Atmospheric greenhouse gases retrieved from SCIAMACHY: comparison to ground-based FTS measurements and model results

SCIAMACHY onboard ENVISAT (launched in 2002) enables the retrieval of global long-term column-averaged dry air mole fractions of the two most important anthropogenic greenhouse gases carbon dioxide and methane (denoted XCO_2 and XCH_4). In order to assess the quality of the greenhouse gas data obtained with the recently introduced v2 of the scientific retrieval algorithm WFM-DOAS, we present validations with ground-based Fourier Transform Spectrometer (FTS) measurements and comparisons with model results at eight Total Carbon Column Observing Network (TCCON) sites providing realistic error estimates of the satellite data. Such validation is a prerequisite to assess the suitability of data sets for their use in inverse modelling. It is shown that there are generally no significant differences between the carbon dioxide annual increases of SCIAMACHY and the assimilation system CarbonTracker (2.00 ± 0.16 ppm yr^(−1) compared to 1.94 ± 0.03 ppm yr−1 on global average). The XCO_2 seasonal cycle amplitudes derived from SCIAMACHY are typically larger than those from TCCON which are in turn larger than those from CarbonTracker. The absolute values of the northern hemispheric TCCON seasonal cycle amplitudes are closer to SCIAMACHY than to CarbonTracker and the corresponding differences are not significant when compared with SCIAMACHY, whereas they can be significant for a subset of the analysed TCCON sites when compared with CarbonTracker. At Darwin we find discrepancies of the seasonal cycle derived from SCIAMACHY compared to the other data sets which can probably be ascribed to occurrences of undetected thin clouds. Based on the comparison with the reference data, we conclude that the carbon dioxide data set can be characterised by a regional relative precision (mean standard deviation of the differences) of about 2.2 ppm and a relative accuracy (standard deviation of the mean differences) of 1.1–1.2 ppm for monthly average composites within a radius of 500 km. For methane, prior to November 2005, the regional relative precision amounts to 12 ppb and the relative accuracy is about 3 ppb for monthly composite averages within the same radius. The loss of some spectral detector pixels results in a degradation of performance thereafter in the spectral range currently used for the methane column retrieval. This leads to larger scatter and lower XCH_4 values are retrieved in the tropics for the subsequent time period degrading the relative accuracy. As a result, the overall relative precision is estimated to be 17 ppb and the relative accuracy is in the range of about 10–20 ppb for monthly averages within a radius of 500 km. The derived estimates show that the SCIAMACHY XCH_4 data set before November 2005 is suitable for regional source/sink determination and regional-scale flux uncertainty reduction via inverse modelling worldwide. In addition, the XCO2 monthly data potentially provide valuable information in continental regions, where there is sparse sampling by surface flask measurements

Measurements of Gas‐Phase Inorganic and Organic Acids from Biomass Fires by Negative‐Ion Proton‐Transfer Chemical‐Ionization Mass Spectrometry

[1] Emissions from 34 laboratory biomass fires were investigated at the combustion facility of the U.S. Department of Agriculture Fire Sciences Laboratory in Missoula, Montana. Gas-phase organic and inorganic acids were quantified using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), open-path Fourier transform infrared spectroscopy (OP-FTIR), and proton-transfer-reaction mass spectrometry (PTR-MS). NI-PT-CIMS is a novel technique that measures the mass-to-charge ratio (m/z) of ions generated from reactions of acetate (CH3C(O)O−) ions with inorganic and organic acids. The emission ratios for various important reactive acids with respect to CO were determined. Emission ratios for isocyanic acid (HNCO), 1,2 and 1,3-benzenediols (catechol, resorcinol), nitrous acid (HONO), acrylic acid, methacrylic acid, propionic acid, formic acid, pyruvic acid, and glycolic acid were measured from biomass burning. Our measurements show that there is a significant amount of HONO in fresh smoke. The NI-PT-CIMS measurements were validated by comparison with OP-FTIR measurements of HONO and formic acid (HCOOH) and with PTR-MS measurements of HCOOH

