945 resultados para Evolved gas analysis
Resumo:
We used ground surveys to identify breeding habitat for Whimbrel (Numenius phaeopus) in the outer Mackenzie Delta, Northwest Territories, and to test the value of high-resolution IKONOS imagery for mapping additional breeding habitat in the Delta. During ground surveys, we found Whimbrel nests (n = 28) in extensive areas of wet-sedge low-centered polygon (LCP) habitat on two islands in the Delta (Taglu and Fish islands) in 2006 and 2007. Supervised classification using spectral analysis of IKONOS imagery successfully identified additional areas of wet-sedge habitat in the region. However, ground surveys to test this classification found that many areas of wet-sedge habitat had dense shrubs, no standing water, and/or lacked polygon structure and did not support breeding Whimbrel. Visual examination of the IKONOS imagery was necessary to determine which areas exhibited LCP structure. Much lower densities of nesting Whimbrel were also found in upland habitats near wetlands. We used habitat maps developed from a combination of methods, to perform scenario analyses to estimate the potential effects of the Mackenzie Gas Project on Whimbrel habitat. Assuming effective complete habitat loss within 20 m, 50 m, or 250 m of any infrastructure or pipeline, the currently proposed pipeline development would result in loss of 8%, 12%, or 30% of existing Whimbrel habitat. If subsidence were to occur, most Whimbrel habitat could become unsuitable. If the facility is developed, follow-up surveys will be required to test these models.
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The photochemical evolution of an anthropogenic plume from the New-York/Boston region during its transport at low altitudes over the North Atlantic to the European west coast has been studied using a Lagrangian framework. This plume, originally strongly polluted, was sampled by research aircraft just off the North American east coast on 3 successive days, and 3 days downwind off the west coast of Ireland where another aircraft re-sampled a weakly polluted plume. Changes in trace gas concentrations during transport were reproduced using a photochemical trajectory model including deposition and mixing effects. Chemical and wet deposition processing dominated the evolution of all pollutants in the plume. The mean net O3 production was evaluated to be -5 ppbv/day leading to low values of O3 by the time the plume reached Europe. Wet deposition of nitric acid was responsible for an 80% reduction in this O3 production. If the plume had not encountered precipitation, it would have reached the Europe with O3 levels up to 80-90 ppbv, and CO levels between 120 and 140 ppbv. Photochemical destruction also played a more important role than mixing in the evolution of plume CO due to high levels of both O3 and water vapour showing that CO cannot always be used as a tracer for polluted air masses, especially for plumes transported at low altitudes. The results also show that, in this case, an important increase in the O3/CO slope can be attributed to chemical destruction of CO and not to photochemical O3 production as is often assumed.
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The accurate prediction of storms is vital to the oil and gas sector for the management of their operations. An overview of research exploring the prediction of storms by ensemble prediction systems is presented and its application to the oil and gas sector is discussed. The analysis method used requires larger amounts of data storage and computer processing time than other more conventional analysis methods. To overcome these difficulties eScience techniques have been utilised. These techniques potentially have applications to the oil and gas sector to help incorporate environmental data into their information systems
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SMPS and DMS500 analysers were used to measure particulate size distributions in the exhaust of a fully annular aero gas turbine engine at two operating conditions to compare and analyse sources of discrepancy. A number of different dilution ratio values were utilised for the comparative analysis, and a Dekati hot diluter operating at a temperature of 623°K was also utilised to remove volatile PM prior to measurements being made. Additional work focused on observing the effect of varying the sample line temperatures to ascertain the impact. Explanations are offered for most of the trends observed, although a new, repeatable event identified in the range from 417°K to 423°K – where there was a three order of magnitude increase in the nucleation mode of the sample – requires further study.
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Stable isotopic characterization of chlorine in chlorinated aliphatic pollution is potentially very valuable for risk assessment and monitoring remediation or natural attenuation. The approach has been underused because of the complexity of analysis and the time it takes. We have developed a new method that eliminates sample preparation. Gas chromatography produces individually eluted sample peaks for analysis. The He carrier gas is mixed with Ar and introduced directly into the torch of a multicollector ICPMS. The MC-ICPMS is run at a high mass resolution of >= 10 000 to eliminate interference of mass 37 ArH with Cl. The standardization approach is similar to that for continuous flow stable isotope analysis in which sample and reference materials are measured successively. We have measured PCE relative to a laboratory TCE standard mixed with the sample. Solvent samples of 200 nmol to 1.3 mu mol ( 24- 165 mu g of Cl) were measured. The PCE gave the same value relative to the TCE as measured by the conventional method with a precision of 0.12% ( 2 x standard error) but poorer precision for the smaller samples.
