Atmospheric hydroxyl radical (OH) abundances from ground-based ultraviolet solar spectra: an improved retrieval method

The Fourier Transform Ultraviolet Spectrometer (FTUVS) instrument has recorded a long-term data record of the atmospheric column abundance of the hydroxyl radical (OH) using the technique of high resolution solar absorption spectroscopy. We report new efforts in improving the precision of the OH measurements in order to better model the diurnal, seasonal, and interannual variability of odd hydrogen (HOx) chemistry in the stratosphere, which, in turn, will improve our understanding of ozone chemistry and its long-term changes. Until the present, the retrieval method has used a single strong OH absorption line P1(1) in the near-ultraviolet at 32,341 cm−1. We describe a new method that uses an average based on spectral fits to multiple lines weighted by line strength and fitting precision. We have also made a number of improvements in the ability to fit a model to the spectral feature, which substantially reduces the scatter in the measurements of OH abundances

Water Vapor Near-UV Absorption: Laboratory Spectrum, Field Evidence, and Atmospheric Impacts

Absorption of solar radiation by water vapor in the near-UV region is a poorly-understood but important issue in atmospheric science. To better understand water vapor near-UV absorption, we constructed a cavity ring-down spectrometer with bandwidth of 5 cm-1 (~0.05 nm) and obtained water vapor absorption cross-sections at 1 nm increments in the 290-350 nm region. Water vapor displays structured absorption over this range with maximum and minimum cross-sections of 8.4×10-25 and 1.6×10-25 cm2/molecule. Major water vapor absorption bands were observed at 293-295, 307-313, 319, 321-322, and 325 nm, with cross-section values higher than 4.0×10-25 cm2/molecule. To obtain further insight into major water vapor absorption bands, we measured water vapor absorption cross-sections at 0.05 nm intervals in the 292-296, 306-314, and 317-326 nm region. Field UV residual spectra not only exhibited increased attenuation at higher atmospheric water vapor loadings but also showed structures suggested by the laboratory water vapor absorption spectrum. Spaceborne UV radiance spectra have spectral structures resembling the differential cross-section spectrum constructed from the laboratory wavelength-dependent water vapor absorption cross-sections presented here. Incorporating water vapor absorption cross-section data into a radiative transfer model yielded an estimated energy budget of 0.26 W/m2 for the standard U.S. atmosphere and 0.76 W/m2 for the tropics. This shows that water vapor near-UV absorption is an important contributor for climate simulation and ozone retrievals

Accounting for aerosol scattering in the CLARS retrieval of column averaged CO_2 mixing ratios

The California Laboratory for Atmospheric Remote Sensing Fourier transform spectrometer (CLARS‐FTS) deployed at Mount Wilson, California, has been measuring column abundances of greenhouse gases in the Los Angeles (LA) basin in the near‐infrared spectral region since August 2011. CLARS‐FTS measures reflected sunlight and has high sensitivity to absorption and scattering in the boundary layer. In this study, we estimate the retrieval biases caused by aerosol scattering and present a fast and accurate approach to correct for the bias in the CLARS column averaged CO2 mixing ratio product, X_(CO2). The high spectral resolution of 0.06 cm^(−1) is exploited to reveal the physical mechanism for the bias. We employ a numerical radiative transfer model to simulate the impact of neglecting aerosol scattering on the CO_2 and O_2 slant column densities operationally retrieved from CLARS‐FTS measurements. These simulations show that the CLARS‐FTS operational retrieval algorithm likely underestimates CO_2 and O_2 abundances over the LA basin in scenes with moderate aerosol loading. The bias in the CO_2 and O_2 abundances due to neglecting aerosol scattering cannot be canceled by ratioing each other in the derivation of the operational product of X_(CO2). We propose a new method for approximately correcting the aerosol‐induced bias. Results for CLARS X_(CO2) are compared to direct‐Sun X_(CO2) retrievals from a nearby Total Carbon Column Observing Network (TCCON) station. The bias‐correction approach significantly improves the correlation between the X_(CO2) retrieved from CLARS and TCCON, demonstrating that this approach can increase the yield of useful data from CLARS‐FTS in the presence of moderate aerosol loading

Constraining Aerosol Vertical Profile in the Boundary Layer Using Hyperspectral Measurements of Oxygen Absorption

