Observations of Atmospheric Gases Using Fourier Transform Spectrometers

Remote sensing of atmospheric gases improves our understanding of the state and evolution of the Earth’s environment. At the beginning of the thesis, the basic principles for the retrieval of concentrations of atmospheric gases from spectra are presented with a focus on ground-based observations. An overview of the characteristic features of different platforms, viewing geometries, measurement sites, and Fourier Transform Spectrometers (FTSs) used in the measurements are provided. The thesis covers four main projects. The first study of the global distribution of atmospheric phosgene was carried out using a total of 5614 measured profiles from the satellite-borne Atmospheric Chemistry Experiment FTS (ACE-FTS) spanning the period February 2004 through May 2006. The phosgene concentrations display a zonally symmetric pattern with the maximum concentration located approximately over the equator, at about 25 km in altitude, and the concentrations decrease towards the poles. A layer of enhanced concentration of phosgene spans the lower stratosphere at all latitudes, with volume mixing ratios of 20-60 pptv. The reasons for the formation of the phosgene distribution pattern are explained by the insolation, lifetime of phosgene and the Brewer-Dobson circulation. The ACE observations show lower phosgene concentrations in the stratosphere than were obtained from previous observations in the 1980s and 1990s due to a significant decrease in source species. The Portable Atmospheric Research Interferometric Spectrometer for the Infrared (PARIS-IR) is a copy of the ACE-FTS that was designed for ground-based and balloon-borne measurements. The first balloon flight was part of the Middle Atmosphere Nitrogen TRend Assessment (MANTRA) 2004 balloon payload. Some useful engineering information was obtained on the thermal performance of the instrument during the flight. As part of the MANTRA program, a ground-based inter-instrument comparison campaign was conducted with the objective of assessing instrument performance, and evaluating data processing routines and retrieval codes. PARIS-IR provides similar quality results for stratospheric species as does the University of Toronto FTS. An advanced study was carried out for the Carbon Cycle science by Fourier Transform Spectroscopy (CC-FTS) mission, which is a proposed future satellite mission to obtain a better understanding of the sources and sinks of greenhouse gases in the Earth’s atmosphere by monitoring total and partial columns of CO2, CH4, N2O, and CO in the near infrared together with the molecular O2 column. To evaluate the spectral regions, resolution, optical components, and spectroscopic parameters required for the mission, ground-based Fourier transform spectra, recorded at Kiruna, Kitt Peak, and Waterloo, were used. Dry air volume mixing ratios of CO2 and CH4 were retrieved from the ground-based observations. A FTS with a spectral resolution of 0.1 cm-1, operating between 2000 and 15000 cm-1, is suggested as the primary instrument for the mission. Further progress in improving the atmospheric retrievals for CO2, CH4 and O2 requires new laboratory measurements to improve the spectroscopic line parameters. Atmospheric observations were made with three FTSs at the Polar Environment Atmospheric Research Laboratory (PEARL) during spring 2006. The vertical column densities of O3, HCl, HNO3, HF, NO2, ClONO2 and NO from PARIS-IR, the Eureka DA8 FTS, and the ACE-FTS show good agreement. Chorine activation and denitrification in the Arctic atmosphere were observed in the extremely cold stratosphere near Eureka, Nunavut, Canada. The observed ozone depletion during the 2006 campaign was attributed to chemical removal

Direct retrieval of isoprene from satellite-based infrared measurements.

