledge of the a priori profiles, the averaging kernels, and the error covariance matrices in the standard data products provided by the instrument teams and understanding their roles in the retrieval products are essential in quantitatively interpreting both retrieved profiles and the derived total or partial columns for scientific applications.

Long‐term trends of inorganic chlorine from ground‐based infrared solar spectra: Past increases and evidence for stabilization

Long-term time series of hydrogen chloride (HCl) and chlorine nitrate (ClONO2) total column abundances has been retrieved from high spectral resolution ground-based solar absorption spectra recorded with infrared Fourier transform spectrometers at nine NDSC (Network for the Detection of Stratospheric Change) sites in both Northern and Southern Hemispheres. The data sets span up to 24 years and most extend until the end of 2001. The time series of Cl-y (defined here as the sum of the HCl and ClONO2 columns) from the three locations with the longest time-span records show rapid increases until the early 1990s superimposed on marked day-to-day, seasonal and inter-annual variability. Subsequently, the buildup in Cl-y slows and reaches a broad plateau after 1996, also characterized by variability. A similar time evolution is also found in the total chlorine concentration at 55 km altitude derived from Halogen Occultation Experiment (HALOE) global observations since 1991. The stabilization of inorganic chlorine observed in both the total columns and at 55 km altitude indicates that the near-global 1993 organic chlorine (CCly) peak at the Earths surface has now propagated over a broad altitude range in the upper atmosphere, though the time lag is difficult to quantify precisely from the current data sets, due to variability. We compare the three longest measured time series with two-dimensional model calculations extending from 1977 to 2010, based on a halocarbon scenario that assumes past measured trends and a realistic extrapolation into the future. The model predicts broad Cl-y maxima consistent with the long-term observations, followed by a slow Cl-y decline reaching 12-14% relative to the peak by 2010. The data reported here confirm the effectiveness of the Montreal Protocol and its Amendments and Adjustments in progressively phasing out the major man-related perturbations of the stratospheric ozone layer, in particular, the anthropogenic chlorine-bearing source gases. (Less)

Airborne observations of SO2, HCl, and O3 in the stratospheric plume of the Pinatubo Volcano in July 1991

We have used a high resolution infrared spectrometer aboard the NASA Wallops Flight Facility Electra aircraft to measure the total column amount of SO2, O3, and HCl above the aircraft while flying over the Caribbean three weeks after the June 15 eruption of Mt. Pinatubo in the Philippines, South of 20°N latitude we observed columns of SO2 ranging from 2.0 × 1016 to 3.7 × 1016 molecules-cm−2. In addition, the column amount of HCl averaged 1.5 × 1015 molecules-cm−2 in the region of the plume. This may represent a small increase in HCl above the amount, estimated from our previous measurements, that would have been present had there been no volcanic eruption, but the increase is substantially less than that seen following the 1982 eruptions of El Chichon [Mankin and Coffey, 1984].

Forward model and Jacobians for Tropospheric Emission Spectrometer retrievals

The Tropospheric Emission Spectrometer (TES) is a high-resolution spaceborne sensor that is capable of observing tropospheric species. In order to exploit fully TESs potential for tropospheric constituent retrievals, an accurate and fast operational forward model was developed for TES. The forward model is an important component of the TES retrieval model, the Earth Limb and Nadir Operational Retrieval (ELANOR), as it governs the accuracy and speed of the calculations for the retrievals. In order to achieve the necessary accuracy and computational efficiency, TES adopted the strategy of utilizing precalculated absorption coefficients generated by the line-by-line calculations provided by line-by-line radiation transfer modeling. The decision to perform the radiative transfer with the highest monochromatic accuracy attainable, rather than with an accelerated scheme that has the potential to add algorithmic forward model error, has proven to be very successful for TES retrievals. A detailed description of the TES forward model and Jacobians is described. A preliminary TES observation is provided as an example to demonstrate that the TES forward model calculations represent TES observations. Also presented is a validation example, which is part of the extensive forward model validation effort.

Intercomparison of UV/visible spectrometers for measurements of stratospheric NO2 for the Network for the Detection of Stratospheric Change

During the period May 12–23, 1992, seven groups from seven countries met in Lauder, New Zealand, to intercompare their remote sensing instruments for the measurement of atmospheric column NO2 from the surface. The purpose of the intercomparison was to determine the degree of intercomparability and to qualify instruments for use in the Network for the Detection of Stratospheric Change (NDSC). Three of the instruments which took part in the intercomparison are slated for deployment at primary NDSC sites. All instruments were successful in obtaining slant column NO2 amounts at sunrise and sunset on most of the 12 days of the intercomparison. The group as a whole was able to make measurements of the 90° solar zenith angle slant path NO2 column amount that agreed to about ±10% most of the time; however, the sensitivity of the individual measurements varied considerably. Part of the sensitivity problem for these measurements is the result of instrumentation, and part is related to the data analysis algorithms used. All groups learned a great deal from the intercomparison and improved their results considerably as a result of this exercise.

Multiyear infrared solar spectroscopic measurements of HCN, CO, C2H6, and C2H2 tropospheric columns above Lauder, New Zealand (45°S latitude)

[i] Near-simultaneous, 0.0035 or 0.007 cm -1 resolution infrared solar absorption spectra of tropospheric HCN, C 2 H 2 , CO, and C 2 H 6 have been recorded from the Network for the Detection of Stratospheric Change station in Lauder, New Zealand (45.04°S, 169.68°E, 0.37 km altitude). All four molecules were measured on over 350 days with HCN and C 2 H 2 reported for the first time based on a new analysis procedure that significantly increases the effective signal-to-noise of weak tropospheric absorption features in the measured spectra. The CO measurements extend by 2.5 years a database of measurements begun in January 1994 for CO with improved sensitivity in the lower and middle troposphere. The C 2 H 6 measurements lengthen a time series begun in July 1993 with peak sensitivity in the upper troposphere. Retrievals of all four molecules were obtained with an algorithm based on the semiempirical application of the Rodgers optimal estimation technique. Columns are reported for the 0.37- to 12-km-altitude region, approximately the troposphere above the station. The seasonal cycles of all four molecules are asymmetric, with minima in March-June and sharp peaks and increased variability during August-November, which corresponds to the period of maximum biomass burning near the end of the Southern Hemisphere tropical dry season. Except for a possible HCN column decrease, no evidence was found for a statistically significant long-term trend.