Correlation-type structure activity relationships for the kinetics of gas-phase RO2 self-reactions and reaction with HO2

Structure activity relationships (SARs) are presented for the gas-phase reactions of RO2 with HO2, and the self- and cross-reactions of RO2. For RO2+HO2 the SAR is based upon a correlation between the logarithm of the measured rate coefficient and a calculated ionisation potential for the molecule R-CH=CH2, R being the same group in both the radical and molecular analogue. The correlation observed is strong and only for one RO2 species does the measured rate coefficient deviate by more than a factor of two from the linear least-squares regression line. For the self- and cross-reactions of RO2 radicals, the SAR is based upon a correlation between the logarithm of the measured rate coefficient and the calculated electrostatic potential (ESP) at the equivalent carbon atom in the RH molecule to which oxygen is attached in RO2, again R being the same group in the molecule and the radical. For cases where R is a simple alkyl-group, a strong linear correlation observed. For RO2 radicals which contain lone pair-bearing substituents and for which the calculated ESP<-0.05 self-reaction rate coefficients appear to be insensitive to the value of the ESP. For RO2 of this type with ESP>-0.05 a linear relationship between log k and the ESP is again observed. Using the relationships, 84 out of the 85 rate coefficients used to develop the SARs are predicted to within a factor of three of their measured values. A relationship is also presented that allows the prediction of the Arrhenius parameters for the self-reactions of simple alkyl RO2 radicals. On the basis of the correlations, predictions of room-temperature rate coefficients are made for a number of atmospherically important peroxyl-peroxyl radical reactions. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis of heterosulfamates. Search for structure-taste relationships

Thirty one new sodium heterosulfamates, RNHSO3Na, where the R portion contains mainly thiazole, benzothiazole, thiadiazole and pyridine ring structures, have been synthesized and their taste portfolios have been assessed. A database of 132 heterosulfamates ( both open-chain and cyclic) has been formed by combining these new compounds with an existing set of 101 heterosulfamates which were previously synthesized and for which taste data are available. Simple descriptors have been obtained using (i) measurements with Corey-Pauling-Koltun (CPK) space- filling models giving x, y and z dimensions and a volume VCPK, (ii) calculated first order molecular connectivities ((1)chi(v)) and (iii) the calculated Spartan program parameters to obtain HOMO, LUMO energies, the solvation energy E-solv and V-SPART AN. The techniques of linear (LDA) and quadratic (QDA) discriminant analysis and Tree analysis have then been employed to develop structure-taste relationships (SARs) that classify the sweet (S) and non-sweet (N) compounds into separate categories. In the LDA analysis 70% of the compounds were correctly classified ( this compares with 65% when the smaller data set of 101 compounds was used) and in the QDA analysis 68% were correctly classified ( compared to 80% previously). TheTree analysis correctly classified 81% ( compared to 86% previously). An alternative Tree analysis derived using the Cerius2 program and a set of physicochemical descriptors correctly classified only 54% of the compounds.

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.

Life cycle GHG assessment of fossil fuel power plants with carbon capture and storage

The evaluation of life cycle greenhouse gas emissions from power generation with carbon capture and storage (CCS) is a critical factor in energy and policy analysis. The current paper examines life cycle emissions from three types of fossil-fuel-based power plants, namely supercritical pulverized coal (super-PC), natural gas combined cycle (NGCC) and integrated gasification combined cycle (IGCC), with and without CCS. Results show that, for a 90% CO2 capture efficiency, life cycle GHG emissions are reduced by 75-84% depending on what technology is used. With GHG emissions less than 170 g/kWh, IGCC technology is found to be favorable to NGCC with CCS. Sensitivity analysis reveals that, for coal power plants, varying the CO2 capture efficiency and the coal transport distance has a more pronounced effect on life cycle GHG emissions than changing the length of CO2 transport pipeline. Finally, it is concluded from the current study that while the global warming potential is reduced when MEA-based CO2 capture is employed, the increase in other air pollutants such as NOx and NH3 leads to higher eutrophication and acidification potentials.

Age relationships beteen low level rock platforms and the high coastal slopes in Jersey and the surrounding area.

Recent research along the coastal cliffs and embayments of Jersey has revealed new aspects of the geomorphology of the rocky shore platform and its relationship with the steep slopes that link it to the island plateau above. Specifically, a rockhead platform meets a 10-30 m high, near vertical cliff at approximately 8-10 m above Jersey Datum (J.D.= ±0 m Ordnance Datum; likewise Guernsey Datum: G.D.), slopes down-towards mid-tide levels becoming ever more deeply dissected. Generalised contours of this platform show it to be distinct from a lower tidal rockhead platform which is comparatively smooth over large areas as it undergoes continuing contemporary abrasion. This lower platform is generally separated from the higher one by low cliffs, less than a metre high at mid-tidal levels, but two to three metres at the base of the backing cliffs. Both of these platforms are shown to antedate the Last Cold Stage (Devensian) head at a number of localities and this relationship is taken to represent the general situation, not only in Jersey, but throughout the other Channel Islands and adjacent coasts of Armorica. Whether either, or both, of these two platforms are older than Marine Oxygen Isotope Substage (MOIS) 5e (Ipswichian) as well is not known. However the considerable age of the numerous and wide intertidal shore platforms of the Channel Islands and adjacent coasts of Amorica makes a greater age quite possible.