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As the ideal method of assessing the nutritive value of a feedstuff, namely offering it to the appropriate class of animal and recording the production response obtained, is neither practical nor cost effective a range of feed evaluation techniques have been developed. Each of these balances some degree of compromise with the practical situation against data generation. However, due to the impact of animal-feed interactions over and above that of feed composition, the target animal remains the ultimate arbitrator of nutritional value. In this review current in vitro feed evaluation techniques are examined according to the degree of animal-feed interaction. Chemical analysis provides absolute values and therefore differs from the majority of in vitro methods that simply rank feeds. However, with no host animal involvement, estimates of nutritional value are inferred by statistical association. In addition given the costs involved, the practical value of many analyses conducted should be reviewed. The in sacco technique has made a substantial contribution to both understanding rumen microbial degradative processes and the rapid evaluation of feeds, especially in developing countries. However, the numerous shortfalls of the technique, common to many in vitro methods, the desire to eliminate the use of surgically modified animals for routine feed evaluation, paralleled with improvements in in vitro techniques, will see this technique increasingly replaced. The majority of in vitro systems use substrate disappearance to assess degradation, however, this provides no information regarding the quantity of derived end-products available to the host animal. As measurement of volatile fatty acids or microbial biomass production greatly increases analytical costs, fermentation gas release, a simple and non-destructive measurement, has been used as an alternative. However, as gas release alone is of little use, gas-based systems, where both degradation and fermentation gas release are measured simultaneously, are attracting considerable interest. Alternative microbial inocula are being considered, as is the potential of using multi-enzyme systems to examine degradation dynamics. It is concluded that while chemical analysis will continue to form an indispensable part of feed evaluation, enhanced use will be made of increasingly complex in vitro systems. It is vital, however, the function and limitations of each methodology are fully understood and that the temptation to over-interpret the data is avoided so as to draw the appropriate conclusions. With careful selection and correct application in vitro systems offer powerful research tools with which to evaluate feedstuffs. (C) 2003 Elsevier B.V. All rights reserved.
In vitro cumulative gas production techniques: History, methodological considerations and challenges
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Methodology used to measure in vitro gas production is reviewed to determine impacts of sources of variation on resultant gas production profiles (GPP). Current methods include measurement of gas production at constant pressure (e.g., use of gas tight syringes), a system that is inexpensive, but may be less sensitive than others thereby affecting its suitability in some situations. Automated systems that measure gas production at constant volume allow pressure to accumulate in the bottle, which is recorded at different times to produce a GPP, and may result in sufficiently high pressure that solubility of evolved gases in the medium is affected, thereby resulting in a recorded volume of gas that is lower than that predicted from stoichiometric calculations. Several other methods measure gas production at constant pressure and volume with either pressure transducers or sensors, and these may be manual, semi-automated or fully automated in operation. In these systems, gas is released as pressure increases, and vented gas is recorded. Agitating the medium does not consistently produce more gas with automated systems, and little or no effect of agitation was observed with manual systems. The apparatus affects GPP, but mathematical manipulation may enable effects of apparatus to be removed. The amount of substrate affects the volume of gas produced, but not rate of gas production, provided there is sufficient buffering capacity in the medium. Systems that use a very small amount of substrate are prone to experimental error in sample weighing. Effect of sample preparation on GPP has been found to be important, but further research is required to determine the optimum preparation that mimics animal chewing. Inoculum is the single largest source of variation in measuring GPP, as rumen fluid is variable and sampling schedules, diets fed to donor animals and ratios of rumen fluid/medium must be selected such that microbial activity is sufficiently high that it does not affect rate and extent of fermentation. Species of donor animal may also cause differences in GPP. End point measures can be mathematically manipulated to account for species differences, but rates of fermentation are not related. Other sources of inocula that have been used include caecal fluid (primarily for investigating hindgut fermentation in monogastrics), effluent from simulated rumen fermentation (e.g., 'Rusitec', which was as variable as rumen fluid), faeces, and frozen or freeze-dried rumen fluid (which were both less active than fresh rumen fluid). Use of mixtures of cell-free enzymes, or pure cultures of bacteria, may be a way of increasing GPP reproducibility, while reducing reliance on surgically modified animals. However, more research is required to develop these inocula. A number of media have been developed which buffer the incubation and provide relevant micro-nutrients to the microorganisms. To date, little research has been completed on relationships between the composition of the medium and measured GPP. However, comparing GPP from media either rich in N or N-free, allows assessment of contributions of N containing compounds in the sample. (c) 2005 Published by Elsevier B.V.