Isoprene is the atmosphere's most important non-methane organic compound, with key impacts on atmospheric oxidation, ozone, and organic aerosols. In-situ isoprene measurements are sparse, and satellite-based constraints have employed an indirect approach using its oxidation product formaldehyde, which is affected by non-isoprene sources plus uncertainty and spatial smearing in the isoprene-formaldehyde relationship. Direct global isoprene measurements are therefore needed to better understand its sources, sinks, and atmospheric impacts. Here we show that the isoprene spectral signatures are detectable from space using the satellite-borne Cross-track Infrared Sounder (CrIS), develop a full-physics retrieval methodology for quantifying isoprene abundances from these spectral features, and apply the algorithm to CrIS measurements over Amazonia. The results are consistent with model output and in-situ data, and establish the feasibility of direct global space-based isoprene measurements. Finally, we demonstrate the potential for combining space-based measurements of isoprene and formaldehyde to constrain atmospheric oxidation over isoprene source regions

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

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

The on-orbit performance of the Orbiting Carbon Observatory-2 (OCO-2) instrument and its radiometrically calibrated products

The Orbiting Carbon Observatory-2 (OCO-2) carries and points a three-channel imaging grating spectrometer designed to collect high-resolution, co-boresighted spectra of reflected sunlight within the molecular oxygen (O_2) A-band at 0.765 microns and the carbon dioxide (CO_2) bands at 1.61 and 2.06 microns. These measurements are calibrated and then combined into soundings that are analyzed to retrieve spatially resolved estimates of the column-averaged CO_2 dry-air mole fraction, XCO_2. Variations of XCO_2 in space and time are then analyzed in the context of the atmospheric transport to quantify surface sources and sinks of CO_2. This is a particularly challenging remote-sensing observation because all but the largest emission sources and natural absorbers produce only small (< 0.25 %) changes in the background XCO_2 field. High measurement precision is therefore essential to resolve these small variations, and high accuracy is needed because small biases in the retrieved XCO_2 distribution could be misinterpreted as evidence for CO_2 fluxes. To meet its demanding measurement requirements, each OCO-2 spectrometer channel collects 24 spectra s^(−1) across a narrow ( 17 000), dynamic range (∼ 10^4), and sensitivity (continuum signal-to-noise ratio > 400). The OCO-2 instrument performance was extensively characterized and calibrated prior to launch. In general, the instrument has performed as expected during its first 18 months in orbit. However, ongoing calibration and science analysis activities have revealed a number of subtle radiometric and spectroscopic challenges that affect the yield and quality of the OCO-2 data products. These issues include increased numbers of bad pixels, transient artifacts introduced by cosmic rays, radiance discontinuities for spatially non-uniform scenes, a misunderstanding of the instrument polarization orientation, and time-dependent changes in the throughput of the oxygen A-band channel. Here, we describe the OCO-2 instrument, its data products, and its on-orbit performance. We then summarize calibration challenges encountered during its first 18 months in orbit and the methods used to mitigate their impact on the calibrated radiance spectra distributed to the science community

Evaluation of single-footprint AIRS CH4 profile retrieval uncertainties using aircraft profile measurements

We evaluate the uncertainties of methane optimal estimation retrievals from single-footprint thermal infrared observations from the Atmospheric Infrared Sounder (AIRS). These retrievals are primarily sensitive to atmospheric methane in the mid-troposphere through the lower stratosphere (&sim;2 to &sim;17&thinsp;km). We compare them to in situ observations made from aircraft during the HIAPER Pole to Pole Observations (HIPPO) and Atmospheric Tomography Mission (ATom) campaigns, and from the NOAA GML aircraft network, between the surface and 5&ndash;13&thinsp;km, across a range of years, latitudes between 60∘&thinsp;S to 80∘&thinsp;N, and over land and ocean. After a global, pressure-dependent bias correction, we find that the land and ocean have similar biases and that the reported observation error (combined measurement and interference errors) of &sim;27&thinsp;ppb is consistent with the SD between aircraft and individual AIRS observations. A single observation has measurement (noise related) uncertainty of &sim;17&thinsp;ppb, a &sim;20&thinsp;ppb uncertainty from radiative interferences (e.g., from water or temperature), and &sim;30&thinsp;ppb due to &ldquo;smoothing error&rdquo;, which is partially removed when making comparisons to in situ measurements or models in a way that accounts for this regularization. We estimate a 10&thinsp;ppb validation uncertainty because the aircraft typically did not measure methane at altitudes where the AIRS measurements have some sensitivity, e.g., the stratosphere, and there is uncertainty in the truth that we validate against. Daily averaging only partly reduces the difference between aircraft and satellite observation, likely because of correlated errors introduced into the retrieval from temperature and water vapor. For example, averaging nine observations only reduces the aircraft&ndash;model difference to &sim;17&thinsp;ppb vs. the expected &sim;10&thinsp;ppb. Seasonal averages can reduce this &sim;17&thinsp;ppb uncertainty further to &sim;10&thinsp;ppb, as determined through comparison with NOAA aircraft, likely because uncertainties related to radiative effects of temperature and water vapor are reduced when averaged over a season. &nbsp;</p