This study attempts to infer aerosol vertical structure in the urban boundary layer using passive hyperspectral measurements. A spectral sorting technique is developed to retrieve total aerosol optical depth (AOD) and effective aerosol layer height (ALH) from hyperspectral measurements in the 1.27‐μm oxygen absorption band by the mountaintop Fourier Transform Spectrometer at the California Laboratory for Atmospheric Remote Sensing instrument (1,673 m above sea level) overlooking the LA basin. Comparison to AOD measurements from Aerosol Robotic Network and aerosol backscatter profile measurements from a Mini MicroPulse Lidar shows agreement, with coefficients of determination (r^2) of 0.74 for AOD and 0.57 for effective ALH. On average, the AOD retrieval has an error of 24.9% and root‐mean‐square error of 0.013, while the effective ALH retrieval has an error of 7.8% and root‐mean‐square error of 67.01 m. The proposed method can potentially be applied to existing and future satellite missions with hyperspectral oxygen measurements to constrain aerosol vertical distribution on a global scale

Direct Sun measurements of NO_2 column abundances from Table Mountain, California: Intercomparison of low- and high-resolution spectrometers

The NO_2 total column abundance, C_(NO_2) was measured with a direct Sun viewing technique using three different instruments at NASA Jet Propulsion Laboratory's (JPL) Table Mountain Facility in California during an instrument intercomparison campaign in July 2007. The instruments are a high‐resolution (∼0.001 nm) Fourier transform ultraviolet spectrometer (FTUVS) from JPL and two moderate‐resolution grating spectrometers, multifunction differential optical absorption spectroscopy (MF‐DOAS) (∼0.8 nm) from Washington State University and Pandora (∼0.4 nm) from NASA Goddard Space Flight Center. FTUVS uses high spectral resolution to determine the absolute NO_2 column abundance independently from the exoatmospheric solar irradiance using rovibrational NO_2 absorption lines. The NO_2 total column is retrieved after removing the solar background using Doppler‐shifted spectra from the east and west limbs of the Sun. The FTUVS measurements were used to validate the independently calibrated measurements of multifunction differential optical absorption spectroscopy (MF‐DOAS) and Pandora. The latter two instruments start with measured high‐Sun spectra as solar references to retrieve relative NO_2 columns and then apply modified Langley or “bootstrap” methods to determine the amounts of NO_2 in the references to obtain the absolute NO_2 columns. The calibration offset derived from the FTUVS measurements is consistent with the values derived from Langley and bootstrap calibration plots of the NO_2 slant column measured by the grating spectrometers. The calibrated total vertical column abundances of NO_2, C_(NO_2) from all three instruments are compared showing that MF‐DOAS and Pandora data agree well with each other, and both data sets agree with FTUVS data to within (1.5 ± 4.1)% and (6.0 ± 6.0)%, respectively

Validation of Aura Microwave Limb Sounder OH measurements with Fourier Transform Ultra-Violet Spectrometer total OH column measurements at Table Mountain, California

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

Midlatitude atmospheric OH response to the most recent 11-y solar cycle

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

Aerosol scattering effects on water vapor retrievals over the Los Angeles Basin

In this study, we propose a novel approach to describe the scattering effects of atmospheric aerosols in a complex urban environment using water vapor (H_2O) slant column measurements in the near infrared. This approach is demonstrated using measurements from the California Laboratory for Atmospheric Remote Sensing Fourier Transform Spectrometer on the top of Mt. Wilson, California, and a two-stream-exact single scattering (2S-ESS) radiative transfer (RT) model. From the spectral measurements, we retrieve H_2O slant column density (SCD) using 15 different absorption bands between 4000 and 8000 cm^(−1). Due to the wavelength dependence of aerosol scattering, large variations in H_2O SCD retrievals are observed as a function of wavelength. Moreover, the variations are found to be correlated with aerosol optical depths (AODs) measured at the AERONET-Caltech station. Simulation results from the RT model reproduce this correlation and show that the aerosol scattering effect is the primary contributor to the variations in the wavelength dependence of the H_2O SCD retrievals. A significant linear correlation is also found between variations in H_2O SCD retrievals from different bands and corresponding AOD data; this correlation is associated with the asymmetry parameter, which is a first-order measure of the aerosol scattering phase function. The evidence from both measurements and simulations suggests that wavelength-dependent aerosol scattering effects can be derived using H_2O retrievals from multiple bands. This understanding of aerosol scattering effects on H_2O retrievals suggests a promising way to quantify the effect of aerosol scattering on greenhouse gas retrievals and could potentially contribute towards reducing biases in greenhouse gas retrievals from space