Coleen M. Roehl

Atmospheric carbon dioxide retrieved from the Greenhouse gases Observing SATellite (GOSAT): Comparison with ground-based TCCON observations and GEOS-Chem model calculations

We retrieved column-averaged dry air mole fractions of atmospheric carbon dioxide (X_CO_2) from backscattered short-wave infrared (SWIR) sunlight measured by the Japanese Greenhouse gases Observing SATellite (GOSAT). Over two years of X_CO_2 retrieved from GOSAT is compared with X_CO_2 inferred from collocated SWIR measurements by seven ground-based Total Carbon Column Observing Network (TCCON) stations. The average difference between GOSAT and TCCON X_CO_2 for individual TCCON sites ranges from −0.87 ppm to 0.77 ppm with a mean value of 0.1 ppm and standard deviation of 0.56 ppm. We find an average bias between all GOSAT and TCCON X_CO_2 retrievals of −0.20 ppm with a standard deviation of 2.26 ppm and a correlation coefficient of 0.75. One year of XCO2 was retrieved from GOSAT globally, which was compared to global 3-D GEOS-Chem chemistry transport model calculations. We find that the latitudinal gradient, seasonal cycles, and spatial variability of GOSAT and GEOS-Chem agree well in general with a correlation coefficient of 0.61. Regional differences between GEOS-Chem model calculations and GOSAT observations are typically less than 1 ppm except for the Sahara and central Asia where a mean difference between 2 to 3 ppm is observed, indicating regional biases in the GOSAT X_CO_2 retrievals unobserved by the current TCCON network. Using a bias correction scheme based on linear regression these regional biases are significantly reduced, approaching the required accuracy for surface flux inversions.

Temperature dependence of UV absorption cross sections and atmospheric implications of several alkyl iodides

The ultraviolet absorption spectra of a number of alkyl iodides which have been found in the troposphere, CH3I, C2H5I, CH3CH2CH2I, CH3CHICH3, CH2I2, and CH2ClI, have been measured over the wavelength range 200–380 nm and at temperatures between 298 and 210 K. The absorption spectra of the monoiodides CH3I, C2H5I, CH3CH2CH2I, and CH3CHICH3 are nearly identical in shape and magnitude and consist of single broad bands centered near 260 nm. The addition of a chlorine atom in CH2ClI shifts its spectrum to longer wavelengths (σmax at 270 nm). The spectrum of CH2I2 is further red-shifted, reaching a maximum of 3.85×10−18 cm2 molecule−1 at 288 nm and exhibiting strong absorption in the solar actinic region, λ>290 nm. Atmospheric photolysis rate constants, J values, have been calculated assuming quantum efficiencies of unity for different solar zenith angles as a function of altitude using the newly measured cross sections. Surface photolysis rate constants, calculated from the absorption cross sections measured at 298 K, range from 3×10−6 s−1 for CH3I to 5×10−3 s−1 for CH2I2 at a solar zenith angle of 40°.

