Summary for policymakers Technical summary 1. The climate system - an overview 2. Observed climate variability and change 3. The carbon cycle and atmospheric CO2 4. Atmospheric chemistry and greenhouse gases 5. Aerosols, their direct and indirect effects 6. Radiative forcing of climate change 7. Physical climate processes and feedbacks 8. Model evaluation 9. Projections of future climate change 10. Regional climate simulation - evaluation and projections 11. Changes in sea level 12. Detection of climate change and attribution of causes 13. Climate scenario development 14. Advancing our understanding Glossary Index Appendix.

Climate change 2001: the scientific basis

A rapid and accurate radiative transfer model (RRTM) for climate applications has been developed and the results extensively evaluated. The current version of RRTM calculates fluxes and cooling rates for the longwave spectral region (10–3000 cm−1) for an arbitrary clear atmosphere. The molecular species treated in the model are water vapor, carbon dioxide, ozone, methane, nitrous oxide, and the common halocarbons. The radiative transfer in RRTM is performed using the correlated-k method: the k distributions are attained directly from the LBLRTM line-by-line model, which connects the absorption coefficients used by RRTM to high-resolution radiance validations done with observations. Refined methods have been developed for treating bands containing gases with overlapping absorption, for the determination of values of the Planck function appropriate for use in the correlated-k approach, and for the inclusion of minor absorbing species in a band. The flux and cooling rate results of RRTM are linked to measurement through the use of LBLRTM, which has been substantially validated with observations. Validations of RRTM using LBLRTM have been performed for the midlatitude summer, tropical, midlatitude winter, subarctic winter, and four atmospheres from the Spectral Radiance Experiment campaign. On the basis of these validations the longwave accuracy of RRTM for any atmosphere is as follows: 0.6 W m−2 (relative to LBLRTM) for net flux in each band at all altitudes, with a total (10–3000 cm−1) error of less than 1.0 W m−2 at any altitude; 0.07 K d−1 for total cooling rate error in the troposphere and lower stratosphere, and 0.75 K d−1 in the upper stratosphere and above. Other comparisons have been performed on RRTM using LBLRTM to gauge its sensitivity to changes in the abundance of specific species, including the halocarbons and carbon dioxide. The radiative forcing due to doubling the concentration of carbon dioxide is attained with an accuracy of 0.24 W m−2, an error of less than 5%. The speed of execution of RRTM compares favorably with that of other rapid radiation models, indicating that the model is suitable for use in general circulation models.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/97JD00237

Radiative transfer for inhomogeneous atmospheres: RRTM, a validated correlated-k model for the longwave

From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids.

The use of fire as a tool to manipulate the environment has been instrumental in the human conquest of Earth, the first evidence of the use of fires by early hominids dating back to 1–1.5 million years ago [1]. Even today, most human-ignited vegetation fires take place on the African continent, and its widespread, frequently burned savannas bear ample witness to this. Although natural fires can occur even in tropical forest regions [2, 3], the extent of fires has greatly expanded on all continents with the arrival of Homo sapiens. Measurements of charcoal in dated sediment cores have shown clear correlations between the rate of burning and human settlement [4]. Pollen records show a shift with human settlement from pyrophobic vegetation to pyrotolerant and pyrophilic species, testimony to the large ecological impact of human-induced fires.

https://science.sciencemag.org/content/sci/250/4988/1669.full.pdf

Biomass Burning in the Tropics: Impact on Atmospheric Chemistry and Biogeochemical Cycles

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.

/pdf/tropospheric-chemistry-a-global-perspective-29u7u1il4s.pdf

Tropospheric chemistry: A global perspective

The reaction rate of N2O5 on sulphate aerosols is included in a model to predict global ozone loss and the column abundances of atmospheric gases Because the reaction of N2O5 and the aerosols can take place in the stratospheric sulphate aerosol layer, it is included in the 2D model so that the results can be compared to abundances derived from satellite data and ground-based measurements The N2O5/sulphate reaction is the only heterogeneous reaction in the model, in which aerosol loading is assumed to be constant and only diurnal values are examined The decadal ozone trends resulting from calculations based on the model are found to be closer to the observed values An important conclusion is that measurements of OH, ClO, HNO3, NO, and NO2 in the region of about 14-25 km are needed to examine significant changes in their abundances resulting from the inclusion of the N2O5/sulphate aerosol reaction

Role of heterogeneous conversion of N2O5 on sulphate aerosols in global ozone losses

The existence of a reverse circulation cell with rising motion in the polar lower stratosphere is suggested as an explanation for the temporal behavior of the ozone column density in the Antarctic region. The upwelling brings ozone-poor air from below 100 mbar to the stratosphere, possibly contributing to the observed ozone decline in early spring. At the same time, the Antarctic stratosphere might contain a very low concentration of NO(x), a condition that could favor a greatly enhanced catalytic removal of O3 by halogen species. It is argued that heterogeneous processes and formation of OClO by the reaction BrO+ClO - OClO+Br before and after the polar night might help to suppress the NO(x) levels during the early spring period.

