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Two distributed-feedback (InGaAsP) diode lasers were used to record high-resolution absorption spectra of the parallel and the perpendicular components of the 2nu(4) band of methyl chloride (CH(3)Cl) and the 2nu(3) band of methane (CH(4)) near 1.65 mum. The room-temperature absorption measurements, which were conducted in a multipass cell with a variable path length (878-1020 cm), were used to determine the mole fractions of the constituent gases and thus demonstrate species-specific, nonintrusive concentration measurements of species with overlapping spectra.
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PMID:Diode laser absorption measurements of CH(3)Cl and CH(4) near 1.65 microm. 1825 37

Single-shot vibrational Raman measurements were performed along an 11-mm-long line crossing the reaction zone in a premixed, fuel-rich (phi = 10), laminar methane-air flame by use of a frequency-tripled Nd:YAG laser with a 355-nm emission wavelength. This laser source seems to have advantages relative to KrF excimer lasers as well as to Nd:YAG lasers at 532 nm for hydrocarbon combustion diagnostics. The Raman emissions of all major species (N(2), O(2), CH(4), H(2), CO(2), H(2)O) were detected simultaneously with a spatial resolution of 0.4 mm. By integration over selected spectral intervals, the mole fractions of all species and subsequently the local gas temperatures have been obtained. A comparison of the temperatures that were found with results from filtered Rayleigh experiments showed good agreement, indicating the success of what are to the best of our knowledge the first one-dimensional single-shot Raman measurements in a sooting hydrocarbon flame.
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PMID:One-Dimensional, Time-Resolved Raman Measurements in a Sooting Flame made with 355-nm Excitation. 1828 63

The design and application of a novel automated room-temperature laser spectrometer are reported. The compact instrument is based on difference-frequency generation in bulk LiNbO(3). The instrument employs a tunable cw external-cavity diode laser (795-825 nm) and a pulsed diode-pumped Nd:YAG laser (1064 nm). The generated mid-IR nanosecond pulses of 50-microW peak power and 6.5-kHz repetition rate, continuously tunable from 3.16 to 3.67 microm, are coupled into a 36-m multipass cell for spectroscopic studies. On-line measurements of methane are performed at concentrations between 200 ppb (parts in 10(9) by mole fraction) and approximately 1%, demonstrating a large dynamic range of 7 orders of magnitude. Furthermore computer-controlled multicomponent analysis of a mixture containing five trace gases and water vapor with an overall response time of 90 s at an averaging time of only approximately 30 s is reported. A minimum detectable absorption coefficient of 1.1 x 10(-7) cm(-1) has been achieved in an averaging time of 60 s, enabling detection limits in the ppb range for many important trace gases, such as CH(4), C(2)H(6), H(2)CO, NO(2), N(2)O, HCl, HBr, CO, and OCS.
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PMID:On-line multicomponent trace-gas analysis with a broadly tunable pulsed difference-frequency laser spectrometer. 1832 56

Biocatalyzed electrolysis is a microbial fuel cell based technology for the generation of hydrogen gas and other reduced products out of electron donors. Examples of electron donors are acetate and wastewater. An external power supply can support the process and therefore circumvent thermodynamical constraints that normally render the generation of compounds such as hydrogen unlikely. We have investigated the possibility of biocatalyzed electrolysis for the generation of methane. The cathodically produced hydrogen could be converted into methane at a ratio of 0.41 mole methane mole(-1) acetate, at temperatures of 22+/-2 degrees C. The anodic oxidation of acetate was not hampered by ammonium concentrations up to 5 g N L(-1). An overview is given of potential applications for biocatalyzed electrolysis.
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PMID:Combining biocatalyzed electrolysis with anaerobic digestion. 1835 98

Producing liquid hydrocarbon fuels with a reduced greenhouse gas emissions profile would ease the transition to a carbon-neutral energy sector with the transportation industry being the immediate beneficiary followed by the power industry. Revolutionary solutions in transportation, such as electricity and hydrogen, depend on the deployment of carbon capture and storage technologies and/or renewable energy systems. Additionally, high oil prices may increase the development of unconventional sources, such as tar sands, that have a higher emissions profile. One process that is gaining interest is a system for producing reduced carbon fuels though chemical looping technologies. An investigation of the implications of such a process using methane and carbon dioxide that is reformed to yield methanol has been done. An important aspect of the investigation is the use of off-the-shelf technologies to achieve the results. The ability of the process to yield reduced emissions fuels depends on the source for the feed and process heat. For the range of conditions considered, the emissions profile of methanol produced in this method varies from 0.475 to 1.645 moles carbon dioxide per mole methanol. The upper bound can be lowered to 0.750 by applying CCS and/ or using nonfossil heat sources for the reforming. The process provides an initial pathway to incorporate CO2 into fuels independent of electrolytic hydrogen or developments in other sectors of the economy.
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PMID:An investigation of synthetic fuel production via chemical looping. 1849 14

