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.

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.

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.

Fine-root turnover rates of European forests revisited: an analysis of data from sequential coring and ingrowth cores

Background and Aims Forest trees directly contribute to carbon cycling in forest soils through the turnover of their fine roots. In this study we aimed to calculate root turnover rates of common European forest tree species and to compare them with most frequently published values. Methods We compiled available European data and applied various turnover rate calculation methods to the resulting database. We used Decision Matrix and Maximum-Minimum formula as suggested in the literature. Results Mean turnover rates obtained by the combination of sequential coring and Decision Matrix were 0.86 yr−1 for Fagus sylvatica and 0.88 yr−1 for Picea abies when maximum biomass data were used for the calculation, and 1.11 yr−1 for both species when mean biomass data were used. Using mean biomass rather than maximum resulted in about 30 % higher values of root turnover. Using the Decision Matrix to calculate turnover rate doubled the rates when compared to the Maximum-Minimum formula. The Decision Matrix, however, makes use of more input information than the Maximum-Minimum formula. Conclusions We propose that calculations using the Decision Matrix with mean biomass give the most reliable estimates of root turnover rates in European forests and should preferentially be used in models and C reporting.

Temporal and spatial variability of surface fluxes over the ice edge zone in the northern Baltic Sea

Three land-fast ice stations (one of them was the Finnish research ice breaker Aranda) and the German research aircraft Falcon were applied to measure the turbulent and radiation fluxes over the ice edge zone in the northern Baltic Sea during the Baltic Air-Sea-Ice Study (BASIS) field experiment from 16 February to 6 March 1998. The temporal and spatial variability of the surface fluxes is discussed. Synoptic weather systems passed the experimental area in a rapid sequence and dominated the conditions (wind speed, airsurface temperature difference, cloud field) for the variability of the turbulent and radiation fluxes. At the ice stations, the largest upward sensible heat fluxes of about 100 Wm�2 were measured during the passage of a cold front when the air cooled faster (�5 K per hour) than the surface. The largest downward flux of about �200 Wm�2 occurred during warm air advection when the air temperature reached +10�C but the surface temperature remained at 0�C. Spatial variability of fluxes was observed from the small scale (scale of ice floes and open water spots) to the mesoscale (width of the ice edge zone). The degree of spatial variability depends on the synoptic situation: during melting conditions downward heat fluxes were the same over ice and open water, whereas during strong cold-air advection upward heat fluxes differed by more than 100 Wm�2. A remarkable amount of grey ice with intermediate surface temperature was observed. The ice in the Baltic Sea cannot be described by one ice type only.