Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization.

Science.gov (United States)

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2008-10-01

Two new procedures for wine ethanol 13C/12C isotope ratio determination, using high-performance liquid chromatography and gas chromatography isotope ratio mass spectrometry (HPLC/IRMS and GC/IRMS), have been developed to improve isotopic methods dedicated to the study of wine authenticity. Parameters influencing separation of ethanol from wine matrix such as column, temperature, mobile phase, flow rates and injection mode were investigated. Twenty-three wine samples from various origins were analyzed for validation of the procedures. The analytical precision was better than 0.15 per thousand, and no significant isotopic fractionation was observed employing both separative techniques coupled to IRMS. No significant differences and a very strong correlation (r = 0.99) were observed between the 13C/12C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The potential advantages of the developed methods over the traditional one are speed (reducing time required from hours to minutes) and simplicity. In addition, these are the first isotopic methods that allow 13C/12C determination directly from a liquid sample with no previous ethanol isolation, overcoming technical difficulties associated with sample treatment.

Genuineness assessment of mandarin essential oils employing gas chromatography-combustion-isotope ratio MS (GC-C-IRMS).

Science.gov (United States)

Schipilliti, Luisa; Tranchida, Peter Quinto; Sciarrone, Danilo; Russo, Marina; Dugo, Paola; Dugo, Giovanni; Mondello, Luigi

2010-03-01

Cold-pressed mandarin essential oils are products of great economic importance in many parts of the world and are used in perfumery, as well as in food products. Reconstituted mandarin oils are easy to find on the market; useful information on essential oil authenticity, quality, extraction technique, geographic origin and biogenesis can be attained through high-resolution GC of the volatile fraction, or enantioselective GC, using different chiral stationary phases. Stable isotope ratio analysis has gained considerable interest for the unveiling of citrus oil adulteration, detecting small differences in the isotopic carbon composition and providing plenty of information concerning the discrimination among products of different geographical origin and the adulteration of natural essential oils with synthetic or natural compounds. In the present research, the authenticity of several mandarin essential oils was assessed through the employment of GC hyphenated to isotope ratio MS, conventional GC flame ionization detector, enantioselective GC and HPLC. Commercial mandarin oils and industrial natural (declared as such) mandarin essential oils, characterized by different harvest periods and geographic origins, were subjected to analysis. The results attained were compared with those of genuine cold-pressed Italian mandarin oils, obtained during the 2008-2009 harvest season.

Stable carbon isotopic composition of gasolines determined by isotope ratio monitoring gas chromatography mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Smallwood, B.J.; Philp, R.P.; Allen, J.D. [University of Oklahoma, Norman, OK (United States). School of Geology and Geophysics

2002-07-01

A large number of underground gasoline storage facilities in the United States continuously leak gasoline into the subsurface, which makes gasoline a major groundwater contaminant. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) are used currently to characterize contaminated groundwater and soils. Correlations of contaminants with suspected source(s) are extremely difficult by these techniques because many gasolines have similar hydrocarbon distributions. The present study applied the technique of isotope ratio monitoring gas chromatography-mass spectrometry (irmGC-MS) to 19 gasoline samples from different areas of the USA. This allows a much better correlation of gasoline contaminants to source. Data obtained indicate a wide range of {sup {delta}}{sup 13}C values for 16 ubiquitous compounds in the gasolines. The majority of samples could be distinguished from each other on the basis of {sup {delta}}{sup 13}C hydrocarbon composition. The oxygenated additive methyl tertiary butyl ether (MTBE) was present in ten of the gasolines analyzed, and had a relatively narrow range of {sup {delta}}{sup 13}C values (-30.4 to -28.3 per mille). Preliminary investigations were also made to determine the extent of carbon isotopic fractionation after simple water washing and evaporation experiments. Results indicate that the majority of compounds did not undergo significant carbon isotopic fractionation as a result of these processes. (author)

Using GC-combustion isotope ratio mass spectrometry for confirming steroid administration from urinary metabolites in humans and animals

International Nuclear Information System (INIS)

Phillips, A.; Churchman, D.; Davis, S.

2000-01-01

Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) was used to study the incorporation of exogenous testosterone enanthate into excreted urinary 5α- and 5β-androstane-3α, 17β-diols

Online gas chromatography combustion/pyrolysis-isotope ratio mass spectrometry (HRGC-C/P-IRMS) of (+/-)-Dihydroactinidiolide from tea ( Camellia sinensis ) and rooibos tea ( Aspalathus linearis ).

Science.gov (United States)

del Mar Caja, María; Preston, Christina; Menzel, Michael; Kempf, Michael; Schreier, Peter

2009-07-08

Online capillary gas chromatography-isotope ratio mass spectrometry in both the combustion and the pyrolysis modes (HRGC-C/P-IRMS) was employed to perform authentication studies of the flavoring agent (+/-)-dihydroactinidiolide. Thus, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values of synthetic (ex synthetic beta-ionone and natural beta-carotene) as well as enzymatically (ex synthetic and natural beta-carotene) produced references were studied in comparison with those of the natural substance isolated from black (n = 17) and green teas (n = 6) ( Camellia sinensis ) as well as Rooibos tea ( Aspalathus linearis ) (n = 7). The isotope values determined for both the synthetic and enzymatically produced samples of (+/-)-dihydroactinidiolide reflected the influence of the origin of their educts. Hence, in cases when synthetic educts were used, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranged from -27.0 to -28.4 per thousand and from -28 to -169 per thousand, respectively, whereas the use of natural educts led to ranges from -30.3 to -31.6 per thousand and from -154 to -228 per thousand, respectively. As to the tea samples, delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranging from -29.0 to -34.1 per thousand and from -153 to -274 per thousand, respectively, were recorded for (+/-)-dihydroactinidiolide from black and green teas, whereas that from Rooibos tea showed (2)H/(1)H ratios ranging from -189 to -210 per thousand as well as slightly enriched values in the (13)C/(12)C ratios ranging from -24.4 to -27.1 per thousand.

Measurement parameter selection for quantitative isotope dilution gas chromatography/mass spectrometry

International Nuclear Information System (INIS)

Colby, B.N.; Rosecrance, A.E.; Colby, M.E.

1981-01-01

By use of the two-isotope model of isotope dilution, selection criteria were developed for identifying optimum m/z's for quantitation of compounds by gas chromatography/mass spectrometry. In addition, it was possible to predict the optimum ratio of naturally abundant to labeled compound and to identify appropriate data reduction methods. The validity of these predictions was confirmed by using experimental GC/MS data for several organic compounds

Inter-laboratory comparison of elemental analysis and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS). Part I: delta13C measurements of selected compounds for the development of an isotopic Grob-test.

Science.gov (United States)

Serra, F; Janeiro, A; Calderone, G; Rojas, J M Moreno; Rhodes, C; Gonthier, L A; Martin, F; Lees, M; Mosandl, A; Sewenig, S; Hener, U; Henriques, B; Ramalho, L; Reniero, F; Teixeira, A J; Guillou, C

2007-03-01

This study was directed towards investigating suitable compounds to be used as stable isotope reference materials for gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) calibration. Several compounds were selected from those used in the 'Grob-test' mixture. Oxygen- and nitrogen-containing substances were added to these compounds to allow the mixture to be used as a possible multi-isotopic calibration tool for 2H/1H, 13C/12C, 15N/14N and 18O/16O ratio determinations. In this paper we present the results of delta13C measurements performed by the consortium of the five laboratories taking part in this inter-calibration exercise. All the compounds were individually assessed for homogeneity, short-term stability and long-term stability by means of EA-IRMS, as required by the bureau communitaire de reference (BCR) Guide for Production of Certified Reference Materials. The results were compared then with the GC-C-IRMS measurements using both polar and non-polar columns, and the final mixture of selected compounds underwent a further certification exercise assessing limits of accuracy and reproducibility under specified GC-C-IRMS conditions. Copyright 2007 John Wiley & Sons, Ltd.

Isotope Fractionation in Methane Reactions Studied by Gas Chromatography and Liquid Scintillation

DEFF Research Database (Denmark)

Andersen, Bertel Lohmann; Bidoglio, G.; Leip, A.

1997-01-01

Determination of C-14-marked methane by gas chromatography and liquid scintillation counting is shown to be useful in studies of isotope effects. Data on the specific activity is used to separate the contributions of (CH4)-C-14, and (CH4)-C-12 to the gas-chromatographic peak area. As an application...

Chemical characterization and stable carbon isotopic composition of particulate Polycyclic Aromatic Hydrocarbons issued from combustion of 10 Mediterranean woods

Directory of Open Access Journals (Sweden)

A. Guillon

2013-03-01

Full Text Available The objectives of this study were to characterize polycyclic aromatic hydrocarbons from particulate matter emitted during wood combustion and to determine, for the first time, the isotopic signature of PAHs from nine wood species and Moroccan coal from the Mediterranean Basin. In order to differentiate sources of particulate-PAHs, molecular and isotopic measurements of PAHs were performed on the set of wood samples for a large panel of compounds. Molecular profiles and diagnostic ratios were measured by gas chromatography/mass spectrometry (GC/MS and molecular isotopic compositions (δ13C of particulate-PAHs were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS. Wood species present similar molecular profiles with benz(aanthracene and chrysene as dominant PAHs, whereas levels of concentrations range from 1.8 to 11.4 mg g−1 OC (sum of PAHs. Diagnostic ratios are consistent with reference ratios from literature but are not sufficient to differentiate the species of woods. Concerning isotopic methodology, PAH molecular isotopic compositions are specific for each species and contrary to molecular fingerprints, significant variations of δ13C are observed for the panel of PAHs. This work allows differentiating wood combustion (with δ13CPAH = −28.7 to −26.6‰ from others origins of particulate matter (like vehicular exhaust using isotopic measurements but also confirms the necessity to investigate source characterisation at the emission in order to help and complete source assessment models. These first results on woodburnings will be useful for the isotopic approach to source tracking.

Measurement of the 13C/12C ratio of soil-plant individual sugars by gas chromatography/combustion/isotope-ratio mass spectrometry of silylated derivatives.

Science.gov (United States)

Derrien, Delphine; Balesdent, Jérôme; Marol, Christine; Santaella, Catherine

2003-01-01

Carbohydrate is an important pool in the terrestrial carbon cycle. The potential offered by natural and artificial 13C-labelling techniques should therefore be applied to the investigation of the dynamics of individual sugars in soils. For this reason, we evaluated the method of 13C sugar analysis by gas chromatography/combustion/isotope-ratio mass spectrometry (GC/C/IRMS) after hydrolysis and direct trimethylsilylation. Trimethylsilylation involved the addition of several carbon atoms per sugar. These atoms have to be taken into account in the estimation of the carbon isotope ratio. The analysis of standard and natural pentoses and hexoses of known 13C enrichments revealed that the number of analysed added carbon atoms was less than expected from stoichiometry. This was attributed to incomplete derivatization and/or incomplete oxidation of methylsilyl carbon before IRMS. Using a calibration of the number of analysed added carbon atoms, the isotope excess of enriched samples could be determined with a relative error close to 5%. Concerning the determination of natural abundances by GC/C/IRMS, we could measure the delta 13C of standard C3- and C4-derived sugars with an accuracy of +/-1.5 per thousand using the previous calibration. We were able to apply this technique to plant-soil systems labelled by pulse-chase of 13CO2, revealing the nature and dynamics of sugars in the plant rhizosphere. Copyright 2003 John Wiley & Sons, Ltd.

On-line gas chromatography combustion/pyrolysis isotope ratio mass spectrometry (HRGC-C/P-IRMS) of pineapple (Ananas comosus L. Merr.) volatiles.

Science.gov (United States)

Preston, Christina; Richling, Elke; Elss, Sandra; Appel, Markus; Heckel, Frank; Hartlieb, Ariane; Schreier, Peter

2003-12-31

By use of extracts prepared by liquid-liquid separation of the volatiles from self-prepared juices of pineapple fruits (Ananas comosus) (n = 14) as well as commercial pineapple recovery aromas/water phases (n = 3), on-line capillary gas chromatography-isotope ratio mass spectrometry was employed in the combustion (C) and the pyrolysis (P) modes (HRGC-C/P-IRMS) to determine the delta(13)C(VPDB) and delta(2)H(VSMOW) values of selected pineapple flavor constituents. In addition to methyl 2-methylbutanoate 1, ethyl 2-methylbutanoate 2, methyl hexanoate 3, ethyl hexanoate 4, and 2,5-dimethyl-4-methoxy-3[2H]-furanone 5, each originating from the fruit, the delta(13)C(VPDB) and delta(2)H(VSMOW) data of commercial synthetic 1-5 and "natural" (biotechnologically derived) 1-4 were determined. With delta(13)C(VPDB) data of pineapple volatiles 1-4 varying from -12.8 to -24.4 per thousand, the range expected for CAM metabolism was observed. Compound 5 showed higher depletion from -20.9 to -28.6 per thousand. A similar situation was given for the delta(2)H(VSMOW) values of 3-5 from pineapple ranging from -118 to -191 per thousand, whereas 1 and 2 showed higher depleted values from -184 to -263 per thousand. In nearly all cases, analytical differentiation of 1-5 from pineapple and natural as well as synthetic origin was possible. In general, natural and synthetic 1-5 exhibited delta(13)C(VPDB) data ranging from -11.8 to -32.2 per thousand and -22.7 to -35.9 per thousand, respectively. Their delta(2)H(VSMOW) data were in the range from -242 to -323 per thousand and -49 to -163 per thousand, respectively.

