Atmospheric and Aerosol Chemistry

Sunlight is a major driving force of atmospheric processes. A detailed knowledge of atmospheric photochemistry is therefore required in order to understand atmospheric chemistry and climate. Considerable progress has been made in this field in recent decades. This contribution will highlight a set of new and emerging ideas (and will therefore not provide a complete review of the field) mainly dealing with long wavelength photochemistry both in the gas phase and on a wide range of environmental surfaces. Besides this, some interesting bulk photochemistry processes are discussed. Altogether these processes have the potential to introduce new chemical pathways into tropospheric chemistry and may impact atmospheric radical formation.

In this chapter we discuss some of the recent work directed at further understanding the chemistry of our atmosphere in regions of low NO _x , such as forests, where there are considerable emissions of biogenic volatile organic compounds, for example reactive hydrocarbons such as isoprene. Recent field measurements have revealed some surprising results, for example that OH concentrations are measured to be considerably higher than can be understood using current chemical mechanisms. It has also not proven possible to reconcile field measurements of other species, such as oxygenated VOCs, or emission fluxes of isoprene, using current mechanisms. Several complementary approaches have been brought to bear on formulating a solution to this problem, namely field studies using state-of-the-art instrumentation, chamber studies to isolate sub-sections of the chemistry, laboratory studies to measure rate coefficients, product branching ratios and photochemical yields, the development of ever more detailed chemical mechanisms, and high quality ab initio quantum theory to calculate the energy landscape for relevant reactions and to enable the rates of formation of products and intermediates for previously unknown and unstudied reactions to be predicted. The last few years have seen significant activity in this area, with several contrasting postulates put forward to explain the experimental findings, and here we attempt to synthesise the evidence and ideas.

Organic-aerosol phase partitioning (volatility) and oxidative aging are inextricably linked in the atmosphere because partitioning largely controls the rates and mechanisms of aging reactions as well as the actual amount of organic aerosol. Here we discuss those linkages, describing the basic theory of partitioning thermodynamics as well as the dynamics that may limit the approach to equilibrium under some conditions. We then discuss oxidative aging in three forms: homogeneous gas-phase oxidation, heterogeneous oxidation via uptake of gas-phase oxidants, and aqueous-phase oxidation. We present general scaling arguments to constrain the relative importance of these processes in the atmosphere, compared to each other and compared to the characteristic residence time of particles in the atmosphere.

Bio-organic chemicals are ubiquitous in the Earth’s atmosphere and at air-snow interfaces, as well as in aerosols and in clouds. It has been known for centuries that airborne biological matter plays various roles in the transmission of disease in humans and in ecosystems. The implication of chemical compounds of biological origins in cloud condensation and in ice nucleation processes has also been studied during the last few decades, and implications have been suggested in the reduction of visibility, in the influence on oxidative potential of the atmosphere and transformation of compounds in the atmosphere, in the formation of haze, change of snow-ice albedo, in agricultural processes, and bio-hazards and bio-terrorism. In this review we critically examine existing observation data on bio-organic compounds in the atmosphere and in snow. We also review both conventional and cutting-edge analytical techniques and methods for measurement and characterisation of bio-organic compounds and specifically for microbial communities, in the atmosphere and snow. We also explore the link between biological compounds and nucleation processes. Due to increased interest in decreasing emissions of carbon-containing compounds, we also briefly review (in an Appendix) methods and techniques that are currently deployed for bio-organic remediation.

Surface-active organic material is a key component of atmospheric aerosols. The presence of surfactants can influence aerosol heterogeneous chemistry, cloud formation, and ice nucleation. We review the current state of the science on the sources, properties, and impacts of surfactants in atmospheric aerosols.