Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations

We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg a<sup>−1</sup>, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a<sup>−1</sup>, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NO<sub>x</sub> ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a<sup>−1</sup>. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a<sup>−1</sup>) and anthropogenic emissions (2 Tg a<sup>−1</sup>). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NO<sub>x</sub>: we find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a<sup>−1</sup> and 7.8 Tg a<sup>−1</sup>, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel

Cougars in Kansas

The presence of the cougar (Puma concolor) in the state of Kansas is a controversial issue. Since 1999, 234 cougar sightings have been reported to the Extension Wildlife Specialist at Kansas State University. To those who have reported such sightings, the existence of cougars in Kansas is undeniable. Others, however, question the validity of such sightings as providing evidence of cougars. After surveying other governmental agencies and organizations, we discovered that acceptable identification criteria for rare or unusual felines included things beside sightings: voucher specimens, DNA from hair or scat, tracks, prey carcasses, and photographs or videos. The cougar sightings from Kansas were plotted on a map using ArcGIS 9.1, and the Spatial Analyst Tool was used to test the 3 hypotheses of: 1) cougar sightings are located near rivers, as cover is provided; 2) sightings of cougars are located around captive felines that may be potential breeding partners; and 3) cougar sightings are located within the vicinity of cities with populations greater than or equal to 35,000 people, as the higher densities of observers may be associated with more opportunities for sightings. Our data led us to accept all 3 hypotheses

Cougars in Kansas

The presence of the cougar (Puma concolor) in the state of Kansas is a controversial issue. Since 1999, 234 cougar sightings have been reported to the Extension Wildlife Specialist at Kansas State University. To those who have reported such sightings, the existence of cougars in Kansas is undeniable. Others, however, question the validity of such sightings as providing evidence of cougars. After surveying other governmental agencies and organizations, we discovered that acceptable identification criteria for rare or unusual felines included things beside sightings: voucher specimens, DNA from hair or scat, tracks, prey carcasses, and photographs or videos. The cougar sightings from Kansas were plotted on a map using ArcGIS 9.1, and the Spatial Analyst Tool was used to test the 3 hypotheses of: 1) cougar sightings are located near rivers, as cover is provided; 2) sightings of cougars are located around captive felines that may be potential breeding partners; and 3) cougar sightings are located within the vicinity of cities with populations greater than or equal to 35,000 people, as the higher densities of observers may be associated with more opportunities for sightings. Our data led us to accept all 3 hypotheses

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

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

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

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

Importance of secondary sources in the atmospheric budgets of formic and acetic acids

We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ~1200 and ~1400 Gmol yr^(−1), dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of formic and acetic acids well but generally underestimates their concentration, particularly in the Northern midlatitudes. We infer that the source of both carboxylic acids may be up to 50% greater than our estimate and report evidence for a long-lived missing secondary source of carboxylic acids that may be associated with the aging of organic aerosols. Vertical profiles of formic acid in the upper troposphere support a negative temperature dependence of the reaction between formic acid and the hydroxyl radical as suggested by several theoretical studies