This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 300 additional molecules important in different areas of atmospheric science have been added to the database. The compilation can be accessed through www.hitran.org. Most of the HITRAN data have now been cast into an underlying relational database structure that offers many advantages over the long-standing sequential text-based structure. The new structure empowers the user in many ways. It enables the incorporation of an extended set of fundamental parameters per transition, sophisticated line-shape formalisms, easy user-defined output formats, and very convenient searching, filtering, and plotting of data. A powerful application programming interface making use of structured query language (SQL) features for higher-level applications of HITRAN is also provided.

/pdf/the-hitran-2008-molecular-spectroscopic-database-1ud8clpej3.pdf

The HITRAN 2008 molecular spectroscopic database

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Methane is not considered here and has been reviewed in detail elsewhere. The model has a highly resolved spatial grid (0.5° × 0.5° latitude/longitude) and generates hourly average emission estimates. Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. Foliar density estimates are based on climatic variables and satellite data. Temporal variations in the model are driven by monthly estimates of biomass and temperature and hourly light estimates. The annual global VOC flux is estimated to be 1150 Tg C, composed of 44% isoprene, 11% monoterpenes, 22.5% other reactive VOC, and 22.5% other VOC. Large uncertainties exist for each of these estimates and particularly for compounds other than isoprene and monoterpenes. Tropical woodlands (rain forest, seasonal, drought-deciduous, and savanna) contribute about half of all global natural VOC emissions. Croplands, shrublands and other woodlands contribute 10–20% apiece. Isoprene emissions calculated for temperate regions are as much as a factor of 5 higher than previous estimates.

/pdf/a-global-model-of-natural-volatile-organic-compound-546vyk3ww5.pdf

A global model of natural volatile organic compound emissions

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

/pdf/the-formation-properties-and-impact-of-secondary-organic-4x4th6v9ke.pdf

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Hydrogen Storage in Metal–Organic Frameworks

The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies.

/pdf/organic-aerosol-and-global-climate-modelling-a-review-4ojfzx6x50.pdf

Organic aerosol and global climate modelling: a review

Vegetation provides a major source of reactive carbon entering the atmosphere. These compounds play an important role in (1) shaping global tropospheric chemistry, (2) regional photochemical oxidant formation, (3) balancing the global carbon cycle, and (4) production of organic acids which contribute to acidic deposition in rural areas. Present estimates place the total annual global emission of these compounds between approximately 500 and 825 Tg yr−1. The volatile olefinic compounds, such as isoprene and the monoterpenes, are thought to constitute the bulk of these emissions. However, it is becoming increasingly clear that a variety of partially oxidized hydrocarbons, principally alcohols, are also emitted. The available information concerning the terrestrial vegetation as sources of volatile organic compounds is reviewed. The biochemical processes associated with these emissions of the compounds and the atmospheric chemistry of the emitted compounds are discussed.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/92GB02125%4010.1002/%28ISSN%291944-9224.NATSOUR1

Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry

Diverse chemical pathways in the troposphere convert sulphur and nitrogen oxides and organic compounds into acids, involving the gas phase, the liquid phase (cloud, fog and rain water) and, possibly, certain suspended aerosols. The rates of acid generation are critically affected by the extent of generation of the oxidizing species and the kinetics of the reactions. Precipitation in the eastern United States shows a strong seasonal variation in deposition of sulphates in contrast to nitrates. Computer simulations can now rationalize the observed seasonal trends. Recent tropospheric measurements of gaseous hydrogen peroxide show that this gas is a major oxidant leading to sulphuric acid generation in cloud water.

Chemical mechanisms of acid generation in the troposphere

Organic peroxy radicals are important intermediates in the atmospheric photooxidation of hydrocarbons. Laboratory studies indicate that these radicals react among themselves (permutation reactions) at rates which should compete with those for reaction with HO2 and NOx under some atmospheric conditions. Using the available laboratory data, we have developed a simplified method of representing the large number of atmospheric peroxy radical permutation reactions, and have included this in a detailed mechanism of hydrocarbon photooxidation. The potential importance of these reactions was studied for relatively low NOx conditions such as may be observed in the marine planetary boundary layer (PBL) and the Amazon PBL. The effects of the permutation reactions include suppression of organic peroxy radical concentrations, higher HO2 and H2O2 concentrations, shorter lifetimes for PAN and other peroxyacyl nitrates (with concomitant faster release of NOx), and production of substantial concentrations of alcohols and organic acids (including acetic acid). If the kinetic and mechanistic data used in the present study are at least roughly realistic, the peroxy radical reactions probably play an important role in the photochemistry of the clean troposphere.

Permutation reactions of organic peroxy radicals in the troposphere

The mechanism of the HO-SO2 reaction

I. Importance of Alkanes in Atmospheric Chemistry of the Urban, Regional, and Global Scales II. Reactions of Alkanes with the Hydroxy Radical (OH) III. Kinetics and Mechanisms of Reactions of Cl, O(3P), NO3, and O3 with Alkanes IV. Mechanisms and End-Products of the Atmospheric Oxidation of Alkanes V. Reactions of Products of Alkane Reactions VI. Atmospheric Chemistry of the Haloalkanes VII. The Primary Photochemical Processes in the Alkanes, Haloalkanes, and Some of Their Oxidation Products VIII. Representation of the Atmospheric Chemistry of Alkanes in Models References

Jack G. Calvert

Papers

Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry

Chemical mechanisms of acid generation in the troposphere

Permutation reactions of organic peroxy radicals in the troposphere

The mechanism of the HO-SO2 reaction

The Mechanisms of Atmospheric Oxidation of the Alkenes