The development of granular sludge in thermophilic (55 degrees C) upflow anaerobic sludge blanket reactors was investigated. Acetate and a mixture of acetate and butyrate were used as substrates, serving as models for acidified waste-waters. Granular sludge with either Methanothrix or Methanosarcina as the predominant acetate utilizing methanogen was cultivated by allowing the loading rate to increase whenever the acetate concentration in the effluent dropped below 200 and 700 mg COD/L, respectively. The highest methane generation rates, up to 162 kg CH(4)-COD/m(3) day, or 2.53 mole CH(4)/L day, were achieved at hydraulic retention times down to 21 min, with granules consisting of Methanothrix. The formation of Methanothrix granules did not depend on the type of seed material, nor on the addition of inert support particles. The growth of granules proceeded rapidly with adapted seed material, even when the reactors were inoculated with low concentrations. With mesophilic seed materials growth of granules took much longer. Thermophilic Methanothrix granules strongly resemble mesophilic granules of the "filamentous" type. Some factors governing the thermophilic granulation process are discussed.
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PMID:Granulation of biomass in thermophilic upflow anaerobic sludge blanket reactors treating acidified wastewaters. 1855 83

Methanogenesis was studied in downflow stationary fixed-film bioreactors. The support materials in this study included ceramic Raschig rings, hardwood chips, and sized charcoal. The performances of these support materials have been compared using both synthetic acid mixture and acid products obtained from paper mill sludge. Woodchips appeared to be the most promising support material: The maximum methane productivity of 3.56 L/L day at a nominal retention time of 0.78 day was obtained using initial total acid concentrations of 9.125 g/L. Higher productivity was achieved at the cost of efficiency of the process in terms of conversion of acids. From nitrogen balances, it was deduced that ammonia supplemented methane generation by supplying hydrogen for there duction of carbon dioxide.An ionic balance was developed to ascertain the relationship between the composition and the pH of the liquid and the mole fraction of carbon dioxide in the gas phase. From these ionic balance equations, it was possible to predict the gas phase composition at various retention times. The maximum error between the computed and the experimental values was less than 13%.
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PMID:Methanogenesis from volatile fatty acids in downflow stationary fixed-film reactor. 1858 14

Kinetics of methanogenesis from acetate was studied using pure cultures of Methanosarcina barkeri and Methanosarcina mazei. Methane formation was found to be associated with cell growth. Nearly equimolar methane was produced from acetate during the methanogenic growth, and about 1.94 g of cells were formed from each mole of acetate consumed. Cell growth can be estimated from methane production. Significant substrate inhibition was found when acetate concentration was higher than 0.12 M. Among the three methanogenic strains studied, M. mazei strain S6 had the highest specific growth rate at all acetate concentrations studied and was least sensitive to environmental factors investigated (e.g., acetate concentration). The maximum specific growth rate found for strain S6 was 0.022 hr(-1) at acetic acid concentration around 7 g/L. The other two strains studied were M. barkeri strain 227 and strain MS. Growth of M. barkeri was completely inhibited at sodium acetate concentrations higher than 0.24 M. The maximum specific growth rate found for strains 227 and MS was 0.019 and 0.021 h(-1) at acetic acid concentrations of 3.6 and 6.8 g/L, respectively. A kinetic model with substrate inhibition was developed and can be used to simulate the methane formation from M. mazei strain S6 grown on acetate at 35 degrees C, pH 7.
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PMID:Kinetic study and mathematical modeling of methanogenesis of acetate using pure cultures of methanogens. 1858 53

The defined microbial cultures for methane generation from lactose were investigated. A mixed culture consisting of homolactic (Streptococcus lactis), homoacetic (Clostridium formicoaceticum), and acetate-utilizing methanogenic (Methanococcus mazei) bacteria was used to convert lactose and whey permeate to methane at mesophilic temperatures (35-37 degrees C) and a pH around 7.0. Lactose was first converted to lactic acid by S. lactis, then to acetic acid by C. formicoaceticum, and finally to methane and CO(2) by M. mazei. About 5.3 mol methane were obtained from each mole of lactose consumed, and the conversion of acetate to methane was the rate-limiting step for this mixed-culture fermentation.
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PMID:Defined bacterial culture development for methane generation from lactose. 1858 15

Anaerobic oxidation of methane (AOM) in anoxic marine sediments is a significant process in the global methane cycle, yet little is known about the role of bulk composition, temperature and pressure on the overall energetics of this process. To better understand the biogeochemistry of AOM, we have calculated and compared the energetics of a number of candidate reactions that microorganisms catalyse during the anaerobic oxidation of methane in (i) a coastal lagoon (Cape Lookout Bight, USA), (ii) the deep Black Sea, and (iii) a deep-sea hydrothermal system (Guaymas basin, Gulf of California). Depending on the metabolic pathway and the environment considered, the amount of energy available to the microorganisms varies from 0 to 184 kJ mol(-1). At each site, the reactions in which methane is either oxidized to HCO3(-), acetate or formate are generally only favoured under a narrow range of pressure, temperature and solution composition--particularly under low (10(-10 )m) hydrogen concentrations. In contrast, the reactions involving sulfate reduction with H2, formate and acetate as electron donors are nearly always thermodynamically favoured. Furthermore, the energetics of ATP synthesis was quantified per mole of methane oxidized. Depending on depth, between 0.4 and 0.6 mol of ATP (mol CH4(-1) was produced in the Black Sea sediments. The largest potential productivity of 0.7 mol of ATP (mol CH4(-1) was calculated for Guaymas Basin, while the lowest values were predicted at Cape Lookout Bight. The approach used in this study leads to a better understanding of the environmental controls on the energetics of AOM.
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PMID:A thermodynamic analysis of the anaerobic oxidation of methane in marine sediments. 1869 83


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