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

The weakly bound HOONO product of the OH+NO2+M reaction is studied using the vibrational predissociation that follows excitation of the first OH overtone (2nu1). We observe formation of both cis-cis and trans-perp conformers of HOONO. The trans-perp HOONO 2nu1 band is observed under thermal (223-238 K) conditions at 6971 cm(-1). We assign the previously published (warmer temperature) HOONO spectrum to the 2nu1 band at 6365 cm(-1) and 2nu1-containing combination bands of the cis-cis conformer of HOONO. The band shape of the trans-perp HOONO spectrum is in excellent agreement with the predicted rotational contour based on previous experimental and theoretical results, but the apparent origin of the cis-cis HOONO spectrum at 6365 cm(-1) is featureless and significantly broader, suggesting more rapid intramolecular vibrational redistribution or predissociation in the latter isomer. The thermally less stable trans-perp HOONO isomerizes rapidly to cis-cis HOONO with an experimentally determined lifetime of 39 ms at 233 K at 13 hPa (in a buffer gas of predominantly Ar). The temperature dependence of the trans-perp HOONO lifetime in the range 223-238 K yields an isomerization barrier of 33+/-12 kJ/mol. New ab initio calculations of the structure and vibrational mode frequencies of the transition state perp-perp HOONO are performed using the coupled cluster singles and doubles with perturbative triples [CCSD(T)] model, using a correlation consistent polarized triple zeta basis set (cc-pVTZ). The energetics of cis-cis, trans-perp, and perp-perp HOONO are also calculated at this level [CCSD(T)/cc-pVTZ] and with a quadruple zeta basis set using the structure determined at the triple zeta basis set [CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ]. These calculations predict that the anti form of perp-perp HOONO has an energy of DeltaE0=42.4 kJ/mol above trans-perp HOONO, corresponding to an activation enthalpy of DeltaH298 (double dagger 0)=41.1 kJ/mol. These results are in good agreement with statistical simulations based on a model developed by Golden, Barker, and Lohr. The simulated isomerization rates match the observed decay rates when modeled with a trans-perp to cis-cis HOONO isomerization barrier of 40.8 kJ/mol and a strong collision model. The quantum yield of cis-cis HOONO dissociation to OH and NO2 is also calculated as a function of photon excitation energy in the range 3500-7500 cm(-1), assuming D0=83 kJ/mol. The quantum yield is predicted to vary from 0.15 to 1 over the observed spectrum at 298 K, leading to band intensities in the action spectrum that are highly temperature dependent; however, the observed relative band strengths in the cis-cis HOONO spectrum do not change substantially with temperature over the range 193-273 K. Semiempirical calculations of the oscillator strengths for 2nu1(cis-cis HOONO) and 2nu1(trans-perp HOONO) are performed using (1) a one-dimensional anharmonic model and (2) a Morse oscillator model for the OH stretch, and ab initio dipole moment functions calculated using Becke, Lee, Yang, and Parr density functional theory (B3LYP), Møller-Plesset pertubation theory truncated at the second and third order (MP2 and MP3), and quadratic configuration interaction theory using single and double excitations (QCISD). The QCISD level calculated ratio of 2nu1 oscillator strengths of trans-perp to cis-cis HOONO is 3.7:1. The observed intensities indicate that the concentration of trans-perp HOONO early in the OH+NO2 reaction is significantly greater than predicted by a Boltzmann distribution, consistent with statistical predictions of high initial yields of trans-perp HOONO from the OH+NO2+M reaction. In the atmosphere, trans-perp HOONO will isomerize nearly instantaneously to cis-cis HOONO. Loss of HOONO via photodissociation in the near-IR limits the lifetime of cis-cis HOONO during daylight to less than 45 h, other loss mechanisms will reduce the lifetime further.

A compact, lightweight gas standards generator for permeation tubes

A lightweight, compact gas standards generator for permeation tubes is described. This system provides reliable temperature control during periods of intermittent power and is ideal for field measurements. A eutectic alloy with a high heat of fusion is used as a phase change material. This thermal source allows the system to maintain a constant permeation tube temperature of 46.6 °C for over 5 h in the absence of external power. This permeation system is currently being used in an aircraft chemical ionization mass spectrometer to provide HNO3 calibration.

Intensity of the second and third OH overtones of H2O2, HNO3, and HO2NO2

The 3ν_(OH) and 4ν_(OH) of H_2O_2, HNO_3, and HO_2NO_2 have been observed. The band strengths of 3ν_(OH) are (7.0±1.8) × 10^(−20), (2.9±0.7) × 10^(−20), and (3.8±1.1) × 10^(−20) cm^2 molecules^(−1) cm^(−1) for H_2O_2, HNO_3, and HO_2NO_2, respectively. Those of 4ν_(OH) are (4.5± .6) × 10^(−21), (2.8± .0) × 10^(−21), and (3.0±1.8) × 10^(−21) cm^2 molecules^(−1) cm^(−1) for H_2O_2, HNO_3, and HO_2NO_2, respectively. The uncertainty is for one standard deviation. Assuming excitation of these modes by solar absorption is dissociative for HO_2NO_2, these measurements confirm that this process will play a small role in the atmospheric photochemistry of the lower stratosphere.

Accounting for aerosol scattering in the CLARS retrieval of column averaged CO2 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.

Vibrational overtone initiated unimolecular dissociation of HOCH2OOH and HOCD2OOH : Evidence for mode selective behavior

The vibrational overtone induced unimolecular dissociation of HMHP (HOCH(2)OOH) and HMHP-d(2) (HOCD(2)OOH) into OH and HOCH(2)O (HOCD(2)O) fragments is investigated in the region of the 4nu(OH) and 5nu(OH) bands. The unimolecular dissociation rates in the threshold region, corresponding to the 4nu(OH) band, exhibit measurable differences associated with excitation of the OH stretch of the alcohol versus the peroxide functional group, with the higher energy alcohol OH stretching state exhibiting a slower dissociation rate compared to the lower energy peroxide OH stretch in both HMHP and HMHP-d(2). Predictions using the Rice-Ramsperger-Kassel-Marcus theory give rates that are in reasonably good agreement with the measured dissociation rate for the alcohol OH stretch but considerably differ from the measured rates for the peroxide OH stretch in both isotopomers. The present results are interpreted as suggesting that the extent of intramolecular vibrational energy redistribution (IVR) is different for the two OH stretching states associated with the two functional groups in HMHP, with IVR being substantially less complete for the peroxide OH stretch. Analysis of the OH fragment product state distributions in conjunction with phase-space theory simulation gives a D(0) value of 38+/-0.7 kcal/mole for breaking the peroxide bond in HMHP.