Capillary gas-solid chromatography

International Nuclear Information System (INIS)

Berezkin, V.G.

1996-01-01

Modern state of gas adsorption chromatography in open capillary columns has been analyzed. The history of the method development and its role in gas chromatography, ways to construct open adsorptional capillary columns, foundations of the theory of retention and washing of chromatographic regions in gas adsorption capillary columns have been considered. The fields is extensively and for analyzing volatile compounds of different isotopic composition, inorganic and organic gases, volatile organic polar compounds, aqueous solutions of organic compounds. Separation of nuclear-spin isomers and isotopes of hydrogen is the first illustrative example of practical application of the adsorption capillary chromatography. It is shown that duration of protium and deuterium nuclear isomers may be reduced if the column temperature is brought to 47 K

Fractionation of mercury stable isotopes during coal combustion and seawater flue gas desulfurization

International Nuclear Information System (INIS)

Huang, Shuyuan; Yuan, Dongxing; Lin, Haiying; Sun, Lumin; Lin, Shanshan

2017-01-01

In the current study, fractionation of mercury isotopes during coal combustion and seawater flue gas desulfurization (SFGD) in a coal-fired power plant using a SFGD system was investigated. Fourteen samples were collected from the power plant. The samples were pretreated with a combustion-trapping method and were analyzed with a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). Compared with the raw coal, the bottom ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −0.45 to −0.03‰. The fly ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −1.49 to −0.73‰ for Chinese coal and from −1.47 to −0.62‰ for Indonesian coal. The δ 202 Hg of fresh seawater and desulfurized seawater was found to be −1.32 and −0.32‰ respectively. These δ 202 Hg values indicated that the desulfurized seawater was enriched with heavier mercury isotopes. Based upon the calculated results obtained from the mass balance equation, it was suggested that the stack emissions were enriched with lighter mercury isotopes. Mass independent fractionation was observed in most of the samples with a Δ 199 Hg/Δ 201 Hg ratio of approximately 0.96. The results help in improving the understanding of mercury isotope fractionation during coal combustion and SFGD, and are also useful in tracing the mercury emissions from coal fired power plants. - Highlights: • Spread of 1.5‰ was observed in δ 202 Hg values of raw coals and coal related samples. • The δ 202 Hg values were more negative in fly ash than those in the raw coal. • The flue gas had a significant Hg fractionation after desulfurization. • The stack emissions were enriched with lighter isotopes compared with the raw coal.

Metal/glass composites for analysis of hydrogen isotopes by gas-chromatography

International Nuclear Information System (INIS)

Nicolae, Constantin Adrian; Sisu, Claudia; Stefanescu, Doina; Stanciu, Vasile

1999-01-01

The separation process of hydrogen isotopes by cryogenic distillation or thermal diffusion is a key technology for tritium separation from heavy water in CANDU reactor and for tritium fuel cycle in thermonuclear fusion reactor. In each process, analytical techniques for analyzing the hydrogen isotope mixture are required. An extensive experimental research has been carried out in order to produce the most suitable adsorbents and to establish the best operating conditions for selective separation and analysis of hydrogen isotopes by gas-chromatography. This paper describes the preparation of adsorbent materials used as stationary phases in the gas-chromatographic column for hydrogen isotope separation and the treatment (activation) of stationary phases. Modified thermoresisting glass with Fe(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O and Cr 2 O 3 respectively have been experimentally investigated at 77 K for H 2 , HD and D 2 separation and the results of chromatographic runs are reported and discussed. The gas-chromatographic apparatus used in this study is composed of a Hewlett-Packard 7620A gas-chromatograph equipped with a gas carrier flow rate controller and a thermal conductivity detector. The apparatus comprises also a Dewar vessel containing the separation column. The hydrogen isotopes, H 2 , HD, D 2 , and their mixture have been obtained in our laboratories. The best operating conditions and parameters of the Fe 3+ /glass adsorbent column , i.e. granulometry, column length, pressure-drop along the column, carrier gas flow rate and sample volume have been studied by means of the analysis of the retention times, separation factors and HETP. (authors)

Simultaneous Detection of Androgen and Estrogen Abuse in Breeding Animals by Gas Chromatography-Mass Spectrometry/Combustion/Isotope Ratio Mass Spectrometry (GC-MS/C/IRMS) Evaluated against Alternative Methods.

Science.gov (United States)

Janssens, Geert; Mangelinckx, Sven; Courtheyn, Dirk; De Kimpe, Norbert; Matthijs, Bert; Le Bizec, Bruno

2015-09-02

The administration of synthetic homologues of naturally occurring steroids can be demonstrated by measuring (13)C/(12)C isotopic ratios of their urinary metabolites. Gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) was used in this study to appraise in a global approach isotopic deviations of two 17β-testosterone metabolites (17α-testosterone and etiocholanolone) and one 17β-estradiol metabolite (17α-estradiol) together with those of 5-androstene-3β,17α-diol as endogenous reference compound (ERC). Intermediate precisions of 0.35‰, 1.05‰, 0.35‰, and 0.21‰, respectively, were observed (n = 8). To assess the performance of the analytical method, a bull and a heifer were treated with 17β-testosterone propionate and 17β-estradiol-3-benzoate. The sensitivity of the method permitted the demonstration of 17β-estradiol treatment up to 24 days. For 17β-testosterone treatment, the detection windows were 3 days and 24 days for the bull and the heifer, respectively. The capability of GC-MS/C/IRMS to demonstrate natural steroid abuse for urinary steroids was eventually compared to those of mass spectrometry (LC-MS/MS) when measuring intact steroid esters in blood and hair.

Detection of Synthetic Testosterone Use by Novel Comprehensive Two-Dimensional Gas Chromatography Combustion Isotope Ratio Mass Spectrometry (GC×GCC-IRMS)

Science.gov (United States)

Tobias, Herbert J.; Zhang, Ying; Auchus, Richard J.; Brenna, J. Thomas

2011-01-01

We report the first demonstration of Comprehensive Two-dimensional Gas Chromatography Combustion Isotope Ratio Mass Spectrometry (GC×GCC-IRMS) for the analysis of urinary steroids to detect illicit synthetic testosterone use, of interest in sport doping. GC coupled to IRMS (GCC-IRMS) is currently used to measure the carbon isotope ratios (CIR, δ13C) of urinary steroids in anti-doping efforts; however, extensive cleanup of urine extracts is required prior to analysis to enable baseline separation of target steroids. With its greater separation capabilities, GC×GC has the potential to reduce sample preparation requirements and enable CIR analysis of minimally processed urine extracts. Challenges addressed include on-line reactors with minimized dimensions to retain narrow peaks shapes, baseline separation of peaks in some cases, and reconstruction of isotopic information from sliced steroid chromatographic peaks. Difficulties remaining include long-term robustness of on-line reactors and urine matrix effects that preclude baseline separation and isotopic analysis of low concentration and trace components. In this work, steroids were extracted, acetylated, and analyzed using a refined, home-built GC×GCC-IRMS system. 11-hydroxy-androsterone (11OHA) and 11-ketoetiocolanolone (11KE) were chosen as endogenous reference compounds (ERC) because of their satisfactory signal intensity, and their CIR was compared to target compounds (TC) androsterone (A) and etiocholanolone (E). Separately, a GC×GC-qMS system was used to measure testosterone (T)/EpiT concentration ratios. Urinary extracts of urine pooled from professional athletes, and urine from one individual that received testosterone gel (T-gel) and one individual that received testosterone injections (T-shot) were analyzed. The average precisions of δ13C and Δδ13C measurements were SD(δ13C) approximately ± 1‰ (n=11). The T-shot sample resulted in a positive for T use with a T/EpiT ratio of > 9 and CIR

Enhanced efficiency of internal combustion engines by employing spinning gas.

Science.gov (United States)

Geyko, V I; Fisch, N J

2014-08-01

The efficiency of the internal combustion engine might be enhanced by employing spinning gas. A gas spinning at near sonic velocities has an effectively higher heat capacity, which allows practical fuel cycles, which are far from the Carnot efficiency, to approach more closely the Carnot efficiency. A remarkable gain in fuel efficiency is shown to be theoretically possible for the Otto and Diesel cycles. The use of a flywheel, in principle, could produce even greater increases in efficiency.

Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.

Science.gov (United States)

Moerdijk-Poortvliet, Tanja C W; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J; Boschker, Henricus T S

2015-07-15

We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although LC/IRMS is expected to be more accurate and precise, no direct comparison has been reported. GC/IRMS with the aldonitrile penta-acetate (ANPA) derivatisation method was compared with LC/IRMS without derivatisation. A large number of glucose standards and a variety of natural samples were analysed for five neutral carbohydrates at natural abundance as well as at (13)C-enriched levels. Gas chromatography/chemical ionisation mass spectrometry (GC/CIMS) was applied to check for incomplete derivatisation of the carbohydrate, which would impair the accuracy of the GC/IRMS method. The LC/IRMS technique provided excellent precision (±0.08‰ and ±3.1‰ at natural abundance and enrichment levels, respectively) for the glucose standards and this technique proved to be superior to GC/IRMS (±0.62‰ and ±19.8‰ at natural abundance and enrichment levels, respectively). For GC/IRMS measurements the derivatisation correction and the conversion of carbohydrates into CO2 had a considerable effect on the measured δ(13)C values. However, we did not find any significant differences in the accuracy of the two techniques over the full range of natural δ(13)C abundances and (13)C-labelled glucose. The difference in the performance of GC/IRMS and LC/IRMS diminished when the δ(13)C values were measured in natural samples, because the chromatographic performance and background correction became critical factors, particularly for LC/IRMS. The derivatisation of carbohydrates for the GC/IRMS method was complete. Although both LC/IRMS and GC/IRMS are reliable techniques for compound-specific stable carbon isotope analysis of carbohydrates (provided that derivatisation is complete and the

Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

International Nuclear Information System (INIS)

Freeman, K.H.; Ricci, S.A.; Studley, A.; Hayes, J.M.

1989-01-01

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values

Chemically modified glasses for analysis of hydrogen isotopes by gas-chromatography

International Nuclear Information System (INIS)

Stanciu, Vasile; Stefanescu, Doina

1999-01-01

Hydrogen isotope separation process by such methods as cryogenic distillation or thermal diffusion method is one of the key technologies of the tritium separation from heavy water of CANDU reactors and in the tritium fuel cycle for a thermonuclear fusion reactor. In each process, the analytical techniques for measuring contents of hydrogen isotope mixture are necessary. An extensive experimental research has been carried out in order to produce the most suitable absorbent and define the best operating conditions for selective separation and analysis of hydrogen isotope by gas-chromatography. This paper describes the preparation of adsorbent materials utilised as stationary phase in the gas-chromatographic column for hydrogen isotope separation and treatment (activation) of stationary phase. Modified thermo-resisting glass with Fe(NH 4 ) 2 (SO 4 ) 2 6H 2 O and Cr 2 O 3 , respectively, have been experimentally investigated at 77 K for H 2 , HD and D 2 separation and the results of chromatographic runs are also reported and discussed. The gas-chromatographic apparatus used is composed of a Hewlett-Packard 7620A gas-chromatograph equipped with a gas carrier flow rate controller and a thermal conductivity detector (TCD). The apparatus comprises also a Dewar vessel containing the separation column. The hydrogen isotopes H 2 , HD, D 2 and their mixture have been obtained in our laboratories. The best operating conditions of the adsorbent column Fe (III)/glass and Cr 2 O 3 /glass, i.e. granulometry, column length, pressure-drop along the column, carrier gas flow rate, sample volume have been studied by means of the analysis of the retention times, separation factors and HETP. (authors)

Using Gas Chromatography/Isotope Ratio Mass Spectrometry to Determine the Fractionation Factor for H2 Production by Hydrogenases

International Nuclear Information System (INIS)

Yang, Hui; Ghandi, H.; Shi, Liang; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

2012-01-01

Hydrogenases catalyze the reversible formation of H2, and they are key enzymes in the biological cycling of H2. H isotopes should be a very useful tool in quantifying proton trafficking in biological H2 production processes, but there are several obstacles that have thus far limited the use of this tool. In this manuscript, we describe a new method that overcomes some of these barriers and is specifically designed to measure isotopic fractionation during enzyme-catalyzed H2 evolution. A key feature of this technique is that purified hydrogenases are employed, allowing precise control over the reaction conditions and therefore a high level of precision. A custom-designed high-throughput gas chromatography-isotope ratio mass spectrometer is employed to measure the isotope ratio of the H2. Using this method, we determined that the fractionation factor of H2 production by the (NiFe)-hydrogenase from Desulfivibrio fructosovran is 0.27. This result indicates that, as expected, protons are highly favored over deuterons during H2 evolution. Potential applications of this new method are discussed.

