Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials

The atmospheric chemistry of several gases used in industrial applications, C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm3 molecule-1 s-1): k(OH + HFE-7200) = (6.9+2.3-1.7) × 10-11 exp(-(2030 ± 190)/T); k(OH + HFE-7100) = (2.8+3.2-1.5) × 10-11 exp(-(2200 ± 490)/T); k(OH + HFE-7000) = (2.0+1.2-0.7) × 10-11 exp(-(2130 ± 290)/T); and k(OH + C3F7CH2OH) = (1.4+0.3-0.2) × 10-11 exp(-(1460 ± 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO2 of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF3CF2CF2CH2OH, respectively.

Perfluorodecalin: global warming potential and first detection in the atmosphere

Perfluorodecalin (C10F18) has a range of medical uses that have led to small releases. Recently, it has been proposed as a carrier of vaccines, which could lead to significantly larger emissions. Since its emissions are controlled under the Kyoto Protocol, it is important that values for the global warming potential (GWP) are available. For a 50:50 mixture of the two isomers of perfluorodecalin, laboratory measurements, supplemented by theoretical calculations, give an integrated absorption cross-section of 3.91 x 10(-16) cm(2) molecule(-1) cm(-1) over the spectral region 0-1500 cm(-1); calculations yield a radiative efficiency of 0.56 W m(-2) ppbv(-1) and a 100-year GWP, relative to carbon dioxide, of 7200 assuming a lifetime of 1000 years. We report the first atmospheric measurements of perfluorodecalin, at Bristol, UK and Mace Head, Ireland, where volume mixing ratios are about 1.5 x 10(-15). At these concentrations, it makes a trivial contribution to climate change, but on a per molecule basis it is a potent greenhouse gas, indicating the need for careful assessment of its possible future usage. (c) 2005 Elsevier Ltd. All rights reserved.

The indirect global warming potential and global temperature change potential due to methane oxidation

Methane is the second most important anthropogenic greenhouse gas in the atmosphere next to carbon dioxide. Its global warming potential (GWP) for a time horizon of 100 years is 25, which makes it an attractive target for climate mitigation policies. Although the methane GWP traditionally includes the methane indirect effects on the concentrations of ozone and stratospheric water vapour, it does not take into account the production of carbon dioxide from methane oxidation. We argue here that this CO2-induced effect should be included for fossil sources of methane, which results in slightly larger GWP values for all time horizons. If the global temperature change potential is used as an alternative climate metric, then the impact of the CO2-induced effect is proportionally much larger. We also discuss what the correction term should be for methane from anthropogenic biogenic sources.

Infrared absorption spectra, radiative efficiencies, and global warming potentials of perfluorocarbons: Comparison between experiment and theory

Experimentally and theoretically determined infrared spectra are reported for a series of straight-chain perfluorocarbons: C2F6, C3F8, C4F10, C5F12, C6F14, and C8F18. Theoretical spectra were determined using both density functional (DFT) and ab initio methods. Radiative efficiencies (REs) were determined using the method of Pinnock et al. (1995) and combined with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). Theoretically determined absorption cross sections were within 10% of experimentally determined values. Despite being much less computationally expensive, DFT calculations were generally found to perform better than ab initio methods. There is a strong wavenumber dependence of radiative forcing in the region of the fundamental C-F vibration, and small differences in wavelength between band positions determined by theory and experiment have a significant impact on the REs. We apply an empirical correction to the theoretical spectra and then test this correction on a number of branched chain and cyclic perfluoroalkanes. We then compute absorption cross sections, REs, and GWPs for an additional set of perfluoroalkenes.

