Radiative efficiency of trace gases is analytically calculated from infrared absorption spectra
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Peer-reviewed literature and scientific studies indicate that the radiative efficiency and climate impact of trace greenhouse gases are determined and calculated using their infrared absorption spectra and molecular properties.
Instantaneous normal mode (INM) theory was used to calculate absolute far-infrared absorption spectra of water, ammonia, and chloroform. Three procedures for weighting the INM density of states to yield absorption intensities were tested against spectra based on dipole time correlation functions generated from molecular dynamics (MD) simulations. Weighting method I, which utilizes only the rotational character of a mode in determining its contribution to absorption, performed slightly better than method II, a more exact treatment which incorporates the extent to which a mode is IR-active. Method III, which includes the contributions of induced dipoles, was successful in describing the influence of induced dipoles on the far-infrared spectra of the model liquids. The contribution to absorption of unstable modes with imaginary frequencies was found to be significant at low frequencies, and was treated by a simple approximation. Agreement between INM theory and the MD analysis was quite good for chloroform and ammonia, but less so for water. Agreement with experimental data in the range of 4–100 cm−1 was generally poor, but no worse than that for the MD calculations, primarily reflecting the simple intermolecular potentials used rather than the computational method itself.
Human activity has led to increased atmospheric concentrations of many gases, including halocarbons, and may lead to emissions of many more gases. Many of these gases are, on a per molecule basis, powerful greenhouse gases, although at present-day concentrations their climate effect is in the so-called weak limit (i.e., their effect scales linearly with concentration). We published a comprehensive review of the radiative efficiencies (RE) and global warming potentials (GWP) for around 200 such compounds in 2013 (Hodnebrog et al., 2013, https://doi.org/10.1002/rog.20013). Here we present updated RE and GWP values for compounds where experimental infrared absorption spectra are available. Updated numbers are based on a revised "Pinnock curve", which gives RE as a function of wave number, and now also accounts for stratospheric temperature adjustment (Shine & Myhre, 2020, https://doi.org/10.1029/2019MS001951). Further updates include the implementation of around 500 absorption spectra additional to those in the 2013 review and new atmospheric lifetimes from the literature (mainly from WMO (2019)). In total, values for 60 of the compounds previously assessed are based on additional absorption spectra, and 42 compounds have REs which differ by >10% from our previous assessment. New RE calculations are presented for more than 400 compounds in addition to the previously assessed compounds, and GWP calculations are presented for a total of around 250 compounds. Present-day radiative forcing due to halocarbons and other weak absorbers is 0.38 [0.33-0.43] W m<sup>-2</sup>, compared to 0.36 [0.32-0.40] W m<sup>-2</sup> in IPCC AR5 (Myhre et al., 2013, https://doi.org/10.1017/CBO9781107415324.018), which is about 18% of the current CO<sub>2</sub> forcing.
CFC-113a (CF3CCl3), CFC-112 (CFCl2CFCl2) and HCFC-133a (CF3CH2Cl) are three newly detected molecules in the atmosphere that are almost certainly emitted as a result of human activity. It is important to characterise the possible contribution of these gases to radiative forcing of climate change and also to provide information on the CO2-equivalence of their emissions. We report new laboratory measurements of absorption cross-sections of these three compounds at a resolution of 0.01 cm−1 for two temperatures 250 K and 295 K in the spectral range of 600–1730 cm−1. These spectra are then used to calculate the radiative efficiencies and global warming potentials (GWP). The radiative efficiencies are found to be between 0.15 and 0.3 W∙m−2∙ppbv−1. The GWP for a 100 year time horizon, relative to carbon dioxide, ranges from 340 for the relatively short-lived HCFC-133a to 3840 for the longer-lived CFC-112. At current (2012) concentrations, these gases make a trivial contribution to total radiative forcing; however, the concentrations of CFC-113a and HCFC-133a are continuing to increase. The 2012 CO2-equivalent emissions, using the GWP (100), are estimated to be about 4% of the current global CO2-equivalent emissions of HFC-134a.