A STUDY ON CARBON ISOTOPE OF CO2 AND CH4 IN WESTERN DIENG PLATEU BY GAS CHROMATOGRAPHY- ISOTOPE RATIO MASS SPECTROMETER (GC-IRMS

Directory of Open Access Journals (Sweden)

Hanik Humaida

2010-06-01

Full Text Available The carbon isotope can be used to evaluate volcanism phenomenon of volcano. The study of carbon isotope of CO2 and CH4 was carried out in western Dieng Plateau by mass-spectrometer. Before analysis, sampel was separated by gas chromatography using a Porapak-Q column and a FID (Flame Ionization Detector detector. The gas was oxidized by copper oxide at 850oC before being ionized in mass-spectrometer for isotope analysis. The CO2 content in Candradimuka crater (-4.10 O/OO, indicated that the gas may be as volcanic gas. The other CO2 from Sumber and western Gua Jimat, had isotope value  of -10.05 and -12.07 O/OO, respectively, indicating contamination from crustal and subduction material. The carbon isotope of CH4 gas from Pancasan village was -63.42 O/OO, that may be categorized as biogenic gas.   Keywords: isotope, CO2, CH4, Dieng.

Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

Science.gov (United States)

Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

1995-01-01

Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

Science.gov (United States)

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that

Stable isotopes and biomarkers in microbial ecology

NARCIS (Netherlands)

Boschker, H.T.S.; Middelburg, J.J.

2002-01-01

The use of biomarkers in combination with stable isotope analysis is a new approach in microbial ecology and a number of papers on a variety of subjects have appeared. We will first discuss the techniques for analysing stable isotopes in biomarkers, primarily gas chromatography-combustion-isotope

Simultaneous determination of creatinine and creatine in human serum by double-spike isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS).

Science.gov (United States)

Fernández-Fernández, Mario; Rodríguez-González, Pablo; Añón Álvarez, M Elena; Rodríguez, Felix; Menéndez, Francisco V Álvarez; García Alonso, J Ignacio

2015-04-07

This work describes the first multiple spiking isotope dilution procedure for organic compounds using (13)C labeling. A double-spiking isotope dilution method capable of correcting and quantifying the creatine-creatinine interconversion occurring during the analytical determination of both compounds in human serum is presented. The determination of serum creatinine may be affected by the interconversion between creatine and creatinine during sample preparation or by inefficient chemical separation of those compounds by solid phase extraction (SPE). The methodology is based on the use differently labeled (13)C analogues ((13)C1-creatinine and (13)C2-creatine), the measurement of the isotopic distribution of creatine and creatinine by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the application of multiple linear regression. Five different lyophilized serum-based controls and two certified human serum reference materials (ERM-DA252a and ERM-DA253a) were analyzed to evaluate the accuracy and precision of the proposed double-spike LC-MS/MS method. The methodology was applied to study the creatine-creatinine interconversion during LC-MS/MS and gas chromatography-mass spectrometry (GC-MS) analyses and the separation efficiency of the SPE step required in the traditional gas chromatography-isotope dilution mass spectrometry (GC-IDMS) reference methods employed for the determination of serum creatinine. The analysis of real serum samples by GC-MS showed that creatine-creatinine separation by SPE can be a nonquantitative step that may induce creatinine overestimations up to 28% in samples containing high amounts of creatine. Also, a detectable conversion of creatine into creatinine was observed during sample preparation for LC-MS/MS. The developed double-spike LC-MS/MS improves the current state of the art for the determination of creatinine in human serum by isotope dilution mass spectrometry (IDMS), because corrections are made for all the possible errors

Gas-chromatographic separation of hydrogen isotopic mixtures

International Nuclear Information System (INIS)

Preda, Anisoara; Bidica, Nicolae

2005-01-01

Full text: Gas chromatographic separation of hydrogen isotopes have been reported in the literature since late of 1950's. Gas chromatography is primarily an analytical method, but because of its properties it may be used in many other fields with excellent results. A simple method is proposed for the gas-chromatographic analysis of complex gas mixtures containing hydrogen isotopes; the method is based on the substantial difference in the thermal conductivity of these isotopes. One of the main disadvantages of the conventional gas chromatography is the long retention times required for the analysis of hydrogen gas mixtures while the column is operated at very low temperature. The method described in this paper was based on using a capillary molecular sieve 5A column operated for this kind of separation at 173 K. The carrier gas was Ne and the detector was TCD. In the paper chromatograms for various carrier flow rates and various hydrogen isotope mixtures are presented. (authors)

The potential of Isotope Ratio Mass Spectrometry (IRMS) and gas chromatography-IRMS analysis of triacetone triperoxide in forensic explosives investigations

NARCIS (Netherlands)

Bezemer, K.D.B.; Koeberg, M.; Heijden, A.E.D.M. van der; Driel, C.A. va; Blaga, C.; Bruinsma, J.; Asten, A.C. van

2016-01-01

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen

Analysis of trace levels of impurities and hydrogen isotopes in helium purge gas using gas chromatography for tritium extraction system of an Indian lead lithium ceramic breeder test blanket module.

Science.gov (United States)

Devi, V Gayathri; Sircar, Amit; Yadav, Deepak; Parmar, Jayraj

2018-01-12

In the fusion fuel cycle, the accurate analysis and understanding of the chemical composition of any gas mixture is of great importance for the efficient design of a tritium extraction and purification system or any tritium handling system. Methods like laser Raman spectroscopy and gas chromatography with thermal conductivity detector have been considered for hydrogen isotopes analyses in fuel cycles. Gas chromatography with a cryogenic separation column has been used for the analysis of hydrogen isotopes gas mixtures in general due to its high reliability and ease of operation. Hydrogen isotopes gas mixture analysis with cryogenic columns has been reported earlier using different column materials for percentage level composition. In the present work, trace levels of hydrogen isotopes (∼100 ppm of H 2 and D 2 ) have been analyzed with a Zeolite 5A and a modified γ-Al 2 O 3 column. Impurities in He gas (∼10 ppm of H 2 , O 2 , and N 2 ) have been analyzed using a Zeolite 13-X column. Gas chromatography with discharge ionization detection has been utilized for this purpose. The results of these experiments suggest that the columns developed were able to separate ppm levels of the desired components with a small response time (<6 min) and good resolution in both cases. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas chromatography and isotope ratio mass spectrometry of Pinot Noir wine volatile compounds (δ13C) and solid residues (δ13C, δ15N) for the reassessment of vineyard water-status.

Science.gov (United States)

Spangenberg, Jorge E; Vogiatzaki, Maria; Zufferey, Vivian

2017-09-29

This paper describes a novel approach to reassess the water status in vineyards based on compound-specific isotope analysis (CSIA) of wine volatile organic compounds (δ 13 C VOC/VPDB ) and bulk carbon and nitrogen isotopes, and the C/N molar ratios of the wine solid residues (δ 13 C SR/VPDB , δ 15 N SR/Air-N2 ). These analyses link gas chromatography/combustion and elemental analysis to isotope ratio mass spectrometry (GC/C/IRMS, EA/IRMS). Field-grown cultivars of Pinot Noir grapevines were exposed during six growing seasons (2009-2014) to controlled soil water availability, while maintaining identical the other environmental variables and agricultural techniques. Wines were produced from the grapes by the same oenological protocol. This permitted for the assessment of the effects in the biochemistry of wines solely induced by the changes in the plant-soil water status. This mimicked the more recurrent and prolonged periods of soil water deficiency due to climate changes. Water stress in grapevine was assessed by the measurement of the predawn leaf water potential (Ψ pd ) and the stable carbon isotope composition of the berry sugars during harvest (must sugars). For quantitation purposes and the normalization of the measured stable carbon isotope ratios of the VOCs, the wine samples were spiked with three standard compounds with known concentration and δ 13 C VPDB values. VOCs were extracted by liquid-liquid extraction and analyzed by gas chromatography/flame ionization detection (GC/FID), gas chromatography/mass spectrometry (GC/MS), and GC/C/IRMS. δ 13 C values were obtained for eighteen VOCs. The solid residues were obtained by freeze-drying wine aliquots and were analyzed for their C and N content and isotope composition by EA/IRMS. All the isotopic ratios (δ 13 C SR , δ 15 N SR , δ 13 C VOC ) are highly correlated with the Ψ pd values, indicating that the proposed gas chromatography and isotope ratio mass spectrometry approach is a useful tool to

Serum/plasma methylmercury determination by isotope dilution gas chromatography-inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Baxter, Douglas C., E-mail: douglas.baxter@alsglobal.com [ALS Scandinavia AB, Aurorum 10, 977 75 Lulea (Sweden); Faarinen, Mikko [ALS Scandinavia AB, Aurorum 10, 977 75 Lulea (Sweden); Osterlund, Helene; Rodushkin, Ilia [ALS Scandinavia AB, Aurorum 10, 977 75 Lulea (Sweden); Division of Geosciences, Lulea University of Technology, 977 87 Lulea (Sweden); Christensen, Morten [ALS Scandinavia AB, Maskinvaegen 2, 183 53 Taeby (Sweden)

2011-09-09

Highlights: {center_dot} We determine methylmercury in serum and plasma using isotope dilution calibration. {center_dot} Separation by gas chromatography and detection by inductively coupled plasma mass spectrometry. {center_dot} Data for 50 specimens provides first reference range for methylmercury in serum. {center_dot} Serum samples shown to be stable for 11 months in refrigerator. - Abstract: A method for the determination of methylmercury in plasma and serum samples was developed. The method uses isotope dilution with {sup 198}Hg-labeled methylmercury, extraction into dichloromethane, back-extraction into water, aqueous-phase ethylation, purge and trap collection, thermal desorption, separation by gas chromatography, and mercury isotope specific detection by inductively coupled plasma mass spectrometry. By spiking 2 mL sample with 1.2 ng tracer, measurements in a concentration interval of (0.007-2.9) {mu}g L{sup -1} could be performed with uncertainty amplification factors <2. A limit of quantification of 0.03 {mu}g L{sup -1} was estimated at 10 times the standard deviation of concentrations measured in preparation blanks. Within- and between-run relative standard deviations were <10% at added concentration levels of 0.14 {mu}g L{sup -1}, 0.35 {mu}g L{sup -1} and 2.8 {mu}g L{sup -1}, with recoveries in the range 82-110%. Application of the method to 50 plasma/serum samples yielded a median (mean; range) concentration of methylmercury of 0.081 (0.091; <0.03-0.19) {mu}g L{sup -1}. This is the first time methylmercury has been directly measured in this kind of specimen, and is therefore the first estimate of a reference range.

The use of stable isotopes and gas chromatography/mass spectrometry in the identification of steroid metabolites in the equine

International Nuclear Information System (INIS)

Houghton, E.; Dumasia, M.C.; Teale, P.; Smith, S.J.; Cox, J.; Marshall, D.; Gower, D.B.

1990-01-01

Stable isotope gas chromatography/mass spectrometry has been used successfully in the elucidation of structures of urinary steroid metabolites in the horse and in the identification of metabolites isolated from in vivo perfusion and in vitro incubation studies using equine tissue preparations. Deuterium-labeled steroids, testosterone, dehydroepiandrosterone, and 5-androstene-3 beta,17 beta-diol have been synthesized by base-catalyzed isotope exchange methods and the products characterized by gas chromatography/mass spectrometry. [16,16(-2)H2]Dehydroepiandrosterone (plus radiolabeled dehydroepiandrosterone) was perfused into a testicular artery of a pony stallion and was shown to be metabolized into 2H2-labeled testosterone, 4-androstenedione, isomers of 5-androstene-3,17-diol, 19-hydroxytestosterone, and 19-hydroxy-4-androstenedione. In further studies, equine testicular minces have been incubated with 2H2-labeled and radiolabeled dehydroepiandrosterone and 5-androstene-3 beta, 17 beta-diol. The metabolites, whose identity was confirmed by stable isotope gas chromatography/mass spectrometry, proved the interconversion of the two substrates, as well as formation of testosterone and 4-androstenedione. The aromatization of dehydroepiandrosterone was also confirmed, together with the formation of an isomer of 5(10)-estrene-3,17-diol from both substrates showing 19-demethylation without concomitant aromatization. In studies of the feto-placental unit, the allantochorion was shown to aromatize [2H5]testosterone to [2H4]estradiol, the loss of one 2H from the substrate being consistent with aromatization of the A ring. The formation of 6-hydroxyestradiol was also confirmed in this study. The same technique has been valuable in determining the structure of two metabolites of nandrolone isolated from horse urine

Differentiation of wood-derived vanillin from synthetic vanillin in distillates using gas chromatography/combustion/isotope ratio mass spectrometry for δ13 C analysis.

