Motivated by increased losses of Antarctic stratospheric ozone and by improved understanding of the mechanism, a concept is suggested for action to arrest this ozone loss: injecting the alkanes ethane or propane (E or P) into the Antarctic stratosphere. A numerical model of chemical processes was used to explore the concept. The model results suggest that annual injections of about 50,000 tons of E or P could suppress ozone loss, but there are some scenarios where smaller E or P injections could increase ozone depletion. Further, key uncertainties must be resolved, induding initial concentrations of nitrogen-oxide species in austral spring, and several poorly defined physical and chemical processes must be quantifed. There would also be major difficulties in delivering and distributing the needed alkanes.

Economic and social projections indicate that during next several decades there will be major geographical redistribution of surface emissions of O3 precursors, such as NO(x), CH4 and CO. A net decrease in their emissions from northern hemispheric mid-latitudes will be accompanied by substantial increases from the tropics. We have investigated a hypothetical scenario of currently underway transition of such emission patterns using a global two-dimensional photochemical model. With overall O3 precursor releases held constant, a simultaneous transfer of their emissions by 25% from the latitude belt 75°N-35°N to 5°S-35°N increases tropospheric oxidizing capacity such that the methane global lifetime and concentrations fall by more than 3%. Seasonally dependent changes in surface O3 concentrations are also calculated. In influencing OH concentration, redistribution of surface NO(x) emissions is 2-3 orders of magnitude more efficient per unit mass than CO emissions. Shifts in methane sources have insignificant effects on global photochemistry, but lead to a decrease in its interhemispheric gradient.

All the signs are that global ozone depletion is increasing. Ideas to mitigate the problem that at first glance may seem far-fetched deserve more serious consideration and a scientific process of evaluation. © 1992 Nature Publishing Group.

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.

Injection of ethane or propane has been suggested as a means for reducing ozone loss within the Antarctic vortex because alkanes can convert active chlorine radicals into hydrochloric acid. In kinetic models of vortex chemistry including as heterogeneous processes only the hydrolysis and HCl reactions of ClONO2 and N2O5, parts per billion by volume levels of the light alkanes counteract ozone depletion by sequestering chlorine atoms. Introduction of the surface reaction of HCl with HOCl causes ethane to deepen baseline ozone holes and generally works to impede any mitigation by hydrocarbons. The increased depletion occurs because HCl + HOCl can be driven by HOx radicals released during organic oxidation. -from Authors

The sources and composition of atmospheric marine aerosol particles (aMA) have been investigated with a range of physical and chemical measurements from open-ocean research cruises. This study uses the characteristic functional group composition (from Fourier transform infrared spectroscopy) of aMA from five ocean regions to show the following: (i) The organic functional group composition of aMA that can be identified as mainly atmospheric primary marine (ocean derived) aerosol particles (aPMA) is 65 ± 12% hydroxyl, 21 ± 9% alkane, 6 ± 6% amine, and 7 ± 8% carboxylic acid functional groups. Contributions from photochemical reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal or continental emissions mix in alkane and carboxylic acid groups. (ii) The organic composition of aPMA is nearly identical to model-generated primary marine aerosol particles from bubbled seawater (gPMA, which has 55 ± 14% hydroxyl, 32 ± 14% alkane, and 13 ± 3% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied and the ratio of organic carbon to sodium (OC/Na+) in the gPMA remained nearly constant over a broad range of chlorophyll a concentrations, the gPMA alkane group fraction appeared to increase with chlorophyll a concentrations (r = 0.66). gPMA from productive seawater had a larger fraction of alkane functional groups (42 ± 9%) compared to gPMA from nonproductive seawater (22 ± 10%), perhaps due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of monosaccharides and disaccharides, where the seawater organic mass hydroxyl group peak location is closer to that of polysaccharides. This may result from the larger saccharides preferentially remaining in the seawater during gPMA and aPMA production.

Organic macromolecules constitute a high percentage of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean ecodynamics model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed for labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of proteins, polysaccharides and refractory heteropolycondensates. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally well within an order of magnitude. Global distributions are further estimated for both fractional coverage of bubble films at the air–water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant patterns. These results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.