The Greenhouse Gas Climate Change Initiative (GHG-CCI): comparative validation of GHG-CCI SCIAMACHY/ENVISAT and TANSO-FTS/GOSAT CO₂ and CH₄ retrieval algorithm products with measurements from the TCCON

Column-averaged dry-air mole fractions of carbon dioxide and methane have been retrieved from spectra acquired by the TANSO-FTS (Thermal And Near-infrared Sensor for carbon Observations-Fourier Transform Spectrometer) and SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric Cartography) instruments on board GOSAT (Greenhouse gases Observing SATellite) and ENVISAT (ENVIronmental SATellite), respectively, using a range of European retrieval algorithms. These retrievals have been compared with data from ground-based high-resolution Fourier transform spectrometers (FTSs) from the Total Carbon Column Observing Network (TCCON). The participating algorithms are the weighting function modified differential optical absorption spectroscopy (DOAS) algorithm (WFMD, University of Bremen), the Bremen optimal estimation DOAS algorithm (BESD, University of Bremen), the iterative maximum a posteriori DOAS (IMAP, Jet Propulsion Laboratory (JPL) and Netherlands Institute for Space Research algorithm (SRON)), the proxy and full-physics versions of SRON's RemoTeC algorithm (SRPR and SRFP, respectively) and the proxy and full-physics versions of the University of Leicester's adaptation of the OCO (Orbiting Carbon Observatory) algorithm (OCPR and OCFP, respectively). The goal of this algorithm inter-comparison was to identify strengths and weaknesses of the various so-called round- robin data sets generated with the various algorithms so as to determine which of the competing algorithms would proceed to the next round of the European Space Agency's (ESA) Greenhouse Gas Climate Change Initiative (GHG-CCI) project, which is the generation of the so-called Climate Research Data Package (CRDP), which is the first version of the Essential Climate Variable (ECV) "greenhouse gases" (GHGs). For XCO₂, all algorithms reach the precision requirements for inverse modelling (< 8 ppm), with only WFMD having a lower precision (4.7 ppm) than the other algorithm products (2.4–2.5 ppm). When looking at the seasonal relative accuracy (SRA, variability of the bias in space and time), none of the algorithms have reached the demanding < 0.5 ppm threshold. For XCH₄, the precision for both SCIAMACHY products (50.2 ppb for IMAP and 76.4 ppb for WFMD) fails to meet the < 34 ppb threshold for inverse modelling, but note that this work focusses on the period after the 2005 SCIAMACHY detector degradation. The GOSAT XCH₄ precision ranges between 18.1 and 14.0 ppb. Looking at the SRA, all GOSAT algorithm products reach the < 10 ppm threshold (values ranging between 5.4 and 6.2 ppb). For SCIAMACHY, IMAP and WFMD have a SRA of 17.2 and 10.5 ppb, respectively

Orbital dynamics of "smart dust" devices with solar radiation pressure and drag

This paper investigates how perturbations due to asymmetric solar radiation pressure, in the presence of Earth shadow, and atmospheric drag can be balanced to obtain long-lived Earth centred orbits for swarms of micro-scale 'smart dust' devices, without the use of active control. The secular variation of Keplerian elements is expressed analytically through an averaging technique. Families of solutions are then identified where Sun-synchronous apse-line precession is achieved passively to maintain asymmetric solar radiation pressure. The long-term orbit evolution is characterized by librational motion, progressively decaying due to the non-conservative effect of atmospheric drag. Long-lived orbits can then be designed through the interaction of energy gain from asymmetric solar radiation pressure and energy dissipation due to drag. In this way, the usual short drag lifetime of such high area-to-mass spacecraft can be greatly extended (and indeed selected). In addition, the effect of atmospheric drag can be exploited to ensure the rapid end-of-life decay of such devices, thus preventing long-lived orbit debris