Science.gov (United States)

van Leeuwen, Katryna A; Prenzler, Paul D; Ryan, Danielle; Paolini, Mauro; Camin, Federica

2018-02-28

Typical storage in oak barrels releases in distillates different degradation products such as vanillin, which play an important role in flavour and aroma. The addition of vanillin, as well as other aroma compounds, of different origin is prohibited by European laws. As vanillin samples from different sources have different δ 13 C values, the δ 13 C value could be used to determine whether the vanillin is authentic (lignin-derived), or if it has been added from another source (e.g. synthetic). The δ 13 C values for vanillin derived from different sources, including natural, synthetic and tannins, were measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), after diethyl ether addition and/or ethanol dilution. A method for analysing vanillin in distillates after dichloromethane extraction was developed. Tests were undertaken to prove the reliability, reproducibility and accuracy of the method with standards and samples. Distillate samples were run to measure the δ 13 C values of vanillin and to compare them with values for other sources of vanillin. δ 13 C values were determined for: natural vanillin extracts (-21.0 to -19.3‰, 16 samples); vanillin ex-lignin (-28.2‰, 1 sample); and synthetic vanillin (-32.6 to -29.3‰, 7 samples). Seventeen tannin samples were found to have δ 13 C values of -29.5 to -26.7‰, which were significantly different (p distillates (-28.9 to -25.7‰) were mainly in the tannin range, although one spirit (-32.5‰) was found to contain synthetic vanillin. The results show that synthetic vanillin added to a distillate could be differentiated from vanillin derived from oak barrels by their respective δ 13 C values. The GC/C/IRMS method could be a useful tool in the determination of adulteration of distillates. Copyright © 2017 John Wiley & Sons, Ltd.

The influence of different referencing methods on the accuracy of δ(13) C value measurement of ethanol fuel by gas chromatography/combustion/isotope ratio mass spectrometry.

Science.gov (United States)

Neves, Laura A; Rodrigues, Janaína M; Daroda, Romeu J; Silva, Paulo R M; Ferreira, Alexandre A; Aranda, Donato A G; Eberlin, Marcos N; Fasciotti, Maíra

2015-11-15

Brazil is the largest producer of sugar cane bioethanol in the world. Isotope ratio mass spectrometry (IRMS) is the technique of choice to certify the origin/raw materials for ethanol production, but the lack of certified reference materials (CRMs) for accurate measurements of δ(13) C values traceable to Vienna Pee Dee Belemnite (VPDB), the international zero point for (13) C/(12) C measurements, certified and compatible with gas chromatography (GC)/IRMS instruments may compromise the accuracy of δ(13) C determinations. We evaluated the influence of methods for the calibration and normalization of raw δ(13) C values of ethanol samples. Samples were analyzed by GC/C/IRMS using two different GC columns. Different substances were used as isotopic standards for the working gas calibration. The δ(13) C values obtained with the three methods of normalization were statistically compared with those obtained with elemental analyzer (EA)/IRMS, since the δ(13) C results obtained using EA are traceable to VPDB via the NBS 22 reference material. It was observed that both the isotopic reference material for CO2 calibration and the GC column have a major effect on the δ(13) C measurements, leading to a bias of almost 2-3 ‰ in the δ(13) C values. All three methods of normalization were equivalent in performance, enabling an improvement in the GC/C/IRMS accuracy, compared with the EA/IRMS reference values for the samples. All the methods of CO2 calibration, chromatography and normalization presented in this work demonstrated several sources of traceability and accuracy loss for the determination of δ(13) C values in ethanol fuel samples by GC/C/IRMS. This work has also shown the importance of using proper CRMs traceable to VPBD that should be compatible and certified using GC/C/IRMS, ideally in a wide range of δ(13) C values. This is important not only for bioethanol fuel samples, but also for many analytes commonly analyzed by IRMS. Copyright © 2015 John Wiley & Sons

ISOFORMAL: isotopic tracing of formaldehyde sources in housing. Intermediary report

International Nuclear Information System (INIS)

2011-01-01

The authors report an investigation which comprised a sampling and a chemical and isotopic analysis of emissions from the main indoor formaldehyde pollution sources in order to create a exhaustive database. Emissions which are characteristic of motorcar traffic, are also sampled in order to asses their possible contribution in the housing air. This step will be used to develop emission simulations of formaldehyde sources in a laboratory-house in order to validate the isotopic approach as tracing tool for sources of this compound. The report describes the carbon and hydrogen steady isotopes. It presents the sampling procedure, reports the determination of formaldehyde concentrations by high performance liquid chromatography with UV detectors, the use of gas source mass spectrometry, and the analytic development of the isotopic analysis of formaldehyde by gas chromatography combustion isotope ratio mass spectrometry. Outdoor and indoor pollution sources are discussed

Isotopic separation by ion chromatography

International Nuclear Information System (INIS)

Albert, M.G.; Barre, Y.; Neige, R.

1994-01-01

The isotopic exchange reaction and the isotopic separation factor are first recalled; the principles of ion chromatography applied to lithium isotope separation are then reviewed (displacement chromatography) and the process is modelled in the view of dimensioning and optimizing the industrial process; the various dimensioning parameters are the isotopic separation factor, the isotopic exchange kinetics and the material flow rate. Effects of the resin type and structure are presented. Dimensioning is also affected by physico-chemical and hydraulic parameters. Industrial implementation features are also discussed. 1 fig., 1 tab., 5 refs

Process for water-gas generation from degassed combustibles

Energy Technology Data Exchange (ETDEWEB)

1906-05-23

A process for water-gas generation in a continuous operation from degassed combustibles in the lower part of a vertical exterior-heated retort, whose middle part can serve to degas the combustibles, is described. It is characterized in that the water vapor employed is obtained by vaporizing water in the upper part of the retort by means of the waste heat from the heating gases, which had effected the coking of the combustibles before the water-gas recovery or after the latter.

Compound-Specific Chlorine Isotope Analysis of Tetrachloromethane and Trichloromethane by Gas Chromatography-Isotope Ratio Mass Spectrometry vs Gas Chromatography-Quadrupole Mass Spectrometry: Method Development and Evaluation of Precision and Trueness.

Science.gov (United States)

Heckel, Benjamin; Rodríguez-Fernández, Diana; Torrentó, Clara; Meyer, Armin; Palau, Jordi; Domènech, Cristina; Rosell, Mònica; Soler, Albert; Hunkeler, Daniel; Elsner, Martin

2017-03-21

Compound-specific chlorine isotope analysis of tetrachloromethane (CCl 4 ) and trichloromethane (CHCl 3 ) was explored by both, gas chromatography-isotope ratio mass spectrometry (GC-IRMS) and GC-quadrupole MS (GC-qMS), where GC-qMS was validated in an interlaboratory comparison between Munich and Neuchâtel with the same type of commercial GC-qMS instrument. GC-IRMS measurements analyzed CCl isotopologue ions, whereas GC-qMS analyzed the isotopologue ions CCl 3 , CCl 2 , CCl (of CCl 4 ) and CHCl 3 , CHCl 2 , CHCl (of CHCl 3 ), respectively. Lowest amount dependence (good linearity) was obtained (i) in H-containing fragment ions where interference of 35 Cl- to 37 Cl-containing ions was avoided; (ii) with tuning parameters favoring one predominant rather than multiple fragment ions in the mass spectra. Optimized GC-qMS parameters (dwell time 70 ms, 2 most abundant ions) resulted in standard deviations of 0.2‰ (CHCl 3 ) and 0.4‰ (CCl 4 ), which are only about twice as large as 0.1‰ and 0.2‰ for GC-IRMS. To compare also the trueness of both methods and laboratories, samples from CCl 4 and CHCl 3 degradation experiments were analyzed and calibrated against isotopically different reference standards for both CCl 4 and CHCl 3 (two of each). Excellent agreement confirms that true results can be obtained by both methods provided that a consistent set of isotopically characterized reference materials is used.

Gas chromatography at the Tritium Laboratory Karlsruhe

International Nuclear Information System (INIS)

Laesser, R.; Gruenhagen, S.

2003-08-01

Among the analytical techniques (mass spectrometry, laser Raman spectroscopy, gas chromatography, use of ionisation chambers) employed at the Tritium Laboratory Karlsruhe (TLK), gas chromatography plays a prominent role. The main reasons for that are the simplicity of the gas chromatographic separation process, the small space required for the equipment, the low investment costs in comparison to other methods, the robustness of the equipment, the simple and straightforward analysis and the fact that all gas species of interest (with the exception of water) can easily be detected by gas chromatographic means. The conventional gas chromatographs GC1 and GC2 used in the Tritium Measurement Techniques (TMT) System of the TLK and the gas chromatograph GC3 of the experiment CAPER are presented in detail, by discussing their flow diagrams, their major components, the chromatograms measured by means of various detectors, shortcomings and possible improvements. One of the main disadvantages of the conventional gas chromatography is the long retention times required for the analysis of hydrogen gas mixtures. To overcome this disadvantage, micro gas chromatography for hydrogen analysis was developed. Reduction of the retention times by one order of magnitude was achieved. (orig.)

Authenticity assessment of gamma- and delta-decalactone from prunus fruits by gas chromatography combustion/pyrolysis isotope ratio mass spectrometry (GC-C/P-IRMS).

Science.gov (United States)

Tamura, Hirotoshi; Appel, Markus; Richling, Elke; Schreier, Peter

2005-06-29

Authenticity assessment of gamma-decalactone (1) and delta-decalactone (2) from peach (Prunus persica var. persica), apricot (Prunus armeniaca), and nectarine (Prunus persica var. nectarina) was performed using gas chromatography-isotope ratio mass spectrometry (GC-IRMS) in the combustion (C) and pyrolysis (P) mode. In addition, commercially available synthetic (nature-identical) 1 and 2 as well as biotechnologically produced samples (declared to be "natural") were characterized by their delta(2)H(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values. For the Prunus fruits under study, rather narrow ranges of delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data of 1, varying from - 34.6 per thousand to - 38.4 per thousand and -160 per thousand to -206 per thousand, respectively, were obtained. Synthetic references of 1 showed delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data ranging from -27.4 per thousand to -28.3 per thousand and -151 per thousand to -184 per thousand, respectively. Samples of 1 declared to be "natural" exhibited ranges from -28.1 per thousand to -29.2 per thousand and -192 per thousand to -286 per thousand for delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW), respectively. For 2 from peach, apricot, and nectarine, delta(13)C(V)(-)(PDB) values ranging from -34.0 per thousand to -37.9 per thousand were determined; the delta(2)H(V)(-)(SMOW) values ranged from -171 per thousand to -228 per thousand. The delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data for synthetic 2 were -28.2 per thousand and -171 per thousand, respectively, that is, similar to those of 2 from "natural" origin, ranging from -27.7 per thousand to -30.1 per thousand and -185 per thousand to -230 per thousand for delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW), respectively. GC-C/P-IRMS allowed clear-cut analytical differentiation of the synthetic and "ex-plant" origin of 1 and 2, whereas narrow ranges of delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data were found for samples of

USE OF GC-MS/COMBUSTION/IRMS TO IDENTIFY AND DETERMINE THE STABLE CARBON ISOTOPIC RATIO OF INDIVIDUAL LIPIDS

Science.gov (United States)

A system that couples a gas chromatograph (GC) via a split to a quadrapole mass spectrometer (MS) and, through a combustion interface, to an isotope ratio mass spectrometer (IRMS) allows the simultaneous detection of electron impact mass spectra and stable carbon isotope ratio an...

Applications of the gas chromatography in the nuclear science and technology

International Nuclear Information System (INIS)

Gasco Sanchez, L.

1972-01-01

This paper is a review on the applications of the gas chromatography in the nuclear science and technology published up to December 1971. Its contents has been classified under the following heads; I) Radiogaschromatography, II) Isotope separation, III) Preparation of labelled molecules, IV) Nuclear fuel cycle, V) Nuclear reactor technology, VI) Irradiation chemistry, VIl) Separation of me tal compounds in gas phase, VIII) Applications of the gas chromatography carried out at the Junta de Energia Nuclear, Spain. Arapter VIII only includes the investigations carried out from January 1969 to December 1971. Previous investigations in this field has been published elsewhere. (Author)

Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

Science.gov (United States)

Ai, Guomin; Sun, Tong; Dong, Xiuzhu

2014-08-15

Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.

Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

Science.gov (United States)

Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

2010-01-01

In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations.

Science.gov (United States)

Bezemer, Karlijn D B; Koeberg, Mattijs; van der Heijden, Antoine E D M; van Driel, Chris A; Blaga, Cornelia; Bruinsma, Jildert; van Asten, Arian C

2016-09-01

Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences.

