A new oxidation catalyst system using fluorous cobalt(II) species in water-supercritical carbon dioxide (C-H free environment)

Stabilized water droplet dispersed in supercritical carbon dioxide fluid is demonstrated to be an excellent alternative solvent system to acetic acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions.

Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C-H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this 'greener' catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

An integrated assessment of carbon dioxide capture and storage in the UK

Geological carbon dioxide storage (CCS) has the potential to make a significant contribution to the decarbonisation of the UK. Amid concerns over maintaining security, and hence diversity, of supply, CCS could allow the continued use of coal, oil and gas whilst avoiding the CO2 emissions currently associated with fossil fuel use. This project has explored some of the geological, environmental, technical, economic and social implications of this technology. The UK is well placed to exploit CCS with a large offshore storage capacity, both in disused oil and gas fields and saline aquifers. This capacity should be sufficient to store CO2 from the power sector (at current levels) for a least one century, using well understood and therefore likely to be lower-risk, depleted hydrocarbon fields and contained parts of aquifers. It is very difficult to produce reliable estimates of the (potentially much larger) storage capacity of the less well understood geological reservoirs such as non-confined parts of aquifers. With the majority of its large coal fired power stations due to be retired during the next 15 to 20 years, the UK is at a natural decision point with respect to the future of power generation from coal; the existence of both national reserves and the infrastructure for receiving imported coal makes clean coal technology a realistic option. The notion of CCS as a ‘bridging’ or ‘stop-gap’ technology (i.e. whilst we develop ‘genuinely’ sustainable renewable energy technologies) needs to be examined somewhat critically, especially given the scale of global coal reserves. If CCS plant is built, then it is likely that technological innovation will bring down the costs of CO2 capture, such that it could become increasingly attractive. As with any capitalintensive option, there is a danger of becoming ‘locked-in’ to a CCS system. The costs of CCS in our model for UK power stations in the East Midlands and Yorkshire to reservoirs in the North Sea are between £25 and £60 per tonne of CO2 captured, transported and stored. This is between about 2 and 4 times the current traded price of a tonne of CO2 in the EU Emissions Trading Scheme. In addition to the technical and economic requirements of the CCS technology, it should also be socially and environmentally acceptable. Our research has shown that, given an acceptance of the severity and urgency of addressing climate change, CCS is viewed favourably by members of the public, provided it is adopted within a portfolio of other measures. The most commonly voiced concern from the public is that of leakage and this remains perhaps the greatest uncertainty with CCS. It is not possible to make general statements concerning storage security; assessments must be site specific. The impacts of any potential leakage are also somewhat uncertain but should be balanced against the deleterious effects of increased acidification in the oceans due to uptake of elevated atmospheric CO2 that have already been observed. Provided adequate long term monitoring can be ensured, any leakage of CO2 from a storage site is likely to have minimal localised impacts as long as leaks are rapidly repaired. A regulatory framework for CCS will need to include risk assessment of potential environmental and health and safety impacts, accounting and monitoring and liability for the long term. In summary, although there remain uncertainties to be resolved through research and demonstration projects, our assessment demonstrates that CCS holds great potential for significant cuts in CO2 emissions as we develop long term alternatives to fossil fuel use. CCS can contribute to reducing emissions of CO2 into the atmosphere in the near term (i.e. peak-shaving the future atmospheric concentration of CO2), with the potential to continue to deliver significant CO2 reductions over the long term.

Interaction of sulphur-containing aroma compounds with proteins in both model systems and real food systems

Irreversible binding of key flavour disulphides to ovalbumin has been shown previously to occur in model systems. The extent of binding is determined by the availability of the sulphydryl groups to participate in disulphide exchange, influenced either by pH, or the state of the protein (native or heat-denatured). In this study, two further proteins, one with sulphydryl groups available in the native state (beta-lactoglobulin) and one with no sulphydryl groups in the native state (lysozyme) were used to confirm this hypothesis. When the investigation was extended to real food systems, a similar effect was shown when a commercial meat flavouring containing disulphides was added to heat-denatured ovalbumin. Furthermore, comparison of the volatiles generated from onions, cooked either alone, or in the presence of meat, showed a significant reduction of key onion-derived disulphides when cooked in the presence of meat, and an even greater reduction of trisulphides. These findings may have implications for consumer acceptance of food products; where these compounds are used as flavourings or where they occur naturally.

