Process-evaluation of tropospheric humidity simulated by general circulation models using water vapor isotopologues: 1. Comparison between models and observations

The goal of this study is to determine how H_2O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H_2O characteristics that are robust across data sets and that can be used to evaluate models. We evaluate the isotopic GCM LMDZ, accounting for the effects of spatiotemporal sampling and instrument sensitivity. We find that LMDZ reproduces the spatial patterns in the lower and mid troposphere remarkably well. However, it underestimates the amplitude of seasonal variations in isotopic composition at all levels in the subtropics and in midlatitudes, and this bias is consistent across all data sets. LMDZ also underestimates the observed meridional isotopic gradient and the contrast between dry and convective tropical regions compared to satellite data sets. Comparison with six other isotope-enabled GCMs from the SWING2 project shows that biases exhibited by LMDZ are common to all models. The SWING2 GCMs show a very large spread in isotopic behavior that is not obviously related to that of humidity, suggesting water vapor isotopic measurements could be used to expose model shortcomings. In a companion paper, the isotopic differences between models are interpreted in terms of biases in the representation of processes controlling humidity

Kinetics and Products of the Acid-Catalyzed Ring-Opening of Atmospherically Relevant Butyl Epoxy Alcohols

Epoxydiols are produced in the gas phase from the photo-oxidation of isoprene in the absence of significant mixing ratios of nitrogen oxides (NO_x). The reactive uptake of these compounds onto acidic aerosols has been shown to produce secondary organic aerosol (SOA). To better characterize the fate of isoprene epoxydiols in the aerosol phase, the kinetics and products of the acid-catalyzed ring-opening reactions of four hydroxy-substituted epoxides were studied by nuclear magnetic resonance (NMR) techniques. Polyols and sulfate esters are observed from the ring-opening of the epoxides in solutions of H_2SO_4/Na_2SO_4. Likewise, polyols and nitrate esters are produced in solutions of HNO_3/NaNO_3. In sulfuric acid, the rate of acid-catalyzed ring-opening is dependent on hydronium ion activity, sulfate ion, and bisulfate. The rates are much slower than the nonhydroxylated equivalent epoxides; however, the hydroxyl groups make them much more water-soluble. A model was constructed with the major channels for epoxydiol loss (i.e., aerosol-phase ring-opening, gas-phase oxidation, and deposition). In the atmosphere, SOA formation from epoxydiols will depend on a number of variables (e.g., pH and aerosol water content) with the yield of ring-opening products varying from less than 1% to greater than 50%

Synthesis of the Southeast Atmosphere Studies: Investigating Fundamental Atmospheric Chemistry Questions

The Southeast Atmosphere Studies (SAS), which included the Southern Oxidant and Aerosol Study (SOAS); the Southeast Nexus (SENEX) study; and the Nitrogen, Oxidants, Mercury and Aerosols: Distributions, Sources and Sinks (NOMADSS) study, was deployed in the field from 1 June to 15 July 2013 in the central and eastern United States, and it overlapped with and was complemented by the Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. SAS investigated atmospheric chemistry and the associated air quality and climate-relevant particle properties. Coordinated measurements from six ground sites, four aircraft, tall towers, balloon-borne sondes, existing surface networks, and satellites provide in situ and remotely sensed data on trace-gas composition, aerosol physicochemical properties, and local and synoptic meteorology. Selected SAS findings indicate 1) dramatically reduced NOx concentrations have altered ozone production regimes; 2) indicators of “biogenic” secondary organic aerosol (SOA), once considered part of the natural background, were positively correlated with one or more indicators of anthropogenic pollution; and 3) liquid water dramatically impacted particle scattering while biogenic SOA did not. SAS findings suggest that atmosphere–biosphere interactions modulate ambient pollutant concentrations through complex mechanisms and feedbacks not yet adequately captured in atmospheric models. The SAS dataset, now publicly available, is a powerful constraint to develop predictive capability that enhances model representation of the response and subsequent impacts of changes in atmospheric composition to changes in emissions, chemistry, and meteorology