Isotopic fractionation of fentanyl and its deuterated analogues by capillary gas chromatography

International Nuclear Information System (INIS)

Sera, Shoji; Goromaru, Tsuyoshi

1997-01-01

Isotopic fractionation of fentanyl (FT) and its deuterated analogues by gas chromatography using capillary columns (CBP1 and CBP5) has been investigated. Seven kinds of analogues were labeled with 5 to 19 deuterium atoms at the anilino, propionyl and/or phenylethyl group of FT. The retention times of deuterated FT in CBP1 and CBP5 columns are inversely proportional to the number of labeled deuterium atoms in the molecule. The difference in free enegy changes (ΔΔG) had a linear relationship with the number of labeled deuterium atoms, except for labeling at anilino and phenylethyl group. The contribution of a deuterium atom to the ΔΔG value was estimated to be 1.13 cal/mol in CBP1 and 1.40 cal/mol in CBP5, respectively. While, its contribution in the propiony group was 2.84 cal/mol in CBP1 and 2.48 cal/mol in CBP5, respectively. An important factor in separation by GC may differences in interactions between the stationary phase of the column with the three dimensional protrusive moiety in the molecule. (author)

Isotopic fractionation of fentanyl and its deuterated analogues by capillary gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Sera, Shoji; Goromaru, Tsuyoshi [Fukuyama Univ., Hiroshima (Japan)

1997-12-01

Isotopic fractionation of fentanyl (FT) and its deuterated analogues by gas chromatography using capillary columns (CBP1 and CBP5) has been investigated. Seven kinds of analogues were labeled with 5 to 19 deuterium atoms at the anilino, propionyl and/or phenylethyl group of FT. The retention times of deuterated FT in CBP1 and CBP5 columns are inversely proportional to the number of labeled deuterium atoms in the molecule. The difference in free enegy changes ({Delta}{Delta}G) had a linear relationship with the number of labeled deuterium atoms, except for labeling at anilino and phenylethyl group. The contribution of a deuterium atom to the {Delta}{Delta}G value was estimated to be 1.13 cal/mol in CBP1 and 1.40 cal/mol in CBP5, respectively. While, its contribution in the propiony group was 2.84 cal/mol in CBP1 and 2.48 cal/mol in CBP5, respectively. An important factor in separation by GC may differences in interactions between the stationary phase of the column with the three dimensional protrusive moiety in the molecule. (author)

Carbon Isotopic Ratios of Amino Acids in Stardust-Returned Samples

Science.gov (United States)

Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

2009-01-01

NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here. we present the carbon isotopic ratios of glycine and E-aminocaproic acid (EACH), the two most abundant amino acids observed, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio crass spectrometry coupled with quadrupole mass spectrometry (GC-QMS/IRMS).

Oxygen isotopic signature of CO2 from combustion processes

Directory of Open Access Journals (Sweden)

W. A. Brand

2011-02-01

Full Text Available For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires, and human induced (fossil fuel combustion, biomass burning in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects on the order of up to 26%permil; became obvious in the derived CO2 from combustion of different kinds of material, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature, sample geometries (e.g. texture and surface-volume ratios and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original total 18O signature of the material appeared to have little influence, however, a contribution of specific bio

Adsorption gas chromatography with 150-ms {sup 216}Po

Energy Technology Data Exchange (ETDEWEB)

Vogt, A [Bern Univ. (Switzerland); Gaeggeler, H W; Tuerler, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-09-01

A gas chromatography apparatus was developed, which allows experiments with volatile radionuclides having shorter half-lives than one second. This apparatus was tested with the 150-ms isotope {sup 216}Po. Experimental data were compared with a Monte Carlo model to determine the adsorption enthalpy {Delta}H{sub a}. (author) 2 figs., 2 refs.

Review: Current applications and challenges for liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS).

Science.gov (United States)

Godin, Jean-Philippe; McCullagh, James S O

2011-10-30

High-precision isotope analysis is recognized as an essential research tool in many fields of study. Until recently, continuous flow isotope ratio mass spectrometry (CF-IRMS) was available via an elemental analyzer or a gas chromatography inlet system for compound-specific analysis of light stable isotopes. In 2004, however, an interface that coupled liquid chromatography with IRMS (LC/IRMS) became commercially available for the first time. This brought the capability for new areas of application, in particular enabling compound-specific δ(13)C analysis of non-volatile, aqueous soluble, compounds from complex mixtures. The interface design brought with it several analytical constraints, however, in particular a lack of compatibility with certain types of chromatography as well as limited flow rates and mobile phase compositions. Routine LC/IRMS methods have, however, been established for measuring the δ(13)C isotopic ratios of underivatized individual compounds for application in archeology, nutrition and physiology, geochemistry, hydrology, soil science and food authenticity. Seven years after its introduction, we review the technical advances and constraints, methodological developments and new applications of liquid chromatography coupled to isotope ratio mass spectrometry. Copyright © 2011 John Wiley & Sons, Ltd.

Biomarkers, carbon isotopic composition and source rock potentials of Awgu coals, middle Benue trough, Nigeria

Science.gov (United States)

Adedosu, Taofik A.; Sonibare, Oluwadayo O.; Tuo, Jincai; Ekundayo, Olusegun

2012-05-01

Coal and carbonaceous shale samples were collected from two boreholes (BH 94 and BH 120) in Awgu formation of Middle Benue Trough, Nigeria. Source rock potentials of the samples were studied using biomarkers and carbon isotopic composition. Biomarkers in the aliphatic fractions in the samples were studied using Gas Chromatography-Mass Spectrometry (GC-MS). The Carbon isotope analysis of individual n-alkanes in the aliphatic fraction was performed using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometer (GC-IRMS). The abundance of hopanes, homohopanes (C31-C35), and C29 steranes in the samples indicate terrestrial plant, phytoplankton and cyanobacteria contributions to the organic matter that formed the coal. High (Pr/Ph) ratio (3.04-11.07) and isotopic distribution of individual alkanes showed that the samples consisted of mixed terrestrial/marine organic matter deposited under oxic condition in lacustrine-fluvial/deltaic depositional environment. The maturity parameters derived from biomarker distributions showed that the samples are in the main phase of oil window.

A Computational Fluid Dynamics Study of Turbulence, Radiation, and Combustion Models for Natural Gas Combustion Burner

Directory of Open Access Journals (Sweden)

Yik Siang Pang

2018-01-01

Full Text Available This paper presents a Computational Fluid Dynamics (CFD study of a natural gas combustion burner focusing on the effect of combustion, thermal radiation and turbulence models on the temperature and chemical species concentration fields. The combustion was modelled using the finite rate/eddy dissipation (FR/EDM and partially premixed flame models. Detailed chemistry kinetics CHEMKIN GRI-MECH 3.0 consisting of 325 reactions was employed to model the methane combustion. Discrete ordinates (DO and spherical harmonics (P1 model were employed to predict the thermal radiation. The gas absorption coefficient dependence on the wavelength is resolved by the weighted-sum-of-gray-gases model (WSGGM. Turbulence flow was simulated using Reynolds-averaged Navier-Stokes (RANS based models. The findings showed that a combination of partially premixed flame, P1 and standard k-ε (SKE gave the most accurate prediction with an average deviation of around 7.8% of combustion temperature and 15.5% for reactant composition (methane and oxygen. The results show the multi-step chemistry in the partially premixed model is more accurate than the two-step FR/EDM. Meanwhile, inclusion of thermal radiation has a minor effect on the heat transfer and species concentration. SKE turbulence model yielded better prediction compared to the realizable k-ε (RKE and renormalized k-ε (RNG. The CFD simulation presented in this work may serve as a useful tool to evaluate a performance of a natural gas combustor. Copyright © 2018 BCREC Group. All rights reserved Received: 26th July 2017; Revised: 9th October 2017; Accepted: 30th October 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Pang, Y.S., Law, W.P., Pung, K.Q., Gimbun, J. (2018. A Computational Fluid Dynamics Study of Turbulence, Radiation, and Combustion Models for Natural Gas Combustion Burner. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 155-169 (doi:10.9767/bcrec

Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry.

Science.gov (United States)

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2010-01-27

A novel procedure was established for the simultaneous characterization of wine glycerol and ethanol (13)C/(12)C isotope ratio, using liquid chromatography/isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing separation of glycerol and ethanol from wine matrix were optimized. Results obtained for 35 Spanish samples exposed no significant differences and very strong correlations (r = 0.99) between the glycerol (13)C/(12)C ratios obtained by an alternative method (gas chromatography/isotope ratio mass spectrometry) and the proposed new methodology, and between the ethanol (13)C/(12)C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The accuracy of the proposed method varied from 0.01 to 0.19 per thousand, and the analytical precision was better than 0.25 per thousand. The new developed LC-IRMS method it is the first isotopic method that allows (13)C/(12)C determination of both analytes in the same run directly from a liquid sample with no previous glycerol or ethanol isolation, overcoming technical difficulties associated with complex sample treatment and improving in terms of simplicity and speed.

Gas Phase Chromatography of some Group 4, 5, and 6 Halides

Energy Technology Data Exchange (ETDEWEB)

Sylwester, Eric Robert [Univ. of California, Berkeley, CA (United States)

1998-10-01

Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr₄, HfBr₄, RfBr₄, NbBr₅, TaOBr₃, HaCl₅, WBr₆, FrBr, and BiBr₃. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography. Adsorption Enthalpy (ΔH_a) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔH_a was observed: RfBr₄ > ZrBr₄ > HfBr₄. The ΔH_a values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of ²⁶¹Rf was performed. ²⁶¹Rf was produced via the ²⁴⁸Cm(¹⁸O, 5n) reaction and observed with a half-life of 74_-6⁺⁷ seconds, in excellent agreement with the previous measurement of 78_-6⁺¹¹ seconds. We recommend a new half-life of 75±7 seconds for ²⁶¹Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant

Dual element ((15)N/(14)N, (13)C/(12)C) isotope analysis of glyphosate and AMPA by derivatization-gas chromatography isotope ratio mass spectrometry (GC/IRMS) combined with LC/IRMS.

Science.gov (United States)

Mogusu, Emmanuel O; Wolbert, J Benjamin; Kujawinski, Dorothea M; Jochmann, Maik A; Elsner, Martin

2015-07-01

To assess sources and degradation of the herbicide glyphosate [N-(phosphonomethyl) glycine] and its metabolite AMPA (aminomethylphosphonic acid), concentration measurements are often inconclusive and even (13)C/(12)C analysis alone may give limited information. To advance isotope ratio analysis of an additional element, we present compound-specific (15)N/(14)N analysis of glyphosate and AMPA by a two step derivatization in combination with gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The N-H group was derivatized with isopropyl chloroformate (iso-PCF), and remaining acidic groups were subsequently methylated with trimethylsilyldiazomethane (TMSD). Iso-PCF treatment at pH 10 indicated decomposition of the derivative. At pH 10, and with an excess of iso-PCF by 10-24, greatest yields and accurate (15)N/(14)N ratios were obtained (deviation from elemental analyzer-IRMS: -0.2 ± 0.9% for glyphosate; -0.4 ± 0.7% for AMPA). Limits for accurate δ(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of δ(15)N and δ(13)C analysis by liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) (1) enabled an improved distinction of commercial glyphosate products and (2) showed that glyphosate isotope values during degradation by MnO2 clearly fell outside the commercial product range. This highlights the potential of combined carbon and nitrogen isotopes analysis to trace sources and degradation of glyphosate.

Rapid measurement of plasma free fatty acid concentration and isotopic enrichment using LC/MS

Science.gov (United States)

Persson, Xuan-Mai T.; Błachnio-Zabielska, Agnieszka Urszula; Jensen, Michael D.

2010-01-01

Measurements of plasma free fatty acids (FFA) concentration and isotopic enrichment are commonly used to evaluate FFA metabolism. Until now, gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) was the best method to measure isotopic enrichment in the methyl derivatives of 13C-labeled fatty acids. Although IRMS is excellent for analyzing enrichment, it requires time-consuming derivatization steps and is not optimal for measuring FFA concentrations. We developed a new, rapid, and reliable method for simultaneous quantification of 13C-labeled fatty acids in plasma using high-performance liquid chromatography-mass spectrometry (HPLC/MS). This method involves a very quick Dole extraction procedure and direct injection of the samples on the HPLC system. After chromatographic separation, the samples are directed to the mass spectrometer for electrospray ionization (ESI) and analysis in the negative mode using single ion monitoring. By employing equipment with two columns connected parallel to a mass spectrometer, we can double the throughput to the mass spectrometer, reducing the analysis time per sample to 5 min. Palmitate flux measured using this approach agreed well with the GC/C/IRMS method. This HPLC/MS method provides accurate and precise measures of FFA concentration and enrichment. PMID:20526002

[Determination of endogenous agmatine in rat plasma by isotope dilution-gas chromatography-mass spectrometry].

Science.gov (United States)

Qiu, Zhongli; Lin, Ying; Xiong, Zhili; Xie, Jianwei

2014-07-01

A method for the determination of endogenous agmatine in rat plasma was developed by isotope dilution-gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The plasma samples were analyzed after protein precipitation, evaporation, derivatization by hexafluoroacetone (HFAA), and clean-up on a Florisil SPE column. The GC-MS analysis utilized stable isotope d8-agmatine as internal standard. The samples after treatme were tested by negative chemical ionization with selected ion monitoring (SIM) which was set at m/z 492 (molecular ion of agmatine) and m/z 500 (molecular ion of internal standard). The limit of detection (LOD) of agmatine standard solution was 0.005 7 ng/mL. The calibration curve of the agmatine spiked in rat plasma showed a good linear relationship at the range of 1.14-57.0 ng/mL (r = 0.997). The recoveries of agmatine spiked in rat plasma ranged from 92.3% to 109.8%. Inter-day and intra-day precisions were less than 15%. The average concentration level of agmatine in rat plasma was (22 +/- 9) ng/mL, and there was no significant difference between male and female SD rats (p > 0.05). The method is high sensitive and specific, and can be used for the determination of endogenous agmatine in plasma. It provides a strong support for the subsequent research of agmatine.