Increased temperature sensitivity of net DOC production from ombrotrophic peat due to water table draw-down.

The production and release of dissolved organic carbon (DOC) from peat soils is thought to be sensitive to changes in climate, specifically changes in temperature and rainfall. However, little is known about the actual rates of net DOC production in response to temperature and water table draw-down, particularly in comparison to carbon dioxide (CO2) fluxes. To explore these relationships, we carried out a laboratory experiment on intact peat soil cores under controlled temperature and water table conditions to determine the impact and interaction of each of these climatic factors on net DOC production. We found a significant interaction (P < 0.001) between temperature, water table draw-down and net DOC production across the whole soil core (0 to −55 cm depth). This corresponded to an increase in the Q10 (i.e. rise in the rate of net DOC production over a 10 °C range) from 1.84 under high water tables and anaerobic conditions to 3.53 under water table draw-down and aerobic conditions between −10 and − 40 cm depth. However, increases in net DOC production were only seen after water tables recovered to the surface as secondary changes in soil water chemistry driven by sulphur redox reactions decreased DOC solubility, and therefore DOC concentrations, during periods of water table draw-down. Furthermore, net microbial consumption of DOC was also apparent at − 1 cm depth and was an additional cause of declining DOC concentrations during dry periods. Therefore, although increased temperature and decreased rainfall could have a significant effect on net DOC release from peatlands, these climatic effects could be masked by other factors controlling the biological consumption of DOC in addition to soil water chemistry and DOC solubility. These findings highlight both the sensitivity of DOC release from ombrotrophic peat to episodic changes in water table draw-down, and the need to disentangle complex and interacting controls on DOC dynamics to fully understand the impact of environmental change on this system.

Effects of sulphur nutrition during potato cultivation on the formation of acrylamide and aroma compounds during cooking

Lack of sulphur nutrition during potato cultivation has been shown to have profound effects on tuber composition, affecting in particular the concentrations of free asparagine, other amino acids and sugars. This is important because free asparagine and sugars react at high temperatures to form acrylamide, a suspect carcinogen. Free amino acids and sugars also form a variety of other compounds associated with colour and flavour. In this study the volatile aroma compounds formed in potato flour heated at 180 °C for 20 min were compared for three varieties of potato grown, with and without sulphur fertiliser. Approximately 50 compounds were quantified in the headspace extracts of the heated flour, of which over 40 were affected by sulphur fertilisation and/or variety. Many of the 41 compounds found at higher concentrations in the sulphur-deficient flour were Strecker aldehydes and compounds formed from their condensation, whereas only one compound, benzaldehyde, behaved in the same way as did acrylamide and was found at higher concentrations in the sulphur-sufficient flour. The reasons for these effects are discussed.

Cavity-enhanced absorption: detection of nitrogen dioxide and iodine monoxide using a violet laser diode

We present an application of cavity-enhanced absorption spectroscopy with an off-axis alignment of the cavity formed by two spherical mirrors and with time integration of the cavity-output intensity for detection of nitrogen dioxide (NO2) and iodine monoxide (IO) radicals using a violet laser diode at lambda = 404.278 nm. A noise-equivalent (1sigma = root-mean-square variation of the signal) fractional absorption for one optical pass of 4.5x10(-8) was demonstrated with a mirror reflectivity of similar to0.99925, a cavity length of 0.22 m and a lock-in-amplifier time constant of 3 s. Noise-equivalent detection sensitivities towards nitrogen dioxide of 1.8x10(10) molecule cm(-3) and towards the IO radical of 3.3x10(9) molecule cm(-3) were achieved in flow tubes with an inner diameter of 4 cm for a lock-in-amplifier time constant of 3 s. Alkyl peroxy radicals were detected using chemical titration with excess nitric oxide (RO2 + NO --> RO + NO2). Measurement of oxygen-atom concentrations was accomplished by determining the depletion of NO2 in the reaction NO2 + O --> NO + O-2. Noise-equivalent concentrations of alkyl peroxy radicals and oxygen atoms were 3x10(10) molecule cm(-3) in the discharge-flow-tube experiments.

