Dimethyl disulfide (DMDS) and dimethyl sulfide (DMS) emissions from biomass burning in Australia

We identify dimethyl disulfide (DMDS) as the major reduced sulfur-containing gas emitted from bushfires in Australia's Northern Territory. Like dimethyl sulfide (DMS), DMDS is oxidized in the atmosphere to sulfur dioxide (SO2) and methane sulfonic acid (MSA), which are intermediates in the formation of sulfuric acid (H2SO4). The mixing ratios of DMDS and DMS were the highest we have ever detected, with maximum values of 113 and 35 ppbv, respectively, whereas background values were below the detection limit (10 pptv). Molar emission ratios relative to carbon monoxide (CO) were [1.6 ± 0.1] × 10-5 and [6.2 ± 0.3] × 10-6, for DMDS and DMS respectively, while molar emission ratios relative to carbon dioxide (CO2) were [4.7 ± 0.4] × 10 6 and [1.4 ± 0.4] × 10 7, respectively. Assuming these observations are representative of biomass burning, we estimate that biomass burning could yield up to 175 Gg/yr of DMDS (119 Gg S/yr) and 13 Gg/yr of DMS

Nonmethane hydrocarbon and halocarbon distributions during Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange, June 1992

Aircraft measurements of selected nonmethane hydrocarbon and halocarbon species were made in the lower troposphere of the NE Atlantic near the Azores, Portugal, during June 1992 as part of the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange. In this paper, the impact of continental outflow from both Europe and North America on the study region were assessed. Four main air mass types were characterized from trajectories and trace gas concentrations: clean marine from the Atlantic, and continental air from the Iberian Peninsula, the British Isles and Northern Europe, and North America. Each classification exhibited trace gas concentrations that had been modified en route by photochemical processes and mixing. Comparison with the clean marine boundary layer (MBL) shows that the boundary layer of the predominantly continental air masses were enhanced in hydrocarbons and halocarbons by factors of approximately 2 for ethane, 5 for propane, 2-6 for ethyne and benzene, and 2-3 for C2Cl4. The same air masses also exhibited large ozone enhancements, with 2 to 3 times higher mixing ratios in the continental boundary layer air compared to the clean MBL. This indicates a primarily anthropogenic photochemical source for a significant fraction of the lower tropospheric ozone in this region. Methyl bromide exhibited on average 10-20% higher concentrations in the boundary layer affected by continental outflow than in the clean MBL, and was seen to be enhanced in individual plumes of air of continental origin. This is consistent with significant anthropogenic sources for methyl bromide. In addition, median MBL concentrations of ethene and methyl iodide showed enhancements of approximately a factor of 2 above free tropospheric values, suggesting primarily coastal/oceanic sources for these species. Copyright 1996 by the American Geophysical Union

The subtropical global plume in the Pacific Exploratory Mission-Tropics A (PEM-Tropics A), PEM-Tropics B, and the Global Atmospheric Sampling Program (GASP): How tropical emissions affect the remote Pacific

[1] An extended southern subtropical plume of CO meanders>15,000 km around the world, gradually spreading around 20 S. This southern pollution plume is most noticeable in the burning season, southern spring; a similar subtropical plume appears in the northern spring. We use tracer maps to guide the use of trajectories to trace observations of the plume to their origins. The MM5 mesoscale model provides high-resolution, near-global synoptic reconstructions of the weather. Two situations are analyzed: NASA’s airborne Pacific Exploratory Mission-Tropics A (PEM-Tropics A) period, September–October 1996 and the PEM-Tropics B period, March–April 1999. Similar features are noted for a much earlier mission in 1977, which apparently captured the first, but never-recognized, samples of the global pollution of the Southern Hemisphere. For PEM-Tropics A, near-source pieces of the plume are clearly seen in the Total Ozone Mapping Spectrometer (TOMS) absorbing aerosol product and are well simulated. Downwind, the aircraft sampling of several strands deriving from a single plume seems representative and well simulated. A general mechanism of the plume emerges: The southern plume arises in surface accumulation regions in Africa and Sout

Long-term decrease in the global atmospheric burden of tetrachloroethene (C2Cl4)

We present a 14-year record of tropospheric tetrachloroethene (C2Cl4) mixing ratios measured each season at remote surface locations throughout the Pacific Basin (71°N-47°S . Our calculated annual mean C2Cl4 mixing ratio for the extra-tropical northern hemisphere (NH) was 13.9 ± 0.5 pptv in 1989, but declined to less than half this value (to 6.5 ± 0.2 pptv) by 2002. Mid-latitude southern hemisphere (SH) mixing ratios, which were much smaller than NH values, showed interannual variations comparable to measured long-term changes, and the SH annual mean was slightly less in 2002 than in 1989. Driven by the relatively large decrease in NH values, the global C2Cl4, mixing ratio declined from 6.3 ± 0.6 pptv in 1989 to 3.5 ± 0.2 pptv in 2002. These values suggest that the global C2Cl4 burden decreased by roughly 205 Gg between 1989-2002, which is consistent with industrial estimates of declining NH emissions over a similar period. Copyright 2004 by the American Geophysical Union