Fractionation of lithium isotopes in cation-exchange chromatography

International Nuclear Information System (INIS)

Oi, Takao; Kawada, Kazuhiko; Kakihana, Hidetake; Hosoe, Morikazu

1991-01-01

Various methods for lithium isotope separation have been developed, and their applicability to large-scale enriched lithium isotope production has been assessed. Ion-exchange chromatography is one such method. Cation-exchange chromatography of lithium was carried out to investigate the lithium isotope effect in aqueous ion-exchange systems. The heavier isotope. 7 Li, was preferentially fractionated into the resin phase in every experiment conducted, and this result is consistent with the results of previous work. The value of the separation factor was 1.00089-1.00171 at 25C. A comparison of lithium isotope effect with those of potassium and rubidium indicated that the isotope effect originating from hydration is larger than the effect due to phase change for lithium, while the opposite is the case with potassium and rubidium

Nitrogen Isotope Composition of Thermally Produced NOx from Various Fossil-Fuel Combustion Sources.

Science.gov (United States)

Walters, Wendell W; Tharp, Bruce D; Fang, Huan; Kozak, Brian J; Michalski, Greg

2015-10-06

The nitrogen stable isotope composition of NOx (δ(15)N-NOx) may be a useful indicator for NOx source partitioning, which would help constrain NOx source contributions in nitrogen deposition studies. However, there is large uncertainty in the δ(15)N-NOx values for anthropogenic sources other than on-road vehicles and coal-fired energy generating units. To this end, this study presents a broad analysis of δ(15)N-NOx from several fossil-fuel combustion sources that includes: airplanes, gasoline-powered vehicles not equipped with a three-way catalytic converter, lawn equipment, utility vehicles, urban buses, semitrucks, residential gas furnaces, and natural-gas-fired power plants. A relatively large range of δ(15)N-NOx values was measured from -28.1‰ to 8.5‰ for individual exhaust/flue samples that generally tended to be negative due to the kinetic isotope effect associated with thermal NOx production. A negative correlation between NOx concentrations and δ(15)N-NOx for fossil-fuel combustion sources equipped with selective catalytic reducers was observed, suggesting that the catalytic reduction of NOx increases δ(15)N-NOx values relative to the NOx produced through fossil-fuel combustion processes. Combining the δ(15)N-NOx measured in this study with previous published values, a δ(15)N-NOx regional and seasonal isoscape was constructed for the contiguous U.S., which demonstrates seasonal and regional importance of various NOx sources.

Development and application of liquid chromatography coupled to isotope ratio mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lijun

2014-02-19

Stable isotope analysis has found widespread applications in various disciplines such as archaeology, geochemistry, biology, food authenticity, and forensic science. Coupling chromatography to isotope ratio mass spectrometry for compound-specific isotope analysis (CSIA) is a trend, as it provides several advantages over bulk isotope analysis, e.g., relatively simple sample preparation, the ability to measure individual compounds in a complex mixture in one run, and the reduced sample size required for precise isotope analysis. Gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS) has been well-established for compound-specific isotope analysis of volatile organic compounds within the last two decades. However, an interface combining liquid chromatography with isotope ratio mass spectrometry (LC/IRMS) was not commercially available until 2004. The current design of the interface requires using a carbon-free eluent in chromatographic separation. This requirement limits the application of the most frequently used reversed-phase liquid chromatography in CSIA, because the elution strength of water at room temperature is too low to serve as mobile phase in reversed-phase separations. In order to increase the elution strength of water, we propose using high temperature water for chromatographic elution. The polarity of water decreases with an increase of temperature, yielding increased elution strength in reversed-phase columns. Therefore, high temperature water can be used as eluent instead of organic solvent for combining reversed-phase liquid chromatography with isotope ratio mass spectrometry (RPLC/IRMS). Additionally, temperature gradients can replace organic solvent gradients to increase chromatographic resolution. This is very important for LC/IRMS analysis, as precise isotope analysis requires baseline separation of analytes. In this thesis, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully

Development and application of liquid chromatography coupled to isotope ratio mass spectrometry

International Nuclear Information System (INIS)

Zhang, Lijun

2014-01-01

Stable isotope analysis has found widespread applications in various disciplines such as archaeology, geochemistry, biology, food authenticity, and forensic science. Coupling chromatography to isotope ratio mass spectrometry for compound-specific isotope analysis (CSIA) is a trend, as it provides several advantages over bulk isotope analysis, e.g., relatively simple sample preparation, the ability to measure individual compounds in a complex mixture in one run, and the reduced sample size required for precise isotope analysis. Gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS) has been well-established for compound-specific isotope analysis of volatile organic compounds within the last two decades. However, an interface combining liquid chromatography with isotope ratio mass spectrometry (LC/IRMS) was not commercially available until 2004. The current design of the interface requires using a carbon-free eluent in chromatographic separation. This requirement limits the application of the most frequently used reversed-phase liquid chromatography in CSIA, because the elution strength of water at room temperature is too low to serve as mobile phase in reversed-phase separations. In order to increase the elution strength of water, we propose using high temperature water for chromatographic elution. The polarity of water decreases with an increase of temperature, yielding increased elution strength in reversed-phase columns. Therefore, high temperature water can be used as eluent instead of organic solvent for combining reversed-phase liquid chromatography with isotope ratio mass spectrometry (RPLC/IRMS). Additionally, temperature gradients can replace organic solvent gradients to increase chromatographic resolution. This is very important for LC/IRMS analysis, as precise isotope analysis requires baseline separation of analytes. In this thesis, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully

Calcium isotope fractionation in liquid chromatography with benzo-18-crown-6 resin in aqueous hydrobromic acid medium

International Nuclear Information System (INIS)

Sato, Takuya; Oi, Takao

2015-01-01

Liquid chromatography operated in a breakthrough mode was employed to study calcium isotope fractionation in the aqueous hydrobromic acid medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of calcium was observed in the frontal part of respective calcium chromatograms. The values of the isotope fractionation coefficient were on the order of 10 -3 . The observed isotope fractionation coefficient was dependent on the concentration of hydrobromic acid in the calcium feed solution; a higher HBr concentration resulted in a smaller fractionation coefficient value. The present calcium isotope effects were most probably mass-dependent, indicating that they mostly came from isotope effects based on molecular vibration. Molecular orbital calculations supported the present experimental results in a qualitative fashion. Chromatography operated in aqueous HBr media is a better system of Ca isotope separation than that operated in aqueous HCl media. (author)

The isotope separation by ion exchange chromatography. Application to the lithium isotopes separation; La separation isotopique par chromatographie ionique

Energy Technology Data Exchange (ETDEWEB)

Albert, M G; Barre, Y; Neige, R

1994-12-31

In this work is described the used study step to demonstrate the industrial feasibility of a lithium isotopes separation process by ion exchange chromatography. After having recalled how is carried out the exchange reaction between the lithium isotopes bound on the cations exchanger resin and those which are in solution and gave the ion exchange chromatography principle, the authors establish a model which takes into account the cascade theory already used for enriched uranium production. The size parameters of this model are: the isotopic separation factor (which depends for lithium of the ligands nature and of the coordination factor), the isotopic exchange kinetics and the mass flow (which depends of the temperature, the lithium concentration, the resins diameter and the front advance). The way they have to be optimized and the implementation of the industrial process are given. (O.M.). 5 refs.

Boron isotopic enrichment by displacement chromatography

International Nuclear Information System (INIS)

Mohapatra, K.K.; Bose, Arun

2014-01-01

10 B enriched boron is used in applications requiring high volumetric neutron absorption (absorption cross section- 3837 barn for thermal and 1 barn for 1 MeV fast neutron). It is used in fast breeder reactor (as control rod material), in neutron counter, in Boron Neutron Capture Therapy etc. Owing to very small separation factor, boron isotopic enrichment is a complex process requiring large number of separation stages. Heavy Water Board has ventured in industrial scale production of 10 B enriched boron using Exchange Distillation Process as well as Ion Displacement Chromatography Process. Ion Displacement Chromatography process is used in Boron Enrichment Plant at HWP, Manuguru. It is based on isotopic exchange between borate ions (B(OH) 4 - ) on anion exchange resin and boric acid passing through resin. The isotopic exchange takes place due to difference in zero point energy of 10 B and 11 B

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part I: Furan.

Science.gov (United States)

Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2014-03-01

Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has - to the best of our knowledge - not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

Isotope ratio monitoring LC/MS (IRM-LC/MS): new applications

International Nuclear Information System (INIS)

Juchelka, D; Hilkert, A.; Krummen, M.

2005-01-01

With the introduction of compound specific isotope analysis by isotope ratio monitoring GC/ MS (IRM-GC/MS) the immediate demand for similar applications using HPLC was created. Many compounds of biological, medical, pharmaceutical and environmental interest are not volatile or too polar. Consequently, they cannot be directly analyzed by gas chromatography. In IRM-GC/MS the carrier is helium, which does not interfere with the essential combust ion step prior to isotope ratio mass spectrometry (IRMS). In opposite the LC mobile phase has inhibited a similar direct conversion up to now. All earlier IRM-LC/MS approaches were based on the removal of the liquid phase prior to combustion risking fractionation of the isotope ratios of the eluted compounds. To avoid such restrictions we developed a new continuous flow concept for the coupling of an HPLC system to the isotope ratio MS for 13 C/ 12C isotope ratio analysis. In the Finnigan LC IsoLink, the liquid phase is not removed from the sample prior to oxidation. The sample is oxidized still in the mobile phase followed by on-line separation of the CO 2 from the liquid phase and transfer into the isotope ratio MS. Therefore, this strategy is based on water and inorganic buffers as mobile phase. The new approach opens up a whole new world in the application of gas isotope ratio mass spectrometry. The 13 C/ 12 C ratio s of organic acids, amino acids, carbohydrates and nucleotides can now be measured. These components typically within a complex matrix are separated by liquid chromatography followed by on-line determination of the isotope ratios. The draw backs of using derivatization and off-line preparation procedures can now be over come. This new technique allow s studying biochemical cycles, running tracer experiments and determining the origin of components. Applications from different scientific areas such as biogeochemistry, molecular biology, and pharmacy as well as authenticity control o f foods will be presented

Exhaust gas recirculation apparatus for internal combustion engine

Energy Technology Data Exchange (ETDEWEB)

Shigemori, M; Eguchi, N

1975-01-07

An exhaust gas recirculation device to reduce nitrogen oxides emission from internal combustion engines is described. The recirculation is achieved by employing a tube connecting between the exhaust pipe and intake tube. A throttle valve is installed within the exhaust pipe between the muffler and recirculation tube, and regulated by exhaust gas temperature. Whenever the gas temperature is high, the valve closes and increases the gas flow to the intake tube. A temperature sensor is installed within the exhaust pipe and controls a solenoid or magnetic air valve linking to the throttle valve through a relay. The recirculation tube can be cooled by a fan to improve the engine power.

Control device for combustible gas concentration

International Nuclear Information System (INIS)

Osawa, Yasuo.

1988-01-01

Purpose: To control the concentration of combustible gases such as hydrogen evolved in a reactor container upon loss-of-coolant accidents. Constitution: Combustible gases evolved from the lower area of a drywell in which a combustible atmosphere is liable to be formed locally are taken out through a take-out pipeway to the outside of a reactor container and processed by a hydrogen-oxygen recombiner. Combustible gases in other areas of the drywell are also introduced to the lower area of the drywell and then taken-out externally for procession. Further, combustible gases in the suppression chamber are introduced by the opening of a vacuum breaking valve through a gas supply pipe to the lower area of the drywell and fluids in the drywell are stirred and diluted with fluids exhausted from the gas supply pipe. Disposition of such take-out pipeway and gas supply pipe can reduce the possibility of forming local combustible atmosphere to improve the integrity of the reactor container. (Kamimura, M.)

Molecular hydrogen (H2) combustion emissions and their isotope (D/H) signatures from domestic heaters, diesel vehicle engines, waste incinerator plants, and biomass burning

NARCIS (Netherlands)

Vollmer, M.K.; Walter, S.; Mohn, J.; Steinbacher, M.; Bond, S.W.; Röckmann, T.; Reimann, S.

2012-01-01

Molecular hydrogen (H2), its stable isotope signature ( D), and the key combustion parameters carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were measured from various combustion processes. H2 in the exhaust of gas and oil-fired heaters and of waste incinerator plants was generally

A simple method for the measurement of radioactivity of samples separated by gas chromatography

International Nuclear Information System (INIS)

Farkas, T.

1981-01-01

Gas chromatographs with flame ionization detector can be used to determine the radioactivity ( 14 C) of separated peaks. After a suitable change in the detector output the combustion product 14 CO 2 can be trapped by hyamine hydroxyde and measured by liquid scintigraphy. 90% of peak activity can be collected and measured, thus the method can be applied to determine the distribution and specific radioactivity of the components separated by gas chromatography. (author)

A predictive model of natural gas mixture combustion in internal combustion engines

Directory of Open Access Journals (Sweden)

Henry Espinoza

2007-05-01

Full Text Available This study shows the development of a predictive natural gas mixture combustion model for conventional com-bustion (ignition engines. The model was based on resolving two areas; one having unburned combustion mixture and another having combustion products. Energy and matter conservation equations were solved for each crankshaft turn angle for each area. Nonlinear differential equations for each phase’s energy (considering compression, combustion and expansion were solved by applying the fourth-order Runge-Kutta method. The model also enabled studying different natural gas components’ composition and evaluating combustion in the presence of dry and humid air. Validation results are shown with experimental data, demonstrating the software’s precision and accuracy in the results so produced. The results showed cylinder pressure, unburned and burned mixture temperature, burned mass fraction and combustion reaction heat for the engine being modelled using a natural gas mixture.