GFIT2: an experimental algorithm for vertical profile retrieval from near-IR spectra

An algorithm for retrieval of vertical profiles from ground-based spectra in the near IR is described and tested. Known as GFIT2, the algorithm is primarily intended for CO₂, and is used exclusively for CO₂ in this paper. Retrieval of CO₂ vertical profiles from ground-based spectra is theoretically possible, would be very beneficial for carbon cycle studies and the validation of satellite measurements, and has been the focus of much research in recent years. GFIT2 is tested by application both to synthetic spectra and to measurements at two Total Carbon Column Observing Network (TCCON) sites. We demonstrate that there are approximately 3° of freedom for the CO2 profile, and the algorithm performs as expected on synthetic spectra. We show that the accuracy of retrievals of CO₂ from measurements in the 1.61μ (6220 cm⁻¹) spectral band is limited by small uncertainties in calculation of the atmospheric spectrum. We investigate several techniques to minimize the effect of these uncertainties in calculation of the spectrum. These techniques are somewhat effective but to date have not been demonstrated to produce CO₂ profile retrievals with sufficient precision for applications to carbon dynamics. We finish by discussing ongoing research which may allow CO₂ profile retrievals with sufficient accuracy to significantly improve the scientific value of the measurements from that achieved with column retrievals

Reducing the impact of source brightness fluctuations on spectra obtained by Fourier-transform spectrometry

We present a method to reduce the impact of source brightness fluctuations (SBFs) on spectra recorded by Fourier-transform spectrometry (FTS). Interferograms are recorded without AC coupling of the detector signal (DC mode). The SBF are determined by low-pass filtering of the DC interferograms, which are then reweighted by the low-pass, smoothed signal. Atmospheric solar absorption interferograms recorded in DC mode have been processed with and without this technique, and we demonstrate its efficacy in producing more consistent retrievals of atmospheric composition. We show that the reweighting algorithm improves retrievals from interferograms subject to both gray and nongray intensity fluctuations, making the algorithm applicable to atmospheric data contaminated by significant amounts of aerosol or cloud cover

Effects of atmospheric light scattering on spectroscopic observations of greenhouse gases from space. Part 2: Algorithm intercomparison in the GOSAT data processing for CO_2 retrievals over TCCON sites

This report is the second in a series of companion papers describing the effects of atmospheric light scattering in observations of atmospheric carbon dioxide (CO_2) by the Greenhouse gases Observing SATellite (GOSAT), in orbit since 23 January 2009. Here we summarize the retrievals from six previously published algorithms; retrieving column‐averaged dry air mole fractions of CO_2 (X_(CO2)) during 22 months of operation of GOSAT from June 2009. First, we compare data products from each algorithm with ground‐based remote sensing observations by Total Carbon Column Observing Network (TCCON). Our GOSAT‐TCCON coincidence criteria select satellite observations within a 5° radius of 11 TCCON sites. We have compared the GOSAT‐TCCON X_(CO2) regression slope, standard deviation, correlation and determination coefficients, and global and station‐to‐station biases. The best agreements with TCCON measurements were detected for NIES 02.xx and RemoTeC. Next, the impact of atmospheric light scattering on X_(CO2) retrievals was estimated for each data product using scan by scan retrievals of light path modification with the photon path length probability density function (PPDF) method. After a cloud pre‐filtering test, approximately 25% of GOSAT soundings processed by NIES 02.xx, ACOS B2.9, and UoL‐FP: 3G and 35% processed by RemoTeC were found to be contaminated by atmospheric light scattering. This study suggests that NIES 02.xx and ACOS B2.9 algorithms tend to overestimate aerosol amounts over bright surfaces, resulting in an underestimation of X_(CO2) for GOSAT observations. Cross‐comparison between algorithms shows that ACOS B2.9 agrees best with NIES 02.xx and UoL‐FP: 3G while RemoTeC X_(CO2) retrievals are in a best agreement with NIES PPDF‐D