Simulating the impacts of global warming on wheat in China using a large area crop model

Temperature is one of the most prominent environmental factors that determine plant growth, devel- opment, and yield. Cool and moist conditions are most favorable for wheat. Wheat is likely to be highly vulnerable to further warming because currently the temperature is already close to or above optimum. In this study, the impacts of warming and extreme high temperature stress on wheat yield over China were investigated by using the general large area model (GLAM) for annual crops. The results showed that each 1±C rise in daily mean temperature would reduce the average wheat yield in China by about 4.6%{5.7% mainly due to the shorter growth duration, except for a small increase in yield at some grid cells. When the maximum temperature exceeded 30.5±C, the simulated grain-set fraction declined from 1 at 30.5±C to close to 0 at about 36±C. When the total grain-set was lower than the critical fractional grain-set (0.575{0.6), harvest index and potential grain yield were reduced. In order to reduce the negative impacts of warming, it is crucial to take serious actions to adapt to the climate change, for example, by shifting sowing date, adjusting crop distribution and structure, breeding heat-resistant varieties, and improving the monitoring, forecasting, and early warning of extreme climate events.

Radiative efficiencies and global warming potentials using theoretically determined absorption cross-sections for several hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs)

Integrated infrared cross-sections and wavenumber positions for the vibrational modes of a range of hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs) have been calculated. Spectra were determined using a density functional method with an empirically derived correction for the wavenumbers of band positions. Radiative efficiencies (REs) were determined using the Pinnock et al. method and were used with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). For the HFEs and the majority of the molecules in the HG series HFPEs, theoretically determined absorption cross-sections and REs lie within ca. 10% of those determined using measured spectra. For the larger molecules in the HG series and the HG′ series of HFPEs, agreement is less good, with theoretical values for the integrated cross-sections being up to 35% higher than the experimental values; REs are up to 45% higher. Our method gives better results than previous theoretical approaches, because of the level of theory chosen and, for REs, because an empirical wavenumber correction derived for perfluorocarbons is effective in predicting the positions of C–F stretching frequencies at around 1250 cm−1 for the molecules considered here.

Radiative efficiencies for fluorinated esters: indirect global warming potentials of hydrofluoroethers

Density Functional Theory (DFT) has been used with an empirically-derived correction for the wavenumbers of vibrational band positions to predict the infrared spectra of several fluorinated esters (FESs). Radiative efficiencies (REs) were then determined using the method of Pinnock et al. and these were used with atmospheric lifetimes from the literature to determine the direct global warming potentials of FESs. FESs, in particular fluoroalkylacetates, alkylfluoroacetates and fluoroalkylformates, are potential greenhouse gases and their likely long atmospheric lifetimes and relatively large REs, compared to their parent HFEs, make them active contributors to global warming. Here, we use the concept of indirect global warming potential (indirect GWP) to assess the contribution to the warming of several commonly used HFEs emitted from the Earth's surface, explicitly taking into account that these HFEs will be converted into the corresponding FESs in the troposphere. The indirect GWP can be calculated using the radiative efficiencies and lifetimes of the HFE and its degradation FES products. We found that the GWPs of those studied HFEs which have the smallest direct GWP can be increased by 100-1600% when taking account of the cumulative effect due to the secondary FESs formed during HFE atmospheric oxidation. This effect may be particularly important for non-segregated HFEs and some segregated HFEs, which may contribute significantly more to global warming than can be concluded from examination of their direct GWPs.

The proportionality of global warming to cumulative carbon emissions

The global temperature response to increasing atmospheric CO2 is often quantified by metrics such as equilibrium climate sensitivity and transient climate response1. These approaches, however, do not account for carbon cycle feedbacks and therefore do not fully represent the net response of the Earth system to anthropogenic CO2 emissions. Climate–carbon modelling experiments have shown that: (1) the warming per unit CO2 emitted does not depend on the background CO2 concentration2; (2) the total allowable emissions for climate stabilization do not depend on the timing of those emissions3, 4, 5; and (3) the temperature response to a pulse of CO2 is approximately constant on timescales of decades to centuries3, 6, 7, 8. Here we generalize these results and show that the carbon–climate response (CCR), defined as the ratio of temperature change to cumulative carbon emissions, is approximately independent of both the atmospheric CO2 concentration and its rate of change on these timescales. From observational constraints, we estimate CCR to be in the range 1.0–2.1 °C per trillion tonnes of carbon (Tt C) emitted (5th to 95th percentiles), consistent with twenty-first-century CCR values simulated by climate–carbon models. Uncertainty in land-use CO2 emissions and aerosol forcing, however, means that higher observationally constrained values cannot be excluded. The CCR, when evaluated from climate–carbon models under idealized conditions, represents a simple yet robust metric for comparing models, which aggregates both climate feedbacks and carbon cycle feedbacks. CCR is also likely to be a useful concept for climate change mitigation and policy; by combining the uncertainties associated with climate sensitivity, carbon sinks and climate–carbon feedbacks into a single quantity, the CCR allows CO2-induced global mean temperature change to be inferred directly from cumulative carbon emissions.

