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).

Alternating copolymerisation of styrene and carbon monoxide in ionic liquids

Room temperature ionic liquids have been used as solvents for the palladium-catalysed copolymerisation of styrene and carbon monoxide. The behaviour of various ionic liquids, the nature and concentration of palladium catalyst, and the reusability of the catalyst-ionic liquid system are discussed. The effects of cation, anion and alkyl chain length of the ionic liquids on the reaction are also addressed. The yield of the polyketone in the ionic liquid systems is enhanced over conventional solvents studied under similar conditions.

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.

Textile wastewater treatment using granular activated carbon adsorption in fixed beds

This work involved the treatment of industrial wastewater from a nylon carpet printing plant which currently receives no treatment and is discharged to sea. As nylon is particularly difficult to dye, acid dyes are required for successful coloration and cause major problems with the plant's effluent disposal in terms of color removal. Granular activated carbon Filtrasorb 400 was used to treat a ternary solution of acid dyes and the process plant effluent containing the dyes in a fixed-bed column system. Experimental data were correlated using the bed depth service time (BDST) model to previously published work by the authors for single dye adsorption. The results were expressed in terms of the BDST adsorption capacity, in milligrams of adsorbate per gram of adsorbent, and indicated that there was a 12-25% decrease iri adsorption capacity in the ternary system compared to the single component system; This reduction has been attributed to competitive adsorption occurring in the ternary component system. Dye adsorption from the process plant effluent showed an approximate 65% decrease in adsorption capacity compared to the ternary solution system. This has been attributed to interference caused by the other colorless textile effluent pollutants found in the process wastewater. A chemical oxygen demand analysis on these components indicated that the dyes accounted for only 14% of the total oxygen demand.

Carbon accumulation in peatlands of West Siberia over the last 2000 years

We use a network of cores from 77 peatland sites to determine controls on peat C content and peat C accumulation over the last 2000 years (since 2 ka) across Russia's West Siberian Lowland (WSL), the world's largest wetland region. Our results show a significant influence of fossil plant composition on peat C content, with peats dominated by Sphagnum having a lower C content. Radiocarbon-derived C accumulation since 2 ka at 23 sites is highly variable from site to site, but displays a significant N–S trend of decreasing accumulation at higher latitudes. Northern WSL peatlands show relatively small C accumulation of 7 to 35 kg C m-2 since 2 ka. In contrast, peatlands south of 60°N show larger accumulation of 42 to 88 kg C m-2. Carbon accumulation since 2 ka varies significantly with modern mean annual air temperature, with maximum C accumulation found between -1 and 0°C. Rates of apparent C accumulation since 2 ka show no significant relationship to long-term Holocene averages based on total C accumulation. A GIS-based extrapolation of our site data suggests that a substantial amount (~40%) of total WSL peat C has accumulated since 2 ka, with much of this accumulation south of 60°N. The large peatlands in the southern WSL may be an important component of the Eurasian terrestrial C sink, and future warming could result in a shift northward in long-term WSL C sequestration.

Carbon chemistry in Galactic bulge planetary nebulae

Galactic bulge planetary nebulae show evidence of mixed chemistry with emission from both silicate dust and polycyclic aromatic hydrocarbons (PAHs). This mixed chemistry is unlikely to be related to carbon dredge-up, as third dredge-up is not expected to occur in the low-mass bulge stars. We show that the phenomenon is widespread and is seen in 30 nebulae out of 40 of our sample, selected on the basis of their infrared flux. Hubble Space Telescope (HST) images and Ultraviolet and Visual Echelle Spectrograph (UVES) spectra show that the mixed chemistry is not related to the presence of emission-line stars, as it is in the Galactic disc population. We also rule out interaction with the interstellar medium (ISM) as origin of the PAHs. Instead, a strong correlation is found with morphology and the presence of a dense torus. A chemical model is presented which shows that hydrocarbon chains can form within oxygen-rich gas through gas-phase chemical reactions. The model predicts two layers, one at A_V~ 1.5, where small hydrocarbons form from reactions with C+, and one at A_V~ 4, where larger chains (and by implication, PAHs) form from reactions with neutral, atomic carbon. These reactions take place in a mini-photon-dominated region (PDR). We conclude that the mixed-chemistry phenomenon occurring in the Galactic bulge planetary nebulae is best explained through hydrocarbon chemistry in an ultraviolet (UV)-irradiated, dense torus.

The carbon abundance in main-sequence B-type stars towards the Galactic anti-centre

Differential carbon abundances (based on the C II doublet at 6580 Angstrom) are presented for eight early type stars, towards the Galactic anti-centre. All the stars have similar atmospheric parameters with effective temperatures in the range 25000-29000 K and surface gravities between log g = 3.9-4.3 dex. The derived photospheric abundances vary by up to 0.6 dex, and with the exception of one star, RLWT-41, the differential abundances are found to be closely correlated with those of nitrogen. This implies that both elements may have been formed by similar mechanisms and that the lack of correlation between the nitrogen and oxygen abundances previously found in this sample is not directly due to CNO-processed core material being mixed to the stellar surface.

Solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon, and carbon monoxide in 1-butyl-3-methylimidazolium tetrafluoroborate between temperatures 283 K and 343 K and at pressures close to atmospheric

Experimental values for the solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon and carbon monoxide in 1-butyl-3- methylimidazolium tetrafluoroborate, [bmim][BF4] - a room temperature ionic liquid - are reported as a function of temperature between 283 K and 343 K and at pressures close to atmospheric. Carbon dioxide is the most soluble gas with mole fraction solubilities of the order of 10-2. Ethane and methane are one order of magnitude more soluble than the other five gases that have mole fraction solubilities of the order of 10-4. Hydrogen is the less soluble of the gaseous solutes studied. From the variation of solubility, expressed as Henry's law constants, with temperature, the partial molar thermodynamic functions of solvation such as the standard Gibbs energy, the enthalpy, and the entropy are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations is of 1%. © 2005 Elsevier Ltd. All rights reserved.

Carbon flow in an upland grassland: effect of liming on the flux of recently photosynthesized carbon to rhizosphere soil

The effect of liming on the flow of recently photosynthesized carbon to rhizosphere soil was studied using (CO2)-C-13 pulse labelling, in an upland grassland ecosystem in Scotland. The use of C-13 enabled detection, in the field, of the effect of a 4-year liming period of selected soil plots on C allocation from plant biomass to soil, in comparison with unlimed plots. Photosynthetic rates and carbon turnover were higher in plants grown in limed soils than in those from unlimed plots. Higher delta(13)C% values were detected in shoots from limed plants than in those from unlimed plants in samples clipped within 15 days of the end of pulse labelling. Analysis of the aboveground plant production corresponding to the 4-year period of liming indicated that the standing biomass was higher in plots that received lime. Lower delta(13)C% values in limed roots compared with unlimed roots were found, whereas no significant difference was detected between soil samples. Extrapolation of our results indicated that more C has been lost through the soil than has been gained via photosynthetic assimilation because of pasture liming in Scotland during the period 1990-1998. However, the uncertainty associated with such extrapolation based on this single study is high and these estimates are provided only to set our findings in the broader context of national soil carbon emissions.

Galactic Bulge PNe:Carbon molecules in oxygen-rich environments

Galactic bulge planetary nebulae show evidence of mixed chemistry with emission from both silicate dust and PAHs. This mixed chemistry is unlikely to be related to carbon dredge up, as third dredge-up is not expected to occur in the low mass bulge stars. We show that the phenomenon is widespread, and is seen in 30 nebulae out of our sample of 40. A strong correlation is found between strength of the PAH bands and morphology, in particular, the presence of a dense torus. A chemical model is presented which shows that hydrocarbon chains can form within oxygen-rich gas through gas-phase chemical reactions. We conclude that the mixed chemistry phenomenon occurring in the galactic bulge planetary nebulae is best explained through hydrocarbon chemistry in an UV-irradiated, dense torus. © 2012 International Astronomical Union.

Tracking the Fate of Microbially Sequestered Carbon Dioxide in Soil Organic Matter

The microbial contribution to soil organic matter (SOM) has recently been shown to be much larger than previously thought and thus its role in carbon sequestration may also be underestimated. In this study we employ C-13 ((CO2)-C-13) to assess the potential CO2 sequestration capacity of soil chemoautotrophic bacteria and combine nuclear magnetic resonance (NMR) with stable isotope probing (SIP), techniques that independently make use of the isotopic enrichment of soil microbial biomass. In this way molecular information generated from NMR is linked with identification of microbes responsible for carbon capture. A mathematical model is developed to determine real-time CO2 flux so that net sequestration can be calculated. Twenty-eight groups of bacteria showing close homologies with existing species were identified. Surprisingly, Ralstonia eutropha was the dominant group. Through NMR we observed the formation of lipids, carbohydrates, and proteins produced directly from CO2 utilized by microbial biomass. The component of SOM directly associated with CO2 capture was calculated at 2.86 mg C (89.21 mg kg(-1)) after 48 h. This approach can,differentiate between SOM derived through microbial uptake of CO2 and other SOM constituents and represents a first step in tracking the fate and dynamics of microbial biomass in soil.

Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile-butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass-transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. Copyright © 2011 Wiley Periodicals, Inc.

Water efficiency as a means of reducing carbon emissions in Northern Ireland (NI) Water

The water and sewerage sectors' combined emissions account for just over 1% of total UK emissions, while household water heating accounts for a further 5%. Energy use, particularly electricity, is the largest source of emissions in the sector. Water efficiency measures should therefore result in reduced emissions from a lower demand for water and wastewater treatment and pumping, as well as from decreased domestic water heating. Northern Ireland Water (NI Water) is actively pursuing measures to reduce its carbon footprint. This paper investigated the carbon impacts of implementing a household water efficiency programme in Northern Ireland. Assuming water savings of 59.6 L/prop/day and 15% uptake among households, carbon savings of 0.6% of NI Water's current net operational emissions are achievable from reduced treatment and pumping. Adding the carbon savings from reduced household water heating gives savings equivalent to 6.2% of current net operational emissions. Cost savings to NI Water are estimated as 300,000 per year. The cost of the water efficiency devices is approximately 1.6 million, but may be higher depending on the number of devices distributed relative to the number installed. This paper has shown clear carbon benefits to water efficiency, but further research is needed to examine social and cost impacts. © IWA Publishing 2013.