A comparison between EGR and lean-burn strategies employed in a natural gas SI engine using a two-zone combustion model

Energy Technology Data Exchange (ETDEWEB)

Ibrahim, Amr; Bari, Saiful [Sustainable Energy Centre, School of Advanced Manufacturing and Mechanical Engineering, Univ. of South Australia, Mawson Lakes SA 5095 (Australia)

2009-12-15

Exhaust gas recirculation (EGR) strategy has been recently employed in natural gas SI engines as an alternative to lean burn technique in order to satisfy the increasingly stringent emission standards. However, the effect of EGR on some of engine performance parameters compared to lean burn is not yet quite certain. In the current study, the effect of both EGR and lean burn on natural gas SI engine performance was compared at similar operating conditions. This was achieved numerically by developing a computer simulation of the four-stroke spark-ignition natural gas engine. A two-zone combustion model was developed to simulate the in-cylinder conditions during combustion. A kinetic model based on the extended Zeldovich mechanism was also developed in order to predict NO emission. The combustion model was validated using experimental data and a good agreement between the results was found. It was demonstrated that adding EGR to the stoichiometric inlet charge at constant inlet pressure of 130 kPa decreased power more rapidly than excess air; however, the power loss was recovered by increasing the inlet pressure from 130 kPa at zero dilution to 150 kPa at 20% EGR dilution. The engine fuel consumption increased by 10% when 20% EGR dilution was added at inlet pressure of 150 kPa compared to using 20% air dilution at 130 kPa. However, it was found that EGR dilution strategy is capable of producing extremely lower NO emission than lean burn technique. NO emission was reduced by about 70% when the inlet charge was diluted at a rate of 20% using EGR instead of excess air. (author)

A comparison between EGR and lean-burn strategies employed in a natural gas SI engine using a two-zone combustion model

International Nuclear Information System (INIS)

Ibrahim, Amr; Bari, Saiful

2009-01-01

Exhaust gas recirculation (EGR) strategy has been recently employed in natural gas SI engines as an alternative to lean burn technique in order to satisfy the increasingly stringent emission standards. However, the effect of EGR on some of engine performance parameters compared to lean burn is not yet quite certain. In the current study, the effect of both EGR and lean burn on natural gas SI engine performance was compared at similar operating conditions. This was achieved numerically by developing a computer simulation of the four-stroke spark-ignition natural gas engine. A two-zone combustion model was developed to simulate the in-cylinder conditions during combustion. A kinetic model based on the extended Zeldovich mechanism was also developed in order to predict NO emission. The combustion model was validated using experimental data and a good agreement between the results was found. It was demonstrated that adding EGR to the stoichiometric inlet charge at constant inlet pressure of 130 kPa decreased power more rapidly than excess air; however, the power loss was recovered by increasing the inlet pressure from 130 kPa at zero dilution to 150 kPa at 20% EGR dilution. The engine fuel consumption increased by 10% when 20% EGR dilution was added at inlet pressure of 150 kPa compared to using 20% air dilution at 130 kPa. However, it was found that EGR dilution strategy is capable of producing extremely lower NO emission than lean burn technique. NO emission was reduced by about 70% when the inlet charge was diluted at a rate of 20% using EGR instead of excess air.

HDT mixtures treatment strategies by gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Laquerbe, C.; Contreras, S.; Demoment, J. [Commissariat a l' Energie Atomique - CEA/Valduc, F-21121 Is sur Tille (France)

2008-07-15

Gas phase chromatographic processes are of interest for the separation of hydrogen isotopes from an HDT mixture. For a certain quantity, they are very competitive and present several benefits. Nevertheless no active packing material allows to have simultaneously good enrichment performances for tritium production and high decontamination capabilities for HD gases. The influence of the packing material is first described in this article. Then two specific processes (TCAP and Reverse Chromatography), each well adapted to perform one target, are presented. Finally, the problematic to propose an optimized treatment scheme associating these two processes is formulated. (authors)

HDT mixtures treatment strategies by gas chromatography

International Nuclear Information System (INIS)

Laquerbe, C.; Contreras, S.; Demoment, J.

2008-01-01

Gas phase chromatographic processes are of interest for the separation of hydrogen isotopes from an HDT mixture. For a certain quantity, they are very competitive and present several benefits. Nevertheless no active packing material allows to have simultaneously good enrichment performances for tritium production and high decontamination capabilities for HD gases. The influence of the packing material is first described in this article. Then two specific processes (TCAP and Reverse Chromatography), each well adapted to perform one target, are presented. Finally, the problematic to propose an optimized treatment scheme associating these two processes is formulated. (authors)

Torrefaction of empty fruit bunches under biomass combustion gas atmosphere.

Science.gov (United States)

Uemura, Yoshimitsu; Sellappah, Varsheta; Trinh, Thanh Hoai; Hassan, Suhaimi; Tanoue, Ken-Ichiro

2017-11-01

Torrefaction of oil palm empty fruit bunches (EFB) under combustion gas atmosphere was conducted in a batch reactor at 473, 523 and 573K in order to investigate the effect of real combustion gas on torrefaction behavior. The solid mass yield of torrefaction in combustion gas was smaller than that of torrefaction in nitrogen. This may be attributed to the decomposition enhancement effect by oxygen and carbon dioxide in combustion gas. Under combustion gas atmosphere, the solid yield for torrefaction of EFB became smaller as the temperature increased. The representative products of combustion gas torrefaction were carbon dioxide and carbon monoxide (gas phase) and water, phenol and acetic acid (liquid phase). By comparing torrefaction in combustion gas with torrefaction in nitrogen gas, it was found that combustion gas can be utilized as torrefaction gas to save energy and inert gas. Copyright © 2017 Elsevier Ltd. All rights reserved.

High-precision measurement of phenylalanine δ15N values for environmental samples: a new approach coupling high-pressure liquid chromatography purification and elemental analyzer isotope ratio mass spectrometry.

Science.gov (United States)

Broek, Taylor A B; Walker, Brett D; Andreasen, Dyke H; McCarthy, Matthew D

2013-11-15

Compound-specific isotope analysis of individual amino acids (CSI-AA) is a powerful new tool for tracing nitrogen (N) source and transformation in biogeochemical cycles. Specifically, the δ(15)N value of phenylalanine (δ(15)N(Phe)) represents an increasingly used proxy for source δ(15)N signatures, with particular promise for paleoceanographic applications. However, current derivatization/gas chromatography methods require expensive and relatively uncommon instrumentation, and have relatively low precision, making many potential applications impractical. A new offline approach has been developed for high-precision δ(15)N measurements of amino acids (δ(15)N(AA)), optimized for δ(15)N(Phe) values. Amino acids (AAs) are first purified via high-pressure liquid chromatography (HPLC), using a mixed-phase column and automated fraction collection. The δ(15)N values are determined via offline elemental analyzer-isotope ratio mass spectrometry (EA-IRMS). The combined HPLC/EA-IRMS method separated most protein AAs with sufficient resolution to obtain accurate δ(15)N values, despite significant intra-peak isotopic fractionation. For δ(15)N(Phe) values, the precision was ±0.16‰ for standards, 4× better than gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS; ±0.64‰). We also compared a δ(15)N(Phe) paleo-record from a deep-sea bamboo coral from Monterey Bay, CA, USA, using our method versus GC/C/IRMS. The two methods produced equivalent δ(15)N(Phe) values within error; however, the δ(15)N(Phe) values from HPLC/EA-IRMS had approximately twice the precision of GC/C/IRMS (average stdev of 0.27‰ ± 0.14‰ vs 0.60‰ ± 0.20‰, respectively). These results demonstrate that offline HPLC represents a viable alternative to traditional GC/C/IMRS for δ(15)N(AA) measurement. HPLC/EA-IRMS is more precise and widely available, and therefore useful in applications requiring increased precision for data interpretation (e.g. δ(15)N paleoproxies

The isotope separation by ion exchange chromatography. Application to the lithium isotopes separation

International Nuclear Information System (INIS)

Albert, M.G.; Barre, Y.; Neige, R.

1993-01-01

In this work is described the used study step to demonstrate the industrial feasibility of a lithium isotopes separation process by ion exchange chromatography. After having recalled how is carried out the exchange reaction between the lithium isotopes bound on the cations exchanger resin and those which are in solution and gave the ion exchange chromatography principle, the authors establish a model which takes into account the cascade theory already used for enriched uranium production. The size parameters of this model are: the isotopic separation factor (which depends for lithium of the ligands nature and of the coordination factor), the isotopic exchange kinetics and the mass flow (which depends of the temperature, the lithium concentration, the resins diameter and the front advance). The way they have to be optimized and the implementation of the industrial process are given. (O.M.)

Statistical model for classifying the feeding systems of Iberian pigs through Gas Chromatography (GC-FID and Isotope Ratio Mass Spectrometry (GC-C-IRMS

Directory of Open Access Journals (Sweden)

García-Casco, J. M.

2013-04-01

Full Text Available In the present work we have analyzed a total of 734 subcutaneous fat samples from Iberian pigs with different feeding systems for fattening (“Bellota”, “Recebo”, “Campo” and “Cebo” over three consecutive years, 2009-2011. Lipids were extracted from the subcutaneous fat on the rump, and after esterification, they were analyzed by Gas Chromatography (GC-FID and Gas Chromatography- Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS. Mean fatty acids and isotope ratios show that there are differences according to the year and feeding systems, two factors that should be taken into account when classifying the animals. The application of different prediction models based on Discriminant analysis has allowed us to establish a method for the classification of animals according to the feeding system type, with a correct percentage of 85% using three or four classification categories (Bellota, Recebo, Campo and/or Cebo and 91% using only two categories, Cebo and Bellota. This model could provide the basis for appropriate classification of Iberian pigs according to their feeding regime.En el presente trabajo se han analizado un total de 734 muestras de tejido subcutáneo de cerdos ibéricos con distintos tipos de alimentación de engorde (Bellota, Recebo, Cebo y Campo a lo largo de tres años consecutivos, 2009-2011. Se han extraído los lípidos de la grasa subcutánea de rabadilla, y después de su esterificación, se han analizado por Cromatografía de gases (GC-FID y por Espectrometría de masas de relaciones isotópicas (GC-C-IRMS. Las medias de los ácidos grasos y de las relaciones isotópicas muestran que existen diferencias según el año y tipo de alimentación, factores que deberían tenerse en cuenta a la hora de clasificar los animales. La aplicación de distintos modelos de predicción basados en análisis discriminante permite establecer un método para la clasificación de los animales según el tipo de alimentación, con

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry.

Science.gov (United States)

Krämer, Lisa; Jäger, Christian; Trezzi, Jean-Pierre; Jacobs, Doris M; Hiller, Karsten

2018-02-14

Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13 C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13 C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS). The limit of quantification was increased by optimizing (1) the metabolite extraction from plasma, (2) the GC-MS measurement, and (3) most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13 C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13 C-labeled bread and quantified 13 C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine). Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated.

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry

Science.gov (United States)

Krämer, Lisa; Jäger, Christian; Jacobs, Doris M.; Hiller, Karsten

2018-01-01

Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS). The limit of quantification was increased by optimizing (1) the metabolite extraction from plasma, (2) the GC-MS measurement, and (3) most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13C-labeled bread and quantified 13C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine). Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated. PMID:29443915

Quantification of Stable Isotope Traces Close to Natural Enrichment in Human Plasma Metabolites Using Gas Chromatography-Mass Spectrometry

Directory of Open Access Journals (Sweden)

Lisa Krämer

2018-02-01

Full Text Available Currently, changes in metabolic fluxes following consumption of stable isotope-enriched foods are usually limited to the analysis of postprandial kinetics of glucose. Kinetic information on a larger diversity of metabolites is often lacking, mainly due to the marginal percentage of fully isotopically enriched plant material in the administered food product, and hence, an even weaker 13C enrichment in downstream plasma metabolites. Therefore, we developed an analytical workflow to determine weak 13C enrichments of diverse plasma metabolites with conventional gas chromatography-mass spectrometry (GC-MS. The limit of quantification was increased by optimizing (1 the metabolite extraction from plasma, (2 the GC-MS measurement, and (3 most importantly, the computational data processing. We applied our workflow to study the catabolic dynamics of 13C-enriched wheat bread in three human subjects. For that purpose, we collected time-resolved human plasma samples at 16 timepoints after the consumption of 13C-labeled bread and quantified 13C enrichment of 12 metabolites (glucose, lactate, alanine, glycine, serine, citrate, glutamate, glutamine, valine, isoleucine, tyrosine, and threonine. Based on isotopomer specific analysis, we were able to distinguish catabolic profiles of starch and protein hydrolysis. More generally, our study highlights that conventional GC-MS equipment is sufficient to detect isotope traces below 1% if an appropriate data processing is integrated.