Hespellia stercorisuis gen. nov., sp nov and Hespellia porcina sp nov., isolated from swine manure storage pits

Four Gram-positive-staining, strictly anaerobic, non-spore-forming, rod-shaped organisms were isolated from a pig manure storage pit. Comparative 16S rRNA gene sequence analysis revealed that the isolates belonged to two related but distinct groups. Sequence analysis showed that the two groups of isolates were highly related to each other (approx. 97% 16S rRNA gene sequence similarity), forming a distinct cluster within the Clostridium coccoides suprageneric rDNA grouping. Biochemical and physiological studies confirmed the division of the isolates into two related, albeit distinct, groups. Based on both phenotypic and phylogenetic evidence, it is proposed that the unidentified rod-shaped isolates from pig manure should be classified in a novel genus, Hespellia gen. nov., as Hespellia stercorisuis sp. nov. and Hespellia porcina sp. nov. The type species of the novel genus is H. stercorisuis (type strain, PC18(T) = NRRL B-23456(T) = CCUG 46279(T) = ATCC BAA-677(T)) and the type strain of H. porcina is PC80(T) (= NRRL B-23458(T) = ATCC BAA-674(T)).

Bacteroides coprosuis sp nov., isolated from swine-manure storage pits

Two Gram-negative, anaerobic, non-spore-forming, rod-shaped organisms were isolated from a swine-manure storage pit. Based on morphological and biochemical criteria, the strains were tentatively identified as belonging to the genus Bacteroides but they did not appear to correspond to any recognized species of the genus. Comparative 16S rRNA gene sequencing studies showed that the strains were related closely to each other and confirmed their placement in the genus Bacteroides, but sequence divergence values of > 10% from reference Bacteroides species demonstrated that the organisms from manure represent a novel species. Based on biochemical criteria and molecular genetic evidence, it is proposed that the unknown isolates from manure be assigned to a novel species of the genus Bacteroides, as Bacteroides coprosuis sp. nov. The type strain is PC139(T) (=CCUG 50528(T)=NRRL B-41113(T)).

Relationships between gluten rheological properties and hearth loaf characteristics

The rheological properties of fresh gluten in small amplitude oscillation in shear (SAOS) and creep recovery after short application of stress was related to the hearth breadbaking performance of wheat flours using the multivariate statistics partial least squares (PLS) regression. The picture was completed by dough mixing and extensional properties, flour protein size distribution determined by SE-HPLC, and high molecular weight glutenin subunit (HMW-GS) composition. The sample set comprised 20 wheat cultivars grown at two different levels of nitrogen fertilizer in one location. Flours yielding stiffer and more elastic glutens, with higher elastic and viscous moduli (G' and G") and lower tan 8 values in SAOS, gave doughs that were better able to retain their shape during proving and baking, resulting in breads of high form ratios. Creep recovery measurements after short application of stress showed that glutens from flours of good breadmaking quality had high relative elastic recovery. The nitrogen fertilizer level affected the protein size distribution by an increase in monomeric proteins (gliadins), which gave glutens of higher tan delta and flatter bread loaves (lower form ratio).

Effect of storage temperature and media composition on the survivability of Bifidobacterium breve NCIMB 702257 in a malt hydrolisate

The aim of this study was to evaluate the survivability of Bifidobacterium breve NCIMB 702257 in a three malt-based media supplemented with cysteine and yeast extract, and to determine the protective effect of these growth factors. A number of parameterised mathematical models were used to predict of kinetics of viability and total acidity during storage at different temperatures. Results demonstrated a good fit to the experimental mathematical model. The Arrhenius equations showed only reasonable fits and the polynomial plots contained a large area without data between 4 and 25 degrees C. In addition, it was shown that cysteine promotes growth and acid production by bifidobacteria, but does not extend survivability. On the other hand, increasing the yeast extract content of the fermentation media enhances the survivability of B. breve. To our knowledge, this is the first study to address the modelling of the survivability of probiotic bacteria in a cereal based fermentation media at different temperatures, introducing a more quantitative approach to the study of the shelf-life of a probiotic product. (C) 2009 Elsevier B.V. All rights reserved.

Viability of Salmonella enterica subsp. enterica during the preparation and cold storage of Egyptian soft cheeses and ice-cream

Changes occurring in the viability of Salmonella enterica subsp. enterica during the preparation and cold storage of Domiati cheese, Kariesh cheese and ice-cream were examined. A significant decrease in numbers was observed after whey drainage during the manufacture of Domiati cheese, but Salmonella remained viable for 13 weeks in cheeses prepared from milks with between 60 and 100 g/L NaCl; the viability declined in Domiati cheese made from highly salted milk during the later stages of storage. The method of coagulation used in the preparation of Kariesh cheese affected the survival time of the pathogen, and it varied from 2 to 3 weeks in cheeses made with a slow-acid coagulation method to 4-5 weeks for an acid-rennet coagulation method. This difference was attributed to the higher salt-in-moisture levels and lower pH values of Kariesh cheese prepared by the slow-acid coagulation method. A slight decrease in the numbers of Salmonella resulted from ageing ice-cream mix for 24 h at 0degreesC, but a greater reduction was evident after one day of frozen storage at -20degreesC. The pathogen survived further frozen storage for four months without any substantial change in numbers.

Influence of some processing and storage conditions on the mechanical properties of oat flakes

Flake breakage and texture are important quality, criteria in oat flakes. These properties are determined by the mechanical properties of the flakes, which may be influenced by process variables such as kilning and flake thickness. A pin deformation method was used to measure the rupture force of individual oat flakes at different water activities. The monolayer value of ground oat flakes ranged from 5.83 to 684 g/100 g dry matter Thick flakes were strongest, requiring 3.4 N to rupture the flake compared to 2.2 N for the thin flakes. Water softened the flakes, causing a decrease in rupture force from 3.6 N to 2.4 N as water activity; increased from 0.115 to 0.848. Kilning had a significant effect on flake thickness but not on the mechanical properties. This study suggests that oat flakes should be stored at water activity 0.4 or less as there is a sharp loss of flake strength above this point.