Measurements of reactive chlorocarbons over the Surinam tropical rain forest: indications for strong biogenic emissions

International audienceContrary to the understanding of the emissions and chemical behavior of halocarbons from anthropogenic sources (e.g. CFCs and HCFCs), the biogeochemistry of naturally emitted halocarbons is still poorly understood. We present measurements of chloromethane (methyl chloride, CH3Cl), trichloromethane (chloroform, CHCl3), dichloromethane (CH2Cl2), and tetrachloroethylene (C2Cl4) from air samples taken over the Surinam rainforest during the 1998 LBA/CLAIRE campaign. The samples were collected in stainless steel canisters on-board a Cessna Citation jet aircraft and analyzed in the laboratory using a gas chromatograph equipped with FID and ECD. The chlorocarbons we studied have atmospheric lifetimes of ~1 year or less, and appear to have significant emissions from natural sources including oceans, soils and vegetations, as well as biomass burning. These sources are primarily concentrated in the tropics (30º N-30º S). We detected an increase as a function of latitude of methyl chloride, chloroform, and tetrachloroethylene mixing ratios, in pristine air masses advected from the Atlantic Ocean toward the central Amazon. In the absence of significant biomass burning sources, we attribute this increase to biogenic emissions from the Surinam rainforest. From our measurements, we deduce fluxes from the Surinam rainforest of 7.6±1.8 ?g CH3Cl m?2 h?1, 1.11±0.08g CHCl3 ?m?2 h?1, and 0.36±0.07 ?g C2Cl4 m?2 h?1. Extrapolated to a global scale, our emission estimates suggest a large potential source of 2 Tg CH3Cl yr?1 from tropical forests, which could account for the net budget discrepancy (underestimation of sources), as indicated previously. In addition, our estimates suggest a potential emission of 57±17\,Gg C2C4 yr?1 from tropical forest soils, equal to half of the currently missing C2Cl4 sources. We hypothesize that the extensive deforestation over the last two decades relates to the observed global downward trend of atmospheric methyl chloride

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

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

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

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

Total Observed Organic Carbon (TOOC): A synthesis of North American observations

Measurements of organic carbon compounds in both the gas and particle phases measured upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m^−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketene and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink

Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources

[1] A particle-into-liquid sampler (PILS) was coupled to a total organic carbon (TOC) analyzer for 3 s integrated measurements of water-soluble organic carbon (WSOC) in PM 1 ambient particles. The components of the instrument are described in detail. The PILS-TOC was deployed on the NOAA WP-3D aircraft during the NEAQS/ITCT 2004 program to investigate WSOC sources over the northeastern United States and Canada. Two main sources were identified: biomass burning emissions from fires in Alaska and northwestern Canada and emissions emanating from urban centers. Biomass burning WSOC was correlated with carbon monoxide (CO) and acetonitrile (r 2 > 0.88). These plumes were intercepted in layers at altitudes between 3 and 4 km and contained the highest fine particle volume and WSOC concentrations of the mission. Apart from the biomass burning influence, the lowest WSOC concentrations were recorded in rural air masses that included regions of significant biogenic emissions. Highest concentrations were at low altitudes in distinct plumes from urban centers. WSOC and CO were highly correlated (r 2 > 0.78) in these urban plumes. The ratio of the enhancement in WSOC relative to CO enhancement was found to be low ($3 mg C/m 3 /ppmv) in plumes that had been in transit for a short time, and increased with plume age, but appeared to level off at$32 ± 4 mg C/m 3 /ppmv after $1 day of transport from the sources. The results suggest that the production of WSOC in fine particles depends on compounds coemitted with CO and that this process is rapid with a time constant of$1 day. Citation: Sullivan, A. P., R. E. Peltier, C. A. Brock, J. A. de Gouw, J. S. Holloway, C. Warneke, A. G. Wollny, and R. J. Weber (2006), Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources

Intercomparison and evaluation of satellite peroxyacetyl nitrate observations in the upper troposphere-lower stratosphere

Peroxyacetyl nitrate (PAN) is an important chemical species in the troposphere as it aids the long-range transport of NOx and subsequent formation of O3 in relatively clean remote regions. Over the past few decades observations from aircraft campaigns and surface sites have been used to better understand the regional distribution of PAN. However, recent measurements made by satellites allow for a global assessment of PAN in the upper troposphere–lower stratosphere (UTLS). In this study, we investigate global PAN distributions from two independent retrieval methodologies, based on measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, on board Envisat from the Institute of Meteorology and Climate Research (IMK), Karlsruhe Institute of Technology, and the Department of Physics and Astronomy, University of Leicester (UoL). Retrieving PAN from MIPAS is challenging due to the weak signal in the measurements and contamination from other species. Therefore, we compare the two MIPAS datasets with observations from the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), in situ aircraft data and the 3-D chemical transport model TOMCAT. MIPAS shows peak UTLS PAN concentrations over the biomass burning regions (e.g. ranging from 150 to  >  200 pptv at 150 hPa) and during the summertime Asian monsoon as enhanced convection aids the vertical transport of PAN from the lower atmosphere. At 150 hPa, we find significant differences between the two MIPAS datasets in the tropics, where IMK PAN concentrations are larger by 50–100 pptv. Comparisons between MIPAS and ACE-FTS show better agreement with the UoL MIPAS PAN concentrations at 200 hPa, but with mixed results above this altitude. TOMCAT generally captures the magnitude and structure of climatological aircraft PAN profiles within the observational variability allowing it to be used to investigate the MIPAS PAN differences. TOMCAT–MIPAS comparisons show that the model is both positively (UoL) and negatively (IMK) biased against the satellite products. These results indicate that satellite PAN observations are able to detect realistic spatial variations in PAN in the UTLS, but further work is needed to resolve differences in existing retrievals to allow quantitative use of the products