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air water interface which removes material from the air water interface. We present evidence that the NO2 isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO3, and thin organic films as NO2 is usually present in high concentrations in these experimental systems and (2) the effect of NO2 air pollution on the unsaturated fatty acids and lipids found at the air liquid surface of human lung lining fluid.

Linking carbon and sulphur cycling during simulated drought cycles in peat from six sites across the UK

Water table draw-down is thought to increase peat decomposition and, therefore, DOC release. However, several studies have shown lower DOC concentrations during droughts relative to ‘normal’ periods with high water table. We carried out controlled incubation experiments at 10°C on 10x10 cm peat soil cores collected from six UK sites across a sulphur deposition gradient. Our aim was to quantify the balance between microbial consumption and chemical precipitation of DOC due to episodic acidification driven by sulphur redox reactions by comparing changes in soil water chemistry to microbial activity (i.e. soil respiration and trace gas fluxes). During dry periods, all sites showed a concurrent increase in SO4 and soil respiration and a decline in DOC. However, the magnitude of change in both DOC and SO4 varied considerably between sites according to historical sulphur deposition loads and the variation in acid/base chemistry.

Controls of carbon dioxide concentrations and fluxes above central London

Eddy-covariance measurements of carbon dioxide fluxes were taken semi-continuously between October 2006 and May 2008 at 190 m height in central London (UK) to quantify emissions and study their controls. Inner London, with a population of 8.2 million (~5000 inhabitants per km2) is heavily built up with 8% vegetation cover within the central boroughs. CO2 emissions were found to be mainly controlled by fossil fuel combustion (e.g. traffic, commercial and domestic heating). The measurement period allowed investigation of both diurnal patterns and seasonal trends. Diurnal averages of CO2 fluxes were found to be highly correlated to traffic. However changes in heating-related natural gas consumption and, to a lesser extent, photosynthetic activity that controlled the seasonal variability. Despite measurements being taken at ca. 22 times the mean building height, coupling with street level was adequate, especially during daytime. Night-time saw a higher occurrence of stable or neutral stratification, especially in autumn and winter, which resulted in data loss in post-processing. No significant difference was found between the annual estimate of net exchange of CO2 for the expected measurement footprint and the values derived from the National Atmospheric Emissions Inventory (NAEI), with daytime fluxes differing by only 3%. This agreement with NAEI data also supported the use of the simple flux footprint model which was applied to the London site; this also suggests that individual roughness elements did not significantly affect the measurements due to the large ratio of measurement height to mean building height.

The spatial distribution of carbon dioxide in an environmental test chamber

The spatial distribution of CO2 level in a classroom carried out in previous field work research has demonstrated that there is some evidence of variations in CO2 concentration in a classroom space. Significant fluctuations in CO2 concentration were found at different sampling points depending on the ventilation strategies and environmental conditions prevailing in individual classrooms. However, how these variations are affected by the emitting sources and the room air movement remains unknown. Hence, it was concluded that detailed investigation of the CO2 distribution need to be performed on a smaller scale. As a result, it was decided to use an environmental chamber with various methods and rates of ventilation, for the same internal temperature and heat loads, to study the effect of ventilation strategy and air movement on the distribution of CO2 concentration in a room. The role of human exhalation and its interaction with the plume induced by the body's convective flow and room air movement due to different ventilation strategies were studied in a chamber at the University of Reading. These phenomena are considered to be important in understanding and predicting the flow patterns in a space and how these impact on the distribution of contaminants. This paper attempts to study the CO2 dispersion and distribution at the exhalation zone of two people sitting in a chamber as well as throughout the occupied zone of the chamber. The horizontal and vertical distributions of CO2 were sampled at locations with a probability that CO2 variation is considered high. Although the room size, source location, ventilation rate and location of air supply and extract devices all can have influence on the CO2 distribution, this article gives general guidelines on the optimum positioning of CO2 sensor in a room.