Strong evidence for negligible methyl chloroform (CH3CCl3) emissions from biomass burning

With the phase-out of industrial methyl chloroform (MCF) production, the atmospheric burden of this ozone-depleting gas has rapidly declined. Therefore any non-industrial sources are taking on greater significance in the MCF budget. The only natural MCF source that has been proposed, biomass burning, has been reported to emit up to 2-10 Gg MCF yr-1. We have re-examined MCF data for thousands of airborne and ground-based air samples collected by our group since 1990 that were directly impacted by major biomass burning sources. Without exception, we have found no positive evidence that MCF is released from biomass burning. Our results indicate that global biomass burning emissions of MCF have been significantly overestimated and are unlikely to exceed 0.014 Gg MCF yr-1. Lowering the uncertainty regarding the magnitude of the global MCF biomass burning source may extend its period of usefulness for determining global abundances and trends of the hydroxyl radical (OH). Copyright 2007 by the American Geophysical Union

Latitudinal, vertical, and seasonal variations of C-1-C-4 alkyl nitrates in the troposphere over the Pacific Ocean during PEM-Tropics A and B: Oceanic and continental sources

We present concentration distributions of C1‐C4 alkyl nitrates observed during the NASA airborne campaigns Pacific Exploratory Mission (PEM) ‐Tropics A (September–October 1996) and PEM‐Tropics B (March–April 1999). The total geographic range for PEM‐Tropics A was 45°N–72°S latitude and 153°E–75°W longitude, and for PEM‐Tropics B was 40°N–36°S latitude and 149°E–75°W longitude. The maximum altitude for these missions was 12 km. These experiments provide the most extensive set of tropospheric measurements collected to date over the tropical Pacific Ocean. We observed high methyl nitrate (MeONO2, CH3ONO2) mixing ratios (approximately 50 pptv) at low altitudes in a latitude band between 8°N to 13°S stretching across the equatorial Pacific, illustrating the oceanic source of MeONO2. This source may be associated with the high‐nutrient, low‐chlorophyll character of equatorial Pacific waters. We discuss MeONO2 and ethyl nitrate (EtONO2, C2H5ONO2), whose abundance is dominated by equatorial oceanic sources, 2‐Propyl nitrate (2‐PrONO2, 2‐C3H7ONO2), which has significant oceanic and northern hemispheric (NH) sources associated with urban/industrial hydrocarbon emissions, and 2‐butyl nitrate (2‐BuONO2 2‐C4H8ONO2), which has mostly NH sources. PEM‐Tropics A and B resulted in remarkably similar equatorial mixing ratios. The excellent correlations between MeONO2 and the other alkyl nitrates in this region produced comparable correlation slopes between the two expeditions. By contrast, NH air masses influenced by urban/industrial emissions typically exhibited much lower MeONO2:EtONO2, MeONO2:2‐PrONO2, and MeONO2:2‐BuONO2 ratios. These relationships can be useful as a diagnostic of air mass origin. North of 10°N, the springtime PEM‐Tropics B mixing ratios of C2‐C4 alkyl nitrates were many‐fold higher at low‐mid altitudes than for late summer PEM‐Tropics A, consistent with strong continental outflow of NMHC precursors during spring

Hydrocarbon and halocarbon measurements as photochemical and dynamical indicators of atmospheric hydroxyl, atomic chlorine, and vertical mixing obtained during Lagrangian flights

Nonmethane hydrocarbons and halocarbons were measured during two Lagrangian experiments conducted in the lower troposphere of the North Atlantic as part of the June 1992, Atlantic Stratosphere Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) expedition. The first experiment was performed in very clean marine air. Meteorological observations indicate that the height of the marine boundary layer rose rapidly, entraining free tropospheric air. However, the free tropospheric and marine boundary layer halocarbon concentrations were too similar to allow this entrainment to be quantified by these measurements. The second Lagrangian experiment took place along the concentration gradient of an aged continental air mass advecting from Europe. The trace gas measurements confirm that the National Center for Atmospheric Research (NCAR) Electra aircraft successfully intercepted the same air mass on consecutive days. Two layers, a surface layer and a mixed layer with chemically distinct compositions, were present within the marine boundary layer. The composition of the free troposphere was very different from that of the mixed layer, making entrainment from the free troposphere evident Concentrations of the nonmethane hydrocarbons in the Lagrangian surface layer were observed to become depleted relative to the longer-lived tetrachloroethene. A best fit to the observations was calculated using various combinations of the three parameters, loss by reaction with hydroxyl, loss by reaction with chlorine, and/or dilution from the mixed layer. These calculations provided estimated average concentrations in the surface layer for a 5-hour period from dawn to 11 UT of 0.3±0.5 ×106 molecules cm-3 for HO, and 3.3±;1.1 ×104 molecules cm-3 for Cl. Noontime concentration estimates were 2.6±0.7 ×106 molecules cm-3 for HO and 6.5±1.4 ×104 molecules cm-3 for Cl. Copyright 1996 by the American Geophysical Union