Atmospheric Chemistry and Physics: From Air Pollution

Book Preface

The study of atmospheric chemistry as a scientific discipline goes back to the eighteenth century, when the principal issue was identifying the major chemical components of the atmosphere, nitrogen, oxygen, water, carbon dioxide, and the noble gases. In the late nineteenth and early twentieth centuries attention turned to the so-called trace gases, species present at less than 1 part per million parts of air by volume (1 μmol per mole). We now know that the atmostphere contains a myriad of trace species, some at levels as low as 1 part per trillion parts of air. The role of trace species is disproportionate to their atmospheric abundance; they are responsible for phenomena ranging from urban photochemical smog, to acid deposition, to stratospheric ozone depletion, to potential climate change. Moreover, the composition of the atmosphere is changing; analysis of air trapped in ice cores reveals a record of striking increases in the long-lived so-called greenhouse gases, carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Within the last century, concentrations of tropospheric ozone (O3), sulfate (SO4 2-), and carbonaceous aerosols in the Northern Hemisphere have increased significantly. There is evidence that all these changes are altering the basic chemistry of the atmosphere.

Atmospheric chemistry occurs within a fabric of profoundly complicated atmospheric dynamics. The results of this coupling of dynamics and chemistry are often unexpected. Witness the unique combination of dynamical forces that lead to a wintertime polar vortex over Antarctica, with the concomitant formation of polar stratospheric clouds that serve as sites for heterogeneous chemical reactions involving chlorine compounds resulting from anthropogenic chlorofluorocarbons—all leading to the near total depletion of stratospheric ozone over the South Pole each spring; witness the nonlinear, and counterintuitive, dependence of the amount of ozone generated by reactions involving hydrocarbons and oxides of nitrogen (NOx) at the urban and regional scale—although both hydrocarbons and NOx are ozone precursors, situations exist where continuous emission of more and more NOx actually leads to less ozone.

The chemical constituents of the atmosphere do not go through their life cycles independently; the cycles of the various species are linked together in a complex way. Thus a perturbation of one component can lead to significant, and nonlinear, changes to other components and to feedbacks that can amplify or damp the original perturbation.

In many respects, at once both the most important and the most paradoxical trace gas in the atmosphere is ozone (O3). High in the stratosphere, ozone screens living organisms from biologically harmful solar ultraviolet radiation; ozone at the surface, in the troposphere, can produce adverse effects on human health and plants when present at levels elevated above natural. At the urban and regional scale, significant policy issues concern how to decrease ozone levels by controlling the ozone precursors—hydrocarbons and oxides of nitrogen. At the global scale, understanding both the natural ozone chemistry of the troposphere and the causes of continually increasing background troposheric ozone levels is a major goal.