How difficult is it to recover from dangerous levels of global warming?

Climate models provide compelling evidence that if greenhouse gas emissions continue at present rates, then key global temperature thresholds (such as the European Union limit of two degrees of warming since pre-industrial times) are very likely to be crossed in the next few decades. However, there is relatively little attention paid to whether, should a dangerous temperature level be exceeded, it is feasible for the global temperature to then return to safer levels in a usefully short time. We focus on the timescales needed to reduce atmospheric greenhouse gases and associated temperatures back below potentially dangerous thresholds, using a state-of-the-art general circulation model. This analysis is extended with a simple climate model to provide uncertainty bounds. We find that even for very large reductions in emissions, temperature reduction is likely to occur at a low rate. Policy-makers need to consider such very long recovery timescales implicit in the Earth system when formulating future emission pathways that have the potential to 'overshoot' particular atmospheric concentrations of greenhouse gases and, more importantly, related temperature levels that might be considered dangerous.

Global warming potentials and radiative efficiencies of halocarbons and related compounds: a comprehensive review

In the mid-1970s it was recognized that, as well as being substances that deplete stratospheric ozone, chlorofluorocarbons (CFCs) were strong greenhouse gases that could have substantial impacts on radiative forcing of climate change. Around a decade later, this group of radiatively active compounds was expanded to include a large number of replacements for ozone-depleting substances such as chlorocarbons, hydrochlorocarbons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), bromofluorocarbons, and bromochlorofluorocarbons. This paper systematically reviews the published literature concerning the radiative efficiencies (REs) of CFCs, bromofluorocarbons and bromochlorofluorocarbons (halons), HCFCs, HFCs, PFCs, SF6, NF3, and related halogen containing compounds. In addition we provide a comprehensive and self-consistent set of new calculations of REs and global warming potentials (GWPs) for these compounds, mostly employing atmospheric lifetimes taken from the available literature. We also present Global Temperature change Potentials (GTPs) for selected gases. Infrared absorption spectra used in the RE calculations were taken from databases and individual studies, and from experimental and ab initio computational studies. Evaluations of REs and GWPs are presented for more than 200 compounds. Our calculations yield REs significantly (> 5%) different from those in the Intergovernmental Panel on Climate Change Fourth Assessment Report (AR4) for 49 compounds. We present new RE values for more than 100 gases which were not included in AR4. A widely-used simple method to calculate REs and GWPs from absorption spectra and atmospheric lifetimes is assessed and updated. This is the most comprehensive review of the radiative efficiencies and global warming potentials of halogenated compounds performed to date.

Why is the global warming proceeding much slower than expected?

