A model for the photochemistry of the global troposphere constrained by observed concentrations of H2O, O3, CO, CH4, NO, NO2, and HNO3 is presented. Data for NO and NO2 are insufficient to define the global distribution of these gases but are nonetheless useful in limiting several of the more uncertain parameters of the model. Concentrations of OH, HO2, H2O2, NO, NO2, NO3, N2O5, HNO2, HO2NO2, CH3O2, CH3OOH, CH2O, and CH3CCl3 are calculated as functions of altitude, latitude, and season. Results imply that the source for nitrogen oxides in the remote troposphere is geographically dispersed and surprisingly small, less than 107 tons N yr−1. Global sources for CO and CH4 are 1.5 × 109 tons C yr−1 and 4.5 × 108 tons C yr−1, respectively. Carbon monoxide is derived from combustion of fossil fuel (15%) and oxidation of atmospheric CH4 (25%), with the balance from burning of vegetation and oxidation of biospheric hydrocarbons. Production of CO in the northern hemisphere exceeds that in the southern hemisphere by about a factor of 2. Industrial and agricultural activities provide approximately half the global source of CO. Oxidation of CO and CH4 provides sources of tropospheric O3 similar in magnitude to loss by in situ photochemistry. Observations of CH3CCl3 could offer an important check of the tropospheric model and results shown here suggest that computed concentrations of OH should be reliable within a factor of 2. A more definitive test requires better definition of release rates for CH3CCl3 and improved measurements for its distribution in the atmosphere.

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Tropospheric chemistry: A global perspective

Over the past decade it has become apparent that the atmosphere is a significant pathway for the transport of many natural and pollutant materials from the continents to the ocean. The atmospheric input of many of these species can have an impact (either positive or negative) on biological processes in the sea and on marine chemical cycling. For example, there is now evidence that the atmosphere may be an important transport path for such essential nutrients as iron and nitrogen in some regions. In this report we assess current data in this area, develop global scale estimates of the atmospheric fluxes of trace elements, mineral aerosol, nitrogen species, and synthetic organic compounds to the ocean; and compare the atmospheric input rates of these substances to their input via rivers. Trace elements considered were Pb, Cd, Zn, Cu, Ni, As, Hg, Sn, Al, Fe, Si, and P. Oxidized and reduced forms of nitrogen were considered, including nitrate and ammonium ions and the gaseous species NO, NO2, HNO3, and NH3. Synthetic organic compounds considered included polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), DDTs, chlordane, dieldrin, and hexachlorobenzenes (HCBs). Making this assessment was difficult because there are very few actual measurements of deposition rates of these substances to the ocean. However, there are considerably more data on the atmospheric concentrations of these species in aerosol and gaseous form. Mean concentration data for 10° × 10° ocean areas were determined from the available concentration data or from extrapolation of these data into other regions. These concentration distributions were then combined with appropriate exchange coefficients and precipitation fields to obtain the global wet and dry deposition fluxes. Careful consideration was given to atmospheric transport processes as well as to removal mechanisms and the physical and physicochemical properties of aerosols and gases. Only annual values were calculated. On a global scale atmospheric inputs are generally equal to or greater than riverine inputs, and for most species atmospheric input to the ocean is significantly greater in the northern hemisphere than in the southern hemisphere. For dissolved trace metals in seawater, global atmospheric input dominates riverine input for Pb, Cd, and Zn, and the two transport paths are roughly equal for Cu, Ni, As, and Fe. Fluxes and basin-wide deposition of trace metals are generally a factor of 5-10 higher in the North Atlantic and North Pacific regions than in the South Atlantic and South Pacific. Global input of oxidized and reduced nitrogen species are roughly equal to each other, although the major fraction of oxidized nitrogen enters the ocean in the northern hemisphere, primarily as a result of pollution sources. Reduced nitrogen species are much more uniformly distributed, suggesting that the ocean itself may be a significant source. The global atmospheric input of such synthetic organic species as HCH,PCBs, DDT, and HCB completely dominates their input via rivers.

The atmospheric input of trace species to the world ocean

17 ± 2 Tg; and optical depth at 0.63 mm, 0.030 ± 0.004. This emission, burden, and optical depth are significantly lower than some recent estimates. The model underestimates transport and deposition of East Asian and Australian dust to some regions of the Pacific Ocean. An underestimate of long-range transport of particles larger than 3 mm contributes to this bias. Our experiments support the hypothesis that dust emission ‘‘hot spots’’ exist in regions where alluvial sediments have accumulated and may be disturbed. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 4801 Oceanography: Biological and Chemical: Aerosols (0305); 5415 Planetology: Solid Surface Planets: Erosion and weathering; KEYWORDS: mineral dust aerosol, aerosol climatology, mineral deposition, aerosol scavenging, saltation sandblasting, ecosystem fertilization

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Mineral Dust Entrainment and Deposition (DEAD) model: Description and 1990s dust climatology

Preface Acknowledgements 1. Introduction 2. Atmospheric structure, composition and thermodynamics 3. The continuity and thermodynamic energy equations 4. The momentum equation in Cartesian and spherical coordinates 5. Vertical-coordinate conversions 6. Numerical solutions to partial differential equations 7. Finite-differencing the equations of atmospheric dynamics 8. Boundary-layer and surface processes 9. Radiative energy transfer 10. Gas-phase species, chemical reactions and reaction rates 11. Urban, free-tropospheric and stratospheric chemistry 12. Methods of solving chemical ordinary differential equations 13. Particle components, size distributions and size structures 14. Aerosol emission and nucleation 15. Coagulation 16. Condensation, evaporation, deposition and sublimation 17. Chemical equilibrium and dissolution processes 18. Cloud thermodynamics and dynamics 19. Irreversible aqueous chemistry 20. Sedimentation, dry deposition and air-sea exchange 21. Model design, application and testing Appendix A. Conversions and constants Appendix B. Tables References Index.

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Fundamentals of atmospheric modeling

Mass-independent fractionation (MIF) of sulfur isotopes has been reported in sediments of Archean and Early Proterozoic Age (>2.3 Ga) but not in younger rocks. The only fractionation mechanism that is consistent with the data on all four sulfur isotopes involves atmospheric photochemical reactions such as SO2 photolysis. We have used a one-dimensional photochemical model to investigate how the isotopic fractionation produced during SO2 photolysis would have been transferred to other gaseous and particulate sulfur-bearing species in both low-O2 and high-O2 atmospheres. We show that in atmospheres with O2 concentrations <10-5 times the present atmospheric level (PAL), sulfur would have been removed from the atmosphere in a variety of different oxidation states, each of which would have had its own distinct isotopic signature. By contrast, in atmospheres with O2 concentrations ≥10-5 PAL, all sulfur-bearing species would have passed through the oceanic sulfate reservoir before being incorporated into sediment...

W.G.N. Slinn

Papers

Some aspects of the transfer of atmospheric trace constituents past the air-sea interface