Carbon dioxide dynamics and controls in a deep-water wetland on the Qinghai-Tibetan Plateau

To initially characterize the dynamics and environmental controls of CO2, ecosystem CO2 fluxes were measured for different vegetation zones in a deep-water wetland on the Qinghai-Tibetan Plateau during the growing season of 2002. Four zones of vegetation along a gradient from shallow to deep water were dominated, respectively by the emergent species Carex allivescens V. Krez., Scirpus distigmaticus L., Hippuris vulgaris L., and the submerged species Potamogeton pectinatus L. Gross primary production (GPP), ecosystem respiration (Re), and net ecosystem production (NEP) were markedly different among the vegetation zones, with lower Re and GPP in deeper water. NEP was highest in the Scirpus-dominated zone with moderate water depth, but lowest in the Potamogeton-zone that occupied approximately 75% of the total wetland area. Diurnal variation in CO2 flux was highly correlated with variation in light intensity and soil temperature. The relationship between CO2 flux and these environmental variables varied among the vegetation zones. Seasonal CO2 fluxes, including GPP, Re, and NEP, were strongly correlated with aboveground biomass, which was in turn determined by water depth. In the early growing season, temperature sensitivity (Q(10)) for Re varied from 6.0 to 8.9 depending on vegetation zone. Q(10) decreased in the late growing season. Estimated NEP for the whole deep-water wetland over the growing season was 24 g C m(-2). Our results suggest that water depth is the major environmental control of seasonal variation in CO2 flux, whereas photosynthetic photon flux density (PPFD) controls diurnal dynamics.

The potential importance of grazing to the fluxes of carbon dioxide and methane in an alpine wetland on the Qinghai-Tibetan Plateau

To assess the impact of livestock grazing on the emission of greenhouse gases from grazed wetlands, we examined biomass growth of plants, CO2 and CH4 fluxes under grazing and non-grazing conditions on the Qinghai-Tibetan Plateau wetland. After the grazing treatment for a period of about 3 months, net ecosystem CO2 uptake and aboveground biomass were significantly smaller, but ecosystem CH4 emissions were remarkably greater, under grazing conditions than under non-grazing conditions. Examination of the gas-transport system showed that the increased CH4 emissions resulted from mainly the increase of conductance in the gas-transport system of the grazed plants. The sum of global warming potential, which was estimated from the measured CO2 and CH4 fluxes, was 5.6- to 11.3-fold higher under grazing conditions than under non-grazing conditions. The results suggest that livestock grazing may increase the global warming potential of the alpine wetlands. (c) 2005 Elsevier Ltd. All rights reserved.

Electroreduction of sulfur dioxide in some room-temperature ionic liquids

The mechanism of sulfur dioxide reduction at a platinum microelectrode was investigated by cyclic voltammetry in several room-temperature ionic liquids (RTILs)-[C(2)mim][NTf2], [C(4)mim][BF4], [C(4)mim][NO3], [C(4)mim][PF6], and [C(6)mim][Cl] where [C(2)mim] is 1-ethyl-3-methylimidazolium, [C(4)mim] is 1-butyl-3-methylimidazolium, [C(6)mim] is 1-hexyl-3-methylimidazolium, and [NTf2] is bis(trifluoromethylsufonyl)imide-with special attention paid to [C(4)mim][NO3] because of the well-defined voltammetry, high solubility, and relatively low diffusion coefficient of SO2 obtained in that ionic liquid. A cathodic peak is observed in all RTILs between -2.0 and -1.0 V versus a silver quasi-reference electrode. In [C(4)mim][NO3], the peak appears at -1.0 V, and potential step chronoamperometry was used to determine that SO2 has a very high solubility of 3100 (+/-450) mM and a diffusion coefficient of 5.0 (+/-0.8) x 10(-10) m(2) s(-1) in that ionic liquid. On the reverse wave, up to four anodic peaks are observed at ca. -0.4, -0.3, -0.2, and 0.2 V in [C(4)mim][NO3]. The cathodic wave is assigned to the reduction of SO2 to its radical anion, SO2-center dot. The peaks at -0.4 and -0.2 V are assigned to the oxidation of unsolvated and solvated SO2-center dot, respectively. The peak appearing at 0.2 V is assigned to the oxidation of either S2O42- or S2O4-center dot. The activation energy for the reduction of SO2 in [C(4)mim][NO3] was measured to be 10 (+/-2) kJ mol(-1) using chronoamperometric data at different temperatures. The stabilizing interaction of the solvent with the reduced species SO2-center dot leads to a different mechanism than that observed in conventional aprotic solvents. The high sensitivity of the system to SO2 also suggests that [C(4)mim][NO3] may be a viable solvent in gas sensing applications.