Nighttime removal of NOx in the summer marine boundary layer

The nitrate radical, NO3, and dinitrogen pentoxide, N2O5, are two important components of nitrogen oxides that occur predominantly at night in the lower troposphere. Because a large fraction of NO2 reacts to form NO3 and N2O5 during the course of a night, their fate is an important determining factor to the overall fate of NOx (=NO and NO2). As a comprehensive test of nocturnal nitrogen oxide chemistry, concentrations of O3, NO, NO2, NO3, N2O5, HNO3 and a host of other relevant compounds, aerosol abundance and composition, and meteorological conditions were measured in the marine boundary layer from the NOAA research vessel Ronald H. Brown off the East Coast of the United States as part of the New England Air Quality Study (NEAQS) during the summer of 2002. The results confirm the prominent role of NO3 and N2O5 in converting NOx to HNO3 at night with an efficiency on par with daytime photochemical conversion. The findings demonstrate the large role of nighttime chemistry in determining the NOx budget and consequent production of ozone. INDEX TERMS: 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry. Citation: Brown, S. S., et al. (2004), Nighttime removal of NOx in the summer marine boundary layer, Geophys. Res. Lett., 31, L07108, doi:10.1029/2004GL01941

Measurements of hydrogen sulfide (H2S) using PTR-MS: Calibration, humidity dependence, inter-comparison and results from field studies in an oil and gas production region

Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H2S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H2S using proton-transfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H2S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H2S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H2S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H2S is only slightly higher than that of water. The H2S sensitivity of PTR-MS ranged between 0.6–1.4 ncps ppbv−1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H2S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H2S measurements using a PTR time-of-flight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H2S / CH4. On average 0.6 ± 0.3 ppbv H2S was present at Horse Pool during UBWOS 2013. The correlation between H2S and methane enhancements suggests that the source of H2S is associated with oil and gas extraction in the basin. Significant H2S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H2S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of H2S at levels below 1 ppbv

Toward accurate CO_2 and CH_4 observations from GOSAT

The column-average dry air mole fractions of atmospheric carbon dioxide and methane (X_(CO_2) and X_(CH_4)) are inferred from observations of backscattered sunlight conducted by the Greenhouse gases Observing SATellite (GOSAT). Comparing the first year of GOSAT retrievals over land with colocated ground-based observations of the Total Carbon Column Observing Network (TCCON), we find an average difference (bias) of −0.05% and −0.30% for X_(CO_2) and X_(CH_4) with a station-to-station variability (standard deviation of the bias) of 0.37% and 0.26% among the 6 considered TCCON sites. The root-mean square deviation of the bias-corrected satellite retrievals from colocated TCCON observations amounts to 2.8 ppm for X_(CO_2) and 0.015 ppm for X_(CH_4). Without any data averaging, the GOSAT records reproduce general source/sink patterns such as the seasonal cycle of X_(CO_2) suggesting the use of the satellite retrievals for constraining surface fluxes

Improved water vapour spectroscopy in the 4174-4300 cm⁻¹ region and its impact on SCIAMACHY HDO/H₂O measurements

The relative abundance of the heavy water isotopologue HDO provides a deeper insight into the atmospheric hydrological cycle. The SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY) allows for global retrievals of the ratio HDO/HO in the 2.3 micron wavelength range. However, the spectroscopy of water lines in this region remains a large source of uncertainty for these retrievals. We therefore evaluate and improve the water spectroscopy in the range 4174–4300 cm⁻¹ and test if this reduces systematic uncertainties in the SCIAMACHY retrievals of HDO/H₂O. We use a laboratory spectrum of water vapour to fit line intensity, air broadening and wavelength shift parameters. The improved spectroscopy is tested on a series of ground-based high resolution FTS spectra as well as on SCIAMACHY retrievals of H2O and the ratio HDO/H₂O. We find that the improved spectroscopy leads to lower residuals in the FTS spectra compared to HITRAN 2008 and Jenouvrier et al. (2007) spectroscopy, and the retrievals become more robust against changes in the retrieval window. For both the FTS and SCIAMACHY measurements, the retrieved total H₂O columns decrease by 2–4% and we find a negative shift of the HDO/H₂O ratio, which for SCIAMACHY is partly compensated by changes in the retrieval setup and calibration software. The updated SCIAMACHY HDO/H₂O product shows somewhat steeper latitudinal and temporal gradients and a steeper Rayleigh distillation curve, strengthening previous conclusions that current isotope-enabled general circulation models underestimate the variability in the near-surface HDO/H₂O ratio