Atmospheric residence time of CH3Br estimated from the junge spatial variability relation

The atmospheric residence time for methyl bromide (CH3Br) has been estimated as 0.8 +/- 0.1 years from its empirical spatial variability relative to C2H6, C2Cl4, CHCl3, and CH3Cl. This evaluation of the atmospheric residence time, based on Junge's 1963 general proposal, provides an estimate for CH3Br that is independent of source and sink estimates. Methyl bromide from combined natural and anthropogenic sources furnishes about half of the bromine that enters the stratosphere, where it plays an important role in ozone destruction. This residence time is consistent with the 0.7-year value recently calculated for CH3Br from the combined strength estimates for its known significant sinks

methane concentrations and source strengths in urban locations

Higher atmospheric concentrations of methane are found in air samples from urban locations than in contemporary samples at the same latitude in remote locations. Higher concentrations of several trace chlorocarbon gases are also found in the same urban samples than in the corresponding remote samples. The “urban excess”, i.e. urban concentration minus remote concentration, is generally 1000 to 2000 times larger on a molar basis for CH4 than for CCl3F. Because almost all CCl3F is emitted in urban environments, the urban release of CH4 is estimated from the observed molar ratios to be 30 to 60 megatons per year world‐wide. The fraction of world‐wide methane release occurring in the urban environment can be estimated from the concentration ratios, urban to remote, for CH4 vs. CCl3F. About 8% to 15% of the atmospheric methane release is observed to occur in urban locations. Copyright 1984 by the American Geophysical Union

Implications of the recent fluctuations in the growth rate of tropospheric methane

Global measurements show that the mixing ratio of tropospheric methane (CH4) increased by 1.1% (19.5 ± 1.7 ppbv) over the five-year period 1996-2000, with striking fluctuations in its annual growth rate. Whereas the global CH4 growth rate reached 15.9 ± 0.7 ppbv yr-1 in 1998, the growth rate was -2.1 ± 0.8 ppbv yr-1 in 2000. This is the first time in our 23-year global monitoring program that we have measured a negative annual CH4 growth rate. The CH4 growth rate fluctuates in an unpredictable fashion, and we reemphasize that global CH4 concentrations cannot be extrapolated into the future based on past trends. As a result, we suggest that the slowing of the CH4 growth rate during much of the 1980s and 1990s cannot be used to imply that CH4 will no longer be of concern in greenhouse gas studies during this century

Influence of biomass burning during recent fluctuations in the slow growth of global tropospheric methane

During the past 15 years the annual growth rate of tropospheric methane (CH4) has shown striking changes over 2-3 year periods, varying from + 1% yr-1 to slightly negative values (-0.2% yr-1). These fluctuations are superimposed on an overall slowdown of the CH4 growth rate since the 1980s. Here we use our complementary measurement of other compounds (ethane, tetrachloroethene) to confirm the influence of biomass burning on large global CH4 pulses in 1998 and 2002-2003. Methane growth rate fluctuations also track ENSO indices, most likely via the influence of ENSO activity on large-scale biomass burning. We also report the seventh year of near-zero growth of global CH4 levels (Dec. 1998-Dec. 2005). The global CH4 mixing ratio was 1772 ± 1 ppbv in 2005, and CH4 increases of 118-376 ppbv between 2000-2020 (ten scenarios in the 2001 IPCC report, to levels around 1900+ ppbv by 2020, now appear quite unlikely. Copyright 2006 by the American Geophysical Union

Seasonal variation of tropospheric methyl bromide concentrations: Constraints on anthropogenic input

Although removal of tropospheric methyl bromide (CH3Br) is dominated by the reaction with the seasonally varying hydroxyl (HO) radical concentration, the anticipated corresponding seasonal dependence of CH3Br, as found for other gases with major HO sinks, has been sought previously without success [WMO, 1995]. Our observations of northern hemispheric boundary layer CH3Br concentrations do reveal substantial seasonal changes. The high latitude CH3Br North/South interhemispheric concentration ratio (IHR) varies from a maximum of 1.35±0.04 (1σ) in March-April to 1.10±0.04 in September, with an equal area and seasonally (EAS) weighted average IHR of 1.21±0.03. These observations suggest northern hemispheric emissions are about 15 kilotons/year less than when an IHR of 1.3 is considered [WMO, 1995]. The observed seasonality also partially explains the differences in the IHR reported by several research groups [WMO, 1995] and places needed constraints on the magnitude and seasonality of sources and sinks of CH3Br

Spatiotemporal variation of methane and other trace hydrocarbon concentrations in the valley of Mexico

Mexico City is the world's largest and most polluted urban center. We examine the distribution of methane and other hydrocarbons within the Valley of Mexico, using it as a model for the role developing megacities will play in the next century of geochemical cycling. Seventy-five whole air samples were analyzed with multivariate statistical techniques, including factor analysis using principal components. Methane concentrations are highly variable in space and time, due to air circulations and source distribution. Landfills and open sewage canals are major inputs. Emissions into and out from the valley are modeled to be ∼515 t per day. Per capita emission is 0.01 t per annum per person, consistent with the global average for human related anaerobic generation. Natural gas leaks are small, and likely to be higher in other developing megacities; Mexican natural gas use has been discouraged out of earthquake safety concerns. In contrast, liquefied petroleum gas loss constitutes the major emission of propane and butane estimated at a leak rate of 5-10%. Kyoto and other environmental conventions have ignored methane as a greenhouse gas. Our analysis underscores the need to consider methane and other hydrocarbons, and the urbanization process, in future emission protocols. © 2002 Elsevier Science Ltd. All rights reserved

Estimation of global vehicular methyl bromide emissions: Extrapolation from a case study in Santiago, Chile

Between June 1 and June 8, 1996, 144 whole air samples were collected in Santiago, Chile. The temporal and geographical enhancement of CH3Br correlated with incomplete combustion tracers emitted from vehicles during the morning commute. From these, a city-wide CH3Br/CO volume emission ratio of 2.2 × 10-6 was measured in ambient air. Without using the CO measurements, we estimate an annual release of 8.9 tons of CH3Br in Santiago based solely upon enhanced concentrations observed throughout the study area during the morning traffic period. This enhancement corresponds to 8.0 × 10-6 kg CH3Br emitted for each liter of gasoline used (leaded and unleaded). By scaling the annual gasoline usage in Santiago to countries still using leaded gasoline, and assuming the above 8.0 × 10-6 kg/L value holds true, a global vehicular CH3Br emission of 4 ± 3 Gg/year is calculated. This small vehicular CH3Br emission source strength will not improve the current CH3Br budget imbalance