Kinetic analysis of the reaction between electrogenerated superoxide and carbon dioxide in the room temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and hexyltriethylammonium bis(trifluoromethylsulfonyl)imide

The reduction of oxygen in the presence of carbon dioxide has been investigated by cyclic voltammetry at a gold microdisk electrode in the two room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N-6222] [N(Tf)(2)]). With increasing levels of CO2, cyclic voltammetry shows an increase in the reductive wave and diminishing of the oxidative wave, indicating that the generated superoxide readily reacts with carbon dioxide. The kinetics of this reaction are investigated in both ionic liquids. The reaction was found to proceed via a DISP1 type mechanism in [EMIM][N(Tf)(2)] with an overall second-order rate constant of 1.4 +/- 0.4 x 10(3) M-1 s(-1). An ECE or DISP1 mechanism was determined to be the most likely pathway for the reaction in [N-6222][N(Tf)(2)], with an overall second-order rate constant of 1.72 +/- 0.45 x 10(3) m(-1) s(-1).

Effect of acetonitrile on the solubility of carbon dioxide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)amide, [C(2)mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 x 10(-2) in the pure ionic liquid at 303 K to a mole fraction of 1.3 x 10(-2) in the mixture [C(2)mim][NTf2] + CH3CN with x(CH3CN) = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [ C2mim][ NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with x(CH3CN) = 0.46 at 334 K. Negative excess molar volumes of approximately -1 cm(3) mol(-1) at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion-dipole interactions in the mixed liquid solvent.

Voltammetric Currents in Room Temperature Ionic Liquids Can Reflect Solutes Other Than the Electroactive Species and Are Influenced by Carbon Dioxide

The effects of such solutes such as halides and water on the physical properties of room temperature ionic liquids (RTILs) have been extensively studied, This work examines the effect of the solute carbon dioxide on the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C(2)mim][NTf2]) and its influence on the electrochemical characterization of the important redox couple ferrocene/ferrocenium (Fc/Fc(+)). The system was studied using cyclic voltammetry, chronoamperometry, and electron spin resonance (ESR) spectroscopy. Addition Of 100% CO2 to a solution of Fc in [C(2)mim][NTf2] resulted in a substantial increase in both the limiting oxidative current and diffusion coefficient of Fc. Arrhenius plots of Fc diffusion coefficients in the pure and CO2-saturated ionic liquid revealed a decrease in activation energy of translational diffusion from 29.0 (+/- 0.5) kJ mol(-1) to 14.7 (+/- 1.6) kJ mol(-1), suggesting a reduction in the viscosity of the ionic liquid with addition Of CO2. ESR spectroscopy was then used to calculate the rotational correlation coefficients of a probe molecule, 2,2,6,6-tetramethyl-1-piperinyloxyl (TEMPO), to add supporting evidence to this hypothesis. Arrhenius plots of rotational correlation coefficients in the pure and CO2-saturated ionic liquid resulted in a similar drop in activation energy from 28.7 (+/- 2.1) kJ mol(-1) to 18.2 (+/- 5.6) kJ mol(-1). The effect of this solute on the ionic liquid [C(2)mim][NTf2] and on the electrochemical measurements of the Fc/Fc(+) couple emphasizes the necessity of fastidious sample preparation, as it is clear that the voltammetric currents of the electroactive species under study are influenced by the presence of CO2 in solution. The voltammetric response of the electroactive species in RTILs cannot be assumed to be independent of other solutes.

FTIR analysis of water in supercritical carbon dioxide microemulsions using monofunctional perfluoropolyether surfactants

We describe perfluoropolyether (PFPE) surfactants which are capable of stabilising the water/CO2 interface and present FTIR spectroscopic evidence for the formation of water in supercritical carbon dioxide microemulsions. A wide variety of single chain surfactants of differing chain lengths but similar structure has been screened and the effect of the surfactant chain length on the water uptake was studied. The ammonium carboxylate of the PFPE surfactant Krytox FSL(TM) with an average molecular weight of 2500 g mol(-1) was demonstrated to be the surfactant capable of dissolving the most water out of all the tested surfactants and hence to have the optimum chain length. (C) 2002 Elsevier Science B.V. All rights reserved.