We have investigated the physical characteristics of greenhouse gases (GHGs) to assess which properties are most important in determining the efficiency of a GHG. Chlorofluorcarbons (CFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), nitrogen fluorides, and various other known atmospheric trace molecules have been included in this study. Compounds containing the halogens F or Cl have in common very polar X-F or X-Cl bonds, particularly the X-F bonds. It is shown that as more F atoms bond to the same central atom, the bond dipoles become larger as a result of the central atom becoming more positive. This leads to a linear increase in the total or integrated XF bond dipole derivatives for the molecule, which leads to a non-linear (quadratic) increase in infrared (IR) intensity. Moreover, virtually all of the X-F bond stretches occur in the atmospheric IR window as opposed to X-H stretches, which do not occur in the atmospheric window. It is concluded that molecules possessing several F atoms will always have a large radiative forcing parameter in the calculation of their global warming potential. Some of the implications for global warming and climate change are discussed.
radiative heat flow away from it, which reduces the overall rate of upward radiative heat transfer. The increased concentration of greenhouse gases is
Greenhouse gases (GHGs) are the gases in an atmosphere that trap heat, raising the surface temperature of astronomical bodies such as Earth. Unlike other gases, greenhouse gases absorb the radiations that a planet emits, resulting in the greenhouse effect. The Earth is warmed by sunlight, causing its surface to radiate heat, which is then mostly absorbed by greenhouse gases. Without greenhouse gas
Greenhouse gases are infrared active, meaning that they absorb and emit infrared radiation in the same long wavelength range as what is emitted by the Earth's surface, clouds and atmosphere.
99% of the Earth's dry atmosphere (excluding water vapor) is made up of nitrogen (N2) (78%) and oxygen (O2) (21%). Because their molecules contain two atoms of the same element, they have no asymmetry in the distribution of their electrical charges, and so are almost totally unaffected by infrared thermal radiation, with only an extremely minor effect from collision-induced absorption. A further 0.9% of the atmosphere is made up by argon (Ar), which is monatomic, and so completely transparent to thermal radiation. On the other hand, carbon dioxide (0.04%), methane, nitrous oxide and even less abundant trace gases account for less than 0.1% of Earth's atmosphere, but because their molecules contain atoms of different elements, there is an asymmetry in electric charge distribution which allows molecular vibrations to interact with electromagnetic radiation. This makes them infrared active, and so their presence causes greenhouse effect.
The…
Greenhouse gas monitoring involves the direct measurement of atmospheric concentrations and direct and indirect measurement of greenhouse gas emissions. Indirect methods calculate emissions of greenhouse gases based on related metrics such as fossil fuel extraction.
There are several different methods of measuring carbon dioxide concentrations in the atmosphere, including infrared analyzing and manometry. Methane and nitrous oxide are measured by other instruments, such as the range-resolved infrared differential absorption lidar (DIAL). Greenhouse gases are measured from space such as by the Orbiting Carbon Observatory and through networks of ground stations such as the Integrated Carbon Observation System.
The Annual Greenhouse Gas Index (AGGI) is defined by atmospheric scientists at NOAA as the ratio of total direct radiative forcing due to long-lived and well-mixed greenhouse gases for any year for which adequate global measurements exist, to that present in year 1990. These radiative forcing levels are relative to those present in year…
Longwave infrared hyperspectral images can be used for gas plume analysis, as many gases exhibit distinct absorption features in this portion of the electromagnetic spectrum. In practice, accurately identifying weak gas signatures is difficult because the observed radiance is dominated by background radiance, which varies with material, temperature, and viewing conditions. Many gas plume analysis pipelines operate on single images, limiting the ability to leverage spatial and multi-view information that could enhance the analysis. The goal of this dissertation is to explore how machine learning and deep learning methods can complement classical approaches to improve gas plume identification in longwave infrared hyperspectral imagery, and to investigate the use of neural radiance fields for hyperspectral scene reconstruction.
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