Upper air observations from radiosondes and microwave satellite instruments does not indicate any global warming during the last 19 years, contrary to surface measurements, where a warming trend is supposedly being found. This result is somewhat difficult to reconcile, since climate model experiments do indicate a reverse trend, namely, that upper tropospheric air should warm faster than the surface. To contribute toward an understanding of this difficulty, we have here undertaken some specific experiments to study the effect on climate due to the decrease in stratospheric ozone and the Mount Pinatubo eruption in 1991. The associated forcing was added to the forcing from greenhouse gases, sulfate aerosols (direct and indirect effect), and tropospheric ozone, which was investigated in a separate series of experiments. Furthermore, we have undertaken an ensemble study in order to explore the natural variability of an advanced climate model exposed to such a forcing over 19 years. The result shows that the reduction of stratospheric ozone cools not only the lower stratosphere but also the troposphere, in particular, the upper and middle part. In the upper troposphere the cooling from stratospheric ozone leads to a significant reduction of greenhouse warming. The modeled stratospheric aerosols from Mount Pinatubo generate a climate response (stratospheric warming and tropospheric cooling) in good agreement with microwave satellite measurements. Finally, analysis of a series of experiments with both stratospheric ozone and the Mount Pinatubo effect shows considerable variability in climate response, suggesting that an evolution having no warming in the period is as likely as another evolution showing modest warming. However, the observed trend of no warming in the midtroposphere and clear warming at the surface is not found in the model simulations.

Impact of global warming on the interannual and interdecadal climate modes in a coupled GCM

In this study, we investigated the impact of global warming on the variabilities of large-scale interannual and interdecadal climate modes and teleconnection patterns with two long-term integrations of the coupled general circulation model of ECHAM4/OPYC3 at the Max-Planck-Institute for Meteorology, Hamburg. One is the control (CTRL) run with fixed present-day concentrations of greenhouse gases. The other experiment is a simulation of transient greenhouse warming, named GHG run. In the GHG run the averaged geopotential height at 500 hPa is increased significantly, and a negative phase of the Pacific/North American (PNA) teleconnection-like distribution pattern is intensified. The standard deviation over the tropics (high latitudes) is enhanced (reduced) on the interdecadal time scales and reduced (enhanced) on the interannual time scales in the GHG run. Except for an interdecadal mode related to the Southern Oscillation (SO) in the GHG run, the spatial variation patterns are similar for different (interannual + interdecadal, interannual, and interdecadal) time scales in the GHG and CTRL runs. Spatial distributions of the teleconnection patterns on the interannual and interdecadal time scales in the GHG run are also similar to those in the CTRL run. But some teleconnection patterns show linear trends and changes of variances and frequencies in the GHG run. Apart from the positive linear trend of the SO, the interdecadal modulation to the El Niño/SO cycle is enhanced during the GHG 2040 ∼ 2099. This is the result of an enhancement of the Walker circulation during that period. La Niña events intensify and El Niño events relatively weaken during the GHG 2070 ∼ 2090. It is interesting to note that with increasing greenhouse gas concentrations the relation between the SO and the PNA pattern is reversed significantly from a negative to a positive correlation on the interdecadal time scales and weakened on the interannual time scales. This suggests that the increase of the greenhouse gas concentrations will trigger the nonstationary correlation between the SO and the PNA pattern both on the interdecadal and interannual time scales.

Impact of global warming on the Asian winter monsoon in a coupled GCM

The Asian winter monsoon (AWM) response to the global warming was investigated through a long-term integration of the transient greenhouse warming with the ECHAM4/OPYC3 CGCM. The physics of the response was studied through analyses of the impact of the global warming on the variations of the ocean and land contrast near the ground in the Asian and western Pacific region and the east Asian trough and jet stream in the middle and upper troposphere. Forcing of transient eddy activity on the zonal circulation over the Asian and western Pacific region was also analyzed. It is found that in the global warming scenario the winter northeasterlies along the Pacific coast of the Eurasian continent weaken systematically and significantly, and intensity of the AWM reduces evidently, but the AWM variances on the interannual and interdecadal scales are not affected much by the global warming. It is suggested that the global warming makes the climate over the most part of Asia to be milder with enhanced moisture in winter. In the global warming scenario the contrasts of the sea level pressure and the near-surface temperature between the Asian continent and the Pacific Ocean become significantly smaller, northward and eastward shifts and weakening of the east Asian trough and jet stream in the middle and upper troposphere are found. As a consequence, the cold air in the AWM originating from the east Asian trough and high latitudes is less powerful. In addition, feedback of the transient activity also makes a considerable contribution to the higher-latitude shift of the jet stream over the North Pacific in the global warming scenario.