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Nested clade phylogeographic analysis (NCPA) is a popular method for reconstructing the demographic history of spatially distributed populations from genetic data. Although some parts of the analysis are automated, there is no unique and widely followed algorithm for doing this in its entirety, beginning with the data, and ending with the inferences drawn from the data. This article describes a method that automates NCPA, thereby providing a framework for replicating analyses in an objective way. To do so, a number of decisions need to be made so that the automated implementation is representative of previous analyses. We review how the NCPA procedure has evolved since its inception and conclude that there is scope for some variability in the manual application of NCPA. We apply the automated software to three published datasets previously analyzed manually and replicate many details of the manual analyses, suggesting that the current algorithm is representative of how a typical user will perform NCPA. We simulate a large number of replicate datasets for geographically distributed, but entirely random-mating, populations. These are then analyzed using the automated NCPA algorithm. Results indicate that NCPA tends to give a high frequency of false positives. In our simulations we observe that 14% of the clades give a conclusive inference that a demographic event has occurred, and that 75% of the datasets have at least one clade that gives such an inference. This is mainly due to the generation of multiple statistics per clade, of which only one is required to be significant to apply the inference key. We survey the inferences that have been made in recent publications and show that the most commonly inferred processes (restricted gene flow with isolation by distance and contiguous range expansion) are those that are commonly inferred in our simulations. However, published datasets typically yield a richer set of inferences with NCPA than obtained in our random-mating simulations, and further testing of NCPA with models of structured populations is necessary to examine its accuracy.
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Objective: To determine the risk of lung cancer associated with exposure at home to the radioactive disintegration products of naturally Occurring radon gas. Design: Collaborative analysis of individual data from 13 case-control studies of residential radon and lung cancer. Setting Nine European countries. Subjects 7148 cases Of lung cancer and 14 208 controls. Main outcome measures: Relative risks of lung cancer and radon gas concentrations in homes inhabited during the previous 5-34 years measured in becquerels (radon disintegrations per second) per cubic incite (Bq/m(3)) Of household air. Results: The mean measured radon concentration in homes of people in tire control group was 97 Bq/m(3), with 11% measuring > 200 and 4% measuring > 400 Bq/m(3). For cases of lung cancer the mean concentration was 104 Bq/m(3). The risk of lung cancer increased by 8.4% (95% confidence interval 3.0% to 15.8%) per 100 Bq/m(3) increase in measured radon (P = 0.0007). This corresponds to an increase of 16% (5% to 31%) per 100 Bq/m(3) increase in usual radon-that is, after correction for the dilution caused by random uncertainties in measuring radon concentrations. The dose-response relation seemed to be linear with no threshold and remained significant (P=0.04) in analyses limited to individuals from homes with measured radon < 200 Bq/m(3). The proportionate excess risk did not differ significantly with study, age, sex, or smoking. In the absence of other causes of death, the absolute risks of lung cancer by age 75 years at usual radon concentrations of 0, 100, and 400 Bq/m(3) would be about 0.4%, 0.5%, and 0.7%, respectively, for lifelong non-smokers, and about 25 times greater (10%, 12%, and 16%) for cigarette smokers. Conclusions: Collectively, though not separately, these studies show appreciable hazards from residential radon, particularly for smokers and recent ex-smokers, and indicate that it is responsible for about 2% of all deaths from cancer in Europe.
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The structures of trimethylchlorogermane ((CH3)(3)GeCl) and trimethylbromogermane ((CH3)(3)GeBr) have been determined by gas-phase electron diffraction (GED), augmented by the results from ab initio calculations employing second-order Moller-Plesset (MP2) level of theory and the 6-311+G(d) basis set. All the electrons were included in the correlation calculation. The results from the ab initio calculations indicated that these molecules have C-3v symmetry, and models with this symmetry were used in the electron diffraction analysis. The results for the principal distances (r(g)) and angles (angle(alpha)) from the combined GED/ab initio study of trimethylchlorogermane (with estimated 2sigma uncertainties) are: r(Ge-C) = 1.950(4) Angstrom, r(Ge-Cl) = 2.173(4) Angstrom, r(C-H) = 1.090(9) Angstrom, angleCGeC = 112.7(7)degrees, angleCGeCl = 106.0(8)degrees, angleGeCH = 107.8(12)degrees. The results for the principal distances (r(g)) and angles (angle(alpha)) from the combined GED/ab initio study of trimethylbromogermane (with estimated 2sigma uncertainties) are: r(Ge-C) = 1.952(7) Angstrom, r(Ge-Br) = 2.325(4) Angstrom, r(C-H) = 1. 140(28) Angstrom, angleCGeC = 114.2(11)degrees, angleCGeBr = 104.2(13)degrees, angleGeCH 106.9(43)degrees. Local C-3v symmetry and staggered conformation were assumed for the methyl groups.