Preflight Spectral Calibration of the Orbiting Carbon Observatory 2

This paper describes the preflight spectral calibration methods and results for the Orbiting Carbon Observatory 2 (OCO-2), following the approach developed for the first OCO. The instrument line shape (ILS) function and dispersion parameters were determined through laser-based spectroscopic measurements, and then further optimized by comparing solar spectra recorded simultaneously on the ground by the OCO-2 flight instrument and a collocated high-resolution Fourier transform spectrometer (FTS). The resulting ILS profiles and dispersion parameters, when applied to the FTS solar data, showed agreement between the spectra recorded by the spectrometers and FTS to approximately 0.2% RMS, satisfying the preflight spectral calibration accuracy requirement of <0.25% RMS. Specific changes to the OCO-2 instrument and calibration process, compared to the original OCO, include stray-light protection; improved laser setup; increased spectral sampling; enhanced data screening, and incremental improvements in the ILS, dispersion, and FTS optimization analyses.

The Orbiting Carbon Observatory (OCO-2) tracks 2-3 peta-gram increase in carbon release to the atmosphere during the 2014-2016 El Niño

The powerful El Niño event of 2015–2016 – the third most intense since the 1950s – has exerted a large impact on the Earth’s natural climate system. The column-averaged CO2 dry-air mole fraction (XCO2) observations from satellites and ground-based networks are analyzed together with in situ observations for the period of September 2014 to October 2016. From the differences between satellite (OCO-2) observations and simulations using an atmospheric chemistry-transport model, we estimate that, relative to the mean annual fluxes for 2014, the most recent El Niño has contributed to an excess CO2 emission from the Earth’s surface (land + ocean) to the atmosphere in the range of 2.4 ± 0.2 PgC (1 Pg = 1015 g) over the period of July 2015 to June 2016. The excess CO2 flux is resulted primarily from reduction in vegetation uptake due to drought, and to a lesser degree from increased biomass burning. It is about the half of the CO2 flux anomaly (range: 4.4–6.7 PgC) estimated for the 1997/1998 El Niño. The annual total sink is estimated to be 3.9 ± 0.2 PgC for the assumed fossil fuel emission of 10.1 PgC. The major uncertainty in attribution arise from error in anthropogenic emission trends, satellite data and atmospheric transport.

Evaluating GPP and Respiration Estimates Over Northern Midlatitude Ecosystems Using Solar‐Induced Fluorescence and Atmospheric CO2 Measurements

On regional to global scales, few constraints exist on gross primary productivity (GPP) and ecosystem respiration (Re) fluxes. Yet, constraints on these fluxes are critical for evaluating and improving terrestrial biosphere models (TBMs). In this study, we evaluate the seasonal cycle of GPP, Re and net ecosystem exchange (NEE) produced by four TBMs and FLUXCOM, a data-driven model, over northern mid-latitude ecosystems. We evaluate the seasonal cycle of GPP and NEE using solar induced fluorescence (SIF) retrieved from the Global Ozone Monitoring Experiment-2 (GOME-2) and column-averaged dry-air mole fractions of CO2 (XCO2) from the Total Carbon Column Observing Network (TCCON), respectively. We then infer Re by combining constraints on GPP with constraints on NEE from two flux inversions. An ensemble of optimized Re seasonal cycles is generated using five GPP estimates and two NEE estimates. The optimized Re curves generally show high consistency with each other, with the largest differences due to the magnitude of GPP. We find optimized Re exhibits a systematically broader summer maximum than modeled Re, with values lower during June–July and higher during the fall than Re. Further analysis suggests that the differences could be due to seasonal variations in the carbon use efficiency (possibly due to an ecosystem scale Kok effect) and to seasonal variations in the leaf litter and fine root carbon pool. The results suggest that the inclusion of variable carbon use efficiency for autotrophic respiration and ©2018 American Geophysical Union. All Rights Reserved. carbon pool dependence for heterotrophic respiration are important for accurately simulating Re. Keypoints: • Top-down constraints on ecosystem respiration are obtained by combining atmospheric CO2 and solar induced fluorescence observations. • Inferred ecosystem respiration suggests a systematically broader summer maximum than bottom-up estimates over the northern mid-latitudes. • Inferred ecosystem respiration shows high sensitivity to the magnitude of gross primary productivity. ©2018 American Geophysical Union. All Rights Reserved.