The on-orbit performance of the Orbiting Carbon Observatory-2 (OCO-2) instrument and its radiometrically calibrated products

The Orbiting Carbon Observatory-2 (OCO-2) carries and points a three-channel imaging grating spectrometer designed to collect high-resolution, co-boresighted spectra of reflected sunlight within the molecular oxygen (O_2) A-band at 0.765 microns and the carbon dioxide (CO_2) bands at 1.61 and 2.06 microns. These measurements are calibrated and then combined into soundings that are analyzed to retrieve spatially resolved estimates of the column-averaged CO_2 dry-air mole fraction, XCO_2. Variations of XCO_2 in space and time are then analyzed in the context of the atmospheric transport to quantify surface sources and sinks of CO_2. This is a particularly challenging remote-sensing observation because all but the largest emission sources and natural absorbers produce only small (< 0.25 %) changes in the background XCO_2 field. High measurement precision is therefore essential to resolve these small variations, and high accuracy is needed because small biases in the retrieved XCO_2 distribution could be misinterpreted as evidence for CO_2 fluxes. To meet its demanding measurement requirements, each OCO-2 spectrometer channel collects 24 spectra s^(−1) across a narrow ( 17 000), dynamic range (∼ 10^4), and sensitivity (continuum signal-to-noise ratio > 400). The OCO-2 instrument performance was extensively characterized and calibrated prior to launch. In general, the instrument has performed as expected during its first 18 months in orbit. However, ongoing calibration and science analysis activities have revealed a number of subtle radiometric and spectroscopic challenges that affect the yield and quality of the OCO-2 data products. These issues include increased numbers of bad pixels, transient artifacts introduced by cosmic rays, radiance discontinuities for spatially non-uniform scenes, a misunderstanding of the instrument polarization orientation, and time-dependent changes in the throughput of the oxygen A-band channel. Here, we describe the OCO-2 instrument, its data products, and its on-orbit performance. We then summarize calibration challenges encountered during its first 18 months in orbit and the methods used to mitigate their impact on the calibrated radiance spectra distributed to the science community

WOF-SWAT: A Web-Based Open-Source Framework for Investigating the Hydrological Impacts of Climate Change and Human Activities Through Online Simulation and Visualization of SWAT Models

This study developed a web-based open-source framework based on the Soil and Water Assessment Tool (SWAT), named WOF-SWAT (web-based open-source framework for SWAT), to investigate individual and combined impacts of climate change, land use change, and point-source pollutants on watershed-scale hydrological and chemical processes. The architecture, workflows, interfaces, and key processes of WOF-SWAT are described and discussed. Using a previously developed well-calibrated hydrological model of the Jinjiang River basin, four scenarios were simulated in WOF-SWAT and other traditional desktop-based tools (i.e., ArcSWAT and SWAT-CUP) to examine the credibility, efficiency, and functionality of WOF-SWAT. The results show that, in combination with a well-calibrated watershed model, WOF-SWAT is sufficiently sound and reasonable to investigate individual and combined impacts of climate change, land use change, and point-source pollutants. We thus conclude that WOF-SWAT can be used as a substitute for other tools to carry out similar tasks in a web-based environment while providing more user-friendly interfaces, accessibility, and efficiency. We also discuss ongoing and possible future efforts to develop WOF-SWAT into a fully-fledged watershed research and management framework