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Time resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethylgermacyclopentene-3, have been carried out to obtain rate constants for its bimolecular reaction with acetylene, C2H2. The reaction was studied in the gas-phase over the pressure range 1-100 Tort, with SF6 as bath gas, at 5 temperatures in the range 297-553 K. The reaction showed a very slight pressure dependence at higher temperatures. The high pressure rate constants (obtained by extrapolation at the three higher temperatures) gave the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1)) (-10.94 +/- 0.05) + (6.10 +/- 0.36 kJ mol(-1))/RTln10. These Arrhenius parameters are consistent with a fast reaction occurring at approximately 30% of the collision rate at 298 K. Quantum chemical calculations (both DFT and ab initio G2//B3LYP and G2//QCISD) of the GeC2H4 potential energy surface (PES), show that GeH2 + C2H2 react initially to form germirene which can isomerise to vinylgermylene with a relatively low barrier. RRKM modelling, based on a loose association transition state, but assuming vinylgermylene is the end product (used in combination with a weak collisional deactivation model) predicts a strong pressure dependence using the calculated energies, in conflict with the experimental evidence. The detailed GeC2H4 PES shows considerable complexity with ten other accessible stable minima (B3LYP level), the three most stable of which are all germylenes. Routes through this complex surface were examined in detail. The only product combination which appears capable of satisfying the (P-3) + C2H4.C2H4 was confirmed as a product by GC observed lack of a strong pressure dependence is Ge(P-3) + C2H4. C2H4 was confirmed as a product by GC analysis. Although the formation of these products are shown to be possible by singlet-triplet curve crossing during dissociation of 1-germiranylidene (1-germacyclopropylidene), it seems more likely (on thermochernical grounds) that the triplet biradical, (GeCH2CH2.)-Ge-., is the immediate product precursor. Comparisons are made with the reaction of SiH2 with C2H2.
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The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.
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New "Pt-in-CeO2" catalyst prepared by microemulsion method is shown to give higher activity for a water-gas shift reaction but with no formation of CH4, the side product from hydrogenation of carbon oxides using a hydrogen-rich reformate as compared to conventional "Pt-on-CeO2" catalysts. Detailed characterization by DRIFT analysis and temperature programmed reduction presented in this work clearly suggest the ceria coverage on Pt inhibits the metal from forming a strong CO adsorption.
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This paper examines the life cycle GHG emissions from existing UK pulverized coal power plants. The life cycle of the electricity Generation plant includes construction, operation and decommissioning. The operation phase is extended to upstream and downstream processes. Upstream processes include the mining and transport of coal including methane leakage and the production and transport of limestone and ammonia, which are necessary for flue gas clean up. Downstream processes, on the other hand, include waste disposal and the recovery of land used for surface mining. The methodology used is material based process analysis that allows calculation of the total emissions for each process involved. A simple model for predicting the energy and material requirements of the power plant is developed. Preliminary calculations reveal that for a typical UK coal fired plant, the life cycle emissions amount to 990 g CO2-e/kWh of electricity generated, which compares well with previous UK studies. The majority of these emissions result from direct fuel combustion (882 g/kWh 89%) with methane leakage from mining operations accounting for 60% of indirect emissions. In total, mining operations (including methane leakage) account for 67.4% of indirect emissions, while limestone and other material production and transport account for 31.5%. The methodology developed is also applied to a typical IGCC power plant. It is found that IGCC life cycle emissions are 15% less than those from PC power plants. Furthermore, upon investigating the influence of power plant parameters on life cycle emissions, it is determined that, while the effect of changing the load factor is negligible, increasing efficiency from 35% to 38% can reduce emissions by 7.6%. The current study is funded by the UK National Environment Research Council (NERC) and is undertaken as part of the UK Carbon Capture and Storage Consortium (UKCCSC). Future work will investigate the life cycle emissions from other power generation technologies with and without carbon capture and storage. The current paper reveals that it might be possible that, when CCS is employed. the emissions during generation decrease to a level where the emissions from upstream processes (i.e. coal production and transport) become dominant, and so, the life cycle efficiency of the CCS system can be significantly reduced. The location of coal, coal composition and mining method are important in determining the overall impacts. In addition to studying the net emissions from CCS systems, future work will also investigate the feasibility and technoeconomics of these systems as a means of carbon abatement.