Are antarctic ozone variations a manifestation of dynamics or chemistry

A two-dimensional model of sulfate aerosols has been developed. The model includes the sulfate precursor species H2S, CS2, DMS, OCS, and SO2. Microphysical processes simulated are homogeneous nucleation, condensation and evaporation, coagulation, and sedimentation. Tropospheric aerosols are removed by washout processes and by surface deposition. We assume that all aerosols are strictly binary water-sulfuric acid solutions without solid cores. The main source of condensation nuclei for the stratosphere is new particle formation by homogeneous nucleation in the upper tropical troposphere. A signficant finding is that the stratospheric aerosol mass may be strongly influenced by deep convection in the troposphere. This process, which could transport gas-phase sulfate precursors into the upper troposphere and lead to elevated levels of SO2 there, could potentially double the stratospheric aerosol mass relative to that due to OCS photooxidation alone. Our model is successful at reproducing the magnitude of stratospheric aerosol loading following the Mount Pinatubo eruption, but the calculated rate of decay of aerosols from the stratosphere is faster than that derived from observations.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/97JD00901

A two‐dimensional model of sulfur species and aerosols

Present anthropogenic emissions of CO are apparently large enough to perturb the natural CO-OH-CH4 cycle, which plays a crucial role in the self-cleansing processes in the troposphere. A significant increase in global concentrations of CO, CH4 CH3Cl, and other trace gases may result from a decrease in the OH concentration caused by continued CO emissions. Even if the CO emissions were maintained at the present rate, increases in CO and CH4 by the year 2025 might be as large as 50 and 25 percent, respectively. The time constants associated with the perturbations of the CO-OH-CH4 cycle are of the order of a few decades. Perturbation of this cycle may also indirectly affect stratospheric chemistry.

http://science.sciencemag.org/content/sci/195/4279/673.full.pdf

Anthropogenic CO Emissions: Implications for the Atmospheric CO-OH-CH4 Cycle

Results from a numerical model of the global emissions, transport, chemistry, and deposition of mercury (Hg) in the atmosphere are presented. Hg (in the form of Hg(0) and Hg(II)) is emitted into the atmosphere from natural and anthropogenic sources (estimated to be 4000 and 2100 Mg yr−1, respectively). It is distributed between gaseous, aqueous and particulate phases. Removal of Hg from the atmosphere occurs via dry deposition and wet deposition, which are calculated by the model to be 3300 and 2800 Mg yr−1, respectively. Deposition on land surfaces accounts for 47% of total global deposition. The simulated Hg ambient surface concentrations and deposition fluxes to the Earth's surface are consistent with available observations. Observed spatial and seasonal trends are reproduced by the model, although larger spatial variations are observed in Hg(0) surface concentrations than are predicted by the model. The calculated atmospheric residence time of Hg is ∼1.7 years. Chemical transformations between Hg(0) and Hg(II) have a strong influence on Hg deposition patterns because Hg(II) is removed faster than Hg(0). Oxidation of Hg(0) to Hg(II) occurs primarily in the gas phase, whereas Hg(II) reduction to Hg(0) occurs solely in the aqueous phase. Our model results indicated that in the absence of the aqueous reactions the atmospheric residence time of Hg is reduced to 1.2 from 1.7 years and the Hg surface concentration is ∼25% lower because of the absence of the Hg(II) reduction pathway. This result suggests that aqueous chemistry is an essential component of the atmospheric cycling of Hg.

Nien Dak Sze

Papers

Role of heterogeneous conversion of N2O5 on sulphate aerosols in global ozone losses

Are antarctic ozone variations a manifestation of dynamics or chemistry

A two‐dimensional model of sulfur species and aerosols

Anthropogenic CO Emissions: Implications for the Atmospheric CO-OH-CH4 Cycle

Global Simulation of Atmospheric Mercury Concentrations and Deposition Fluxes. Appendix Q