Vibrational overtone initiated unimolecular dissociation of HOCH_2OOH and HOCD_2OOH: Evidence for mode selective behavior

The vibrational overtone induced unimolecular dissociation of HMHP (HOCH2OOH) and HMHP-d2 (HOCD2OOH) into OH and HOCH2O (HOCD2O) fragments is investigated in the region of the 4nuOH and 5nuOH bands. The unimolecular dissociation rates in the threshold region, corresponding to the 4nuOH 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-d2. 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 D0 value of 38±0.7 kcal/mole for breaking the peroxide bond in HMHP

Comparison of XH_2O Retrieved from GOSAT Short-Wavelength Infrared Spectra with Observations from the TCCON Network

Understanding the atmospheric distribution of water (H_2O) is crucial for global warming studies and climate change mitigation. In this context, reliable satellite data are extremely valuable for their global and continuous coverage, once their quality has been assessed. Short-wavelength infrared spectra are acquired by the Thermal And Near-infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS) aboard the Greenhouse gases Observing Satellite (GOSAT). From these, column-averaged dry-air mole fractions of carbon dioxide, methane and water vapor (XH_2O) have been retrieved at the National Institute for Environmental Studies (NIES, Japan) and are available as a Level 2 research product. We compare the NIES XH_2O data, Version 02.21, with retrievals from the ground-based Total Carbon Column Observing Network (TCCON, Version GGG2014). The datasets are in good overall agreement, with GOSAT data showing a slight global low bias of −3.1% ± 24.0%, good consistency over different locations (station bias of −1.53% ± 10.35%) and reasonable correlation with TCCON (R = 0.89). We identified two potential sources of discrepancy between the NIES and TCCON retrievals over land. While the TCCON XH_2O amounts can reach 6000–7000 ppm when the atmospheric water content is high, the correlated NIES values do not exceed 5500 ppm. This could be due to a dry bias of TANSO-FTS in situations of high humidity and aerosol content. We also determined that the GOSAT-TCCON differences directly depend on the altitude difference between the TANSO-FTS footprint and the TCCON site. Further analysis will account for these biases, but the NIES V02.21 XH_2O product, after public release, can already be useful for water cycle studies

Atmospheric Acetaldehyde: Importance of Air-Sea Exchange and a Missing Source in the Remote Troposphere

We report airborne measurements of acetaldehyde (CH₃CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH₃CHO is examined using the Community Atmospheric Model with chemistry (CAM‐chem), with a newly‐developed online air‐sea exchange module. The upper limit of the global ocean net emission of CH₃CHO is estimated to be 34 Tg a⁻¹ (42 Tg a⁻¹ if considering bubble‐mediated transfer), and the ocean impacts on tropospheric CH₃CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH₃CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH₃CHO production in the remote troposphere. The higher‐than‐expected CH₃CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry‐climate models

Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide

A new approach for measuring gas-phase methyl hydrogen peroxide [(MHP) CH_3OOH] utilizing chemical ionization mass spectrometry is presented. Tandem mass spectrometry is used to avoid mass interferences that hindered previous attempts to measure atmospheric CH_3OOH with CF_3O− clustering chemistry. CH_3OOH has been successfully measured in situ using this technique during both airborne and ground-based campaigns. The accuracy and precision for the MHP measurement are a function of water vapor mixing ratio. Typical precision at 500 pptv MHP and 100 ppmv H_2O is ±80 pptv (2 sigma) for a 1 s integration period. The accuracy at 100 ppmv H_2O is estimated to be better than ±40%. Chemical ionization tandem mass spectrometry shows considerable promise for the determination of in situ atmospheric trace gas mixing ratios where isobaric compounds or mass interferences impede accurate measurements