Study on atmospheric hydrogen enrichment by cryopump method and isotope separation by gas chromatography

International Nuclear Information System (INIS)

Taniyama, Yuki; Momoshima, Noriyuki

2001-01-01

To obtain the information of source of atmospheric hydrogen tritium an analysis of tritium isotopes is thought to be effective. So an atmospheric hydrogen enrichment apparatus and a cryogenic gas chromatographic column were made. Experiments were carried out to study the performance of cryopump to enrich atmospheric hydrogen and the column to separate hydrogen isotopes that obtained by cryopump method. The cryopump was able to process about 1000 1 atmosphere and the column was able to separate hydrogen isotopes with good resolution. (author)

Identification of fentanyl metabolites in rat urine by gas chromatography-mass spectrometry with stable-isotope tracers

Energy Technology Data Exchange (ETDEWEB)

Goromaru, T.; Matsuura, H.; Furuta, T.; Baba, S.; Yoshimura, N.; Miyawaki, T.; Sameshima, T.

The metabolites of fentanyl (l), which has been widely used as a neuroleptic analgesic agent, were identified in urine of rats by gas chromatography-mass spectrometry combined with a stable-isotope tracer technique. After the oral administration of an equimolar mixture of l and deuterium-labeled l (l/l-d5), the urinary metabolites were extracted with chloroform at pH 9.0. Extracts were derivatized and analyzed by GC/MS. Metabolites were identified by the presence of doublet ion peaks separated by 5 amu, and chemical structures were established from analyses of fragmentation pathways. The metabolites were identified as 4-N-(N-propionylanilino)-piperidine, 4-N-(N-hydroxypropionylanilino)piperidine, 4-N-(N-propionylanilino) hydroxypiperidine, 1-(2-phenethyl)-4-N-(N-hydroxypropionylanilino)piperidine and 1-(2-phenethyl)-4-N-(N-propionylanilino)hydroxypiperidine. These metabolites, together with unchanged l, were also detected in urine of rats receiving l/l-d5 intravenously, by selected-ion monitoring of the specific cluster ions.

Determination of the alkylpyrazine composition of coffee using stable isotope dilution-gas chromatography-mass spectrometry (SIDA-GC-MS).

Science.gov (United States)

Pickard, Stephanie; Becker, Irina; Merz, Karl-Heinz; Richling, Elke

2013-07-03

A stable isotope dilution analysis based on gas chromatography-mass spectrometry analysis (SIDA-GC-MS) was developed for the quantitative analysis of 12 alkylpyrazines found in commercially available coffee samples. These compounds contribute to coffee flavor. The accuracy of this method was tested by analyzing model mixtures of alkylpyrazines. Comparisons of alkylpyrazine-concentrations suggested that water as extraction solvent was superior to dichloromethane. The distribution patterns of alkylpyrazines in different roasted coffees were quite similar. The most abundant alkylpyrazine in each coffee sample was 2-methylpyrazine, followed by 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, and 2,3,5-trimethylpyrazine, respectively. Among the alkylpyrazines tested, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3,5-dimethylpyrazine revealed the lowest concentrations in roasted coffee. By the use of isotope dilution analysis, the total concentrations of alkylpyrazines in commercially available ground coffee ranged between 82.1 and 211.6 mg/kg, respectively. Decaffeinated coffee samples were found to contain lower amounts of alkylpyrazines than regular coffee samples by a factor of 0.3-0.7, which might be a result of the decaffeination procedure.

Possibilities of gas-phase radio-chromatography application to permanent-gas analysis

International Nuclear Information System (INIS)

Dupuis, M.C.; Charrier, G.; Alba, C.; Massimino, D.

1970-01-01

The gas-phase radio-chromatography technique has been applied to the rapid analysis of permanent gases (H 2 , O 2 , N 2 , A, Kr, Xe, CO, CH 4 ) labelled with radioactive indicators ( 3 H, 37 A, 85 Kr, 133 Xe). After calibration, the components of such a mixture can be identified and their concentrations measured in less than two hours, using a sample volume of from 0.1 to 10 cm 3 . The minimum detectable activity is of the order of 10 -4 μC for each radioactive isotope. The measurements are reproducible to about 2 to 3 per cent. This work has been mainly concerned with the influence of parameters affecting the response of the radioactivity detector (ionization chamber or gas flow proportional counter). The method has very numerous applications both theoretically, for the study of chromatographic phenomena under ideal conditions (infinitesimal concentrations made possible by the use of radioactive tracers), and practically, for rapid and accurate radiochemical analysis of radioactive gas mixtures. (authors) [fr

Key factors of combustion from kinetics to gas dynamics

CERN Document Server

Rubtsov, Nikolai M

2017-01-01

This book summarizes the main advances in the mechanisms of combustion processes. It focuses on the analysis of kinetic mechanisms of gas combustion processes and experimental investigation into the interrelation of kinetics and gas dynamics in gas combustion. The book is complimentary to the one previously published, The Modes of Gaseous Combustion.

Simultaneous analysis of (13)C-glutathione as its dimeric form GSSG and its precursor [1-(13)C]glycine using liquid chromatography/isotope ratio mass spectrometry

NARCIS (Netherlands)

Schierbeek, Henk; Rook, Denise; te Braake, Frans W. J.; Dorst, Kristien Y.; Voortman, Gardi; Godin, Jean-Philippe; Fay, Laurent-Bernard; van Goudoever, Johannes B.

2009-01-01

Determination of glutathione kinetics using stable isotopes requires accurate measurement of the tracers and tracees. Previously, the precursor and synthesized product were measured with two separate techniques, liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) and gas

Modeling internal ballistics of gas combustion guns.

Science.gov (United States)

Schorge, Volker; Grossjohann, Rico; Schönekess, Holger C; Herbst, Jörg; Bockholdt, Britta; Ekkernkamp, Axel; Frank, Matthias

2016-05-01

Potato guns are popular homemade guns which work on the principle of gas combustion. They are usually constructed for recreational rather than criminal purposes. Yet some serious injuries and fatalities due to these guns are reported. As information on the internal ballistics of homemade gas combustion-powered guns is scarce, it is the aim of this work to provide an experimental model of the internal ballistics of these devices and to investigate their basic physical parameters. A gas combustion gun was constructed with a steel tube as the main component. Gas/air mixtures of acetylene, hydrogen, and ethylene were used as propellants for discharging a 46-mm caliber test projectile. Gas pressure in the combustion chamber was captured with a piezoelectric pressure sensor. Projectile velocity was measured with a ballistic speed measurement system. The maximum gas pressure, the maximum rate of pressure rise, the time parameters of the pressure curve, and the velocity and path of the projectile through the barrel as a function of time were determined according to the pressure-time curve. The maximum gas pressure was measured to be between 1.4 bar (ethylene) and 4.5 bar (acetylene). The highest maximum rate of pressure rise was determined for hydrogen at (dp/dt)max = 607 bar/s. The muzzle energy was calculated to be between 67 J (ethylene) and 204 J (acetylene). To conclude, this work provides basic information on the internal ballistics of homemade gas combustion guns. The risk of injury to the operator or bystanders is high, because accidental explosions of the gun due to the high-pressure rise during combustion of the gas/air mixture may occur.

Studies on the separation of hydrogen isotopes and spin isomers by gas chromatography

International Nuclear Information System (INIS)

Pushpa, K.K.; Annaji Rao, K.

2000-08-01

Separation and analysis of mixture of hydrogen isotopes has gained considerable importance because of various applications needing different isotopes in lasers, nuclear reactions and tracer or labelled compounds. In the literature gas chromatographic methods are reported using columns packed with partly dehydrated or thoroughly dehydrated alumina/molecular sieve stationary phase at 77 deg K with helium, neon and even hydrogen or deuterium as carrier gas. In the present study an attempt is made to compare the chromatographic behaviour of these two stationary phases using virgin and Fe doped form in partly dehydrated and thoroughly dehydrated state, using helium, neon, hydrogen and deuterium as carrier gas. The results of this study show that helium or neon carrier gas behave similarly broad peaks with some tailing. Sharp symmetric peaks are obtained with hydrogen or deuterium carrier gas. This is attributed to large hold up capacity for H 2 or D 2 at 77 deg K in these materials as compared to helium or neon. Spin isomers of H 2 or D 2 are separated on Fe free stationary phases, though ortho H 2 and HD are not resolved. Using a combination of Fe doped short column and plain alumina column, both maintained in dehydrated form, the effect of Fe doping on thermal equilibrium of ortho/para forms at 77 deg K is clearly demonstrated. (author)

The Relation between Gas Flow and Combustibility using Actual Engine (Basic Experiment of Gas Flow and Combustibility under Low Load Condition)

OpenAIRE

田坂, 英紀; 泉, 立哉; 木村, 正寿

2003-01-01

Abstract ###Consideration of the global environment problems by exhaust gas is becoming important in recent years. ###Especially about internal combustion engine, social demand has been increasing about low pollution, high ###efficiency and so on. Controlling gas flow in cylinder becomes the key getting good combustion state in ###various driving states. ###The purpose of the research is analysis about the relation between gas flow and combustibility in the cylinder. ###So we measured gas flo...

Gas hydrate formation process for pre-combustion capture of carbon dioxide

International Nuclear Information System (INIS)

Lee, Hyun Ju; Lee, Ju Dong; Linga, Praveen; Englezos, Peter; Kim, Young Seok; Lee, Man Sig; Kim, Yang Do

2010-01-01

In this study, gas hydrate from CO 2 /H 2 gas mixtures with the addition of tetrahydrofuran (THF) was formed in a semi-batch stirred vessel at various pressures and temperatures to investigate the CO 2 separation/recovery properties. This mixture is of interest to CO 2 separation and recovery from Integrated Gasification Combine Cycle (IGCC) power plants. During hydrate formation the gas uptake was determined and composition changes in the gas phase were obtained by gas chromatography. The impact of THF on hydrate formation from the CO 2 /H 2 was observed. The addition of THF significantly reduced the equilibrium formation conditions. 1.0 mol% THF was found to be the optimum concentration for CO 2 capture based on kinetic experiments. The present study illustrates the concept and provides thermodynamic and kinetic data for the separation/recovery of CO 2 (pre-combustion capture) from a fuel gas (CO 2 /H 2 ) mixture.

Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

Science.gov (United States)

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

The concentration of carbon dioxide (CO2) in the atmosphere has dramatically increased from the start of the industrial revolution in the mid-1700s to present levels exceeding 400 ppm. Carbon dioxide derived from fossil fuel combustion is a greenhouse gas and a major contributor to on-going climate change. Carbon and oxygen stable isotope geochemistry is a useful tool to help model and predict the contributions of anthropogenic sources of CO2 in the global carbon cycle. Surprisingly few studies have addressed the carbon and oxygen isotopic composition of CO2 derived from coal combustion. The goal of this study is to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions.Six coal samples were selected that represent various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~ 1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory.The major findings of this preliminary work indicate that the isotopic signatures of δ13C (relative to the Vienna Pee Dee Belemnite scale, VPDB) of CO2 resulting from coal combustion are similar to the δ13CVPDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰, see http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2

Magnesium isotope fractionation in cation-exchange chromatography

International Nuclear Information System (INIS)

Oi, T.; Yanase, S.; Kakihana, H.

1987-01-01

Band displacement chromatography of magnesium has been carried out successfully for the purpose of magnesium isotope separation by using a strongly acidic cation-exchange resin and the strontium ion as the replacement ion. A small but definite accumulation of the heavier isotopes ( 25 Mg, 26 Mg) has been observed at the front parts of the magnesium chromatograms. The heavier isotopes have been fractionated preferentially into the solution phase. The single-stage separation factors have been calculated for the 25 Mg/ 24 Mg and 26 Mg/ 24 isotopic pairs at 25 0 C. The reduced partition function ratios of magnesium species involved in the present study have been estimated

Determination of radiochemical purity using gas chromatography

International Nuclear Information System (INIS)

1975-01-01

The concepts of chromatography, gas chromatography, activity, radiochemical impurity are defined; the procedure of the application of gas chromatography for detecting radiochemical purity of substances is standardized. (E.F.)

Effects of stepwise gas combustion on NOx generation

International Nuclear Information System (INIS)

Woperane Seredi, A.; Szepesi, E.

1999-01-01

To decrease NO x emission from gas boilers, the combustion process of gas has been modified from continuous combustion to step-wise combustion. In this process the combustion temperature, the temperature peaks in the flame, the residence time of combustion products in the high-temperature zone and the oxygen partial pressure are changed advantageously. Experiments were performed using multistage burners, and the NO x emission was recorded. It was found that the air factor of the primary combustion space has a determining effect on the NO x reduction. (R.P.)

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part I: Furan

Science.gov (United States)

Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2013-01-01

Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has – to the best of our knowledge – not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

Gas chromatography in space

Science.gov (United States)

Akapo, S. O.; Dimandja, J. M.; Kojiro, D. R.; Valentin, J. R.; Carle, G. C.

1999-01-01

Gas chromatography has proven to be a very useful analytical technique for in situ analysis of extraterrestrial environments as demonstrated by its successful operation on spacecraft missions to Mars and Venus. The technique is also one of the six scientific instruments aboard the Huygens probe to explore Titan's atmosphere and surface. A review of gas chromatography in previous space missions and some recent developments in the current environment of fiscal constraints and payload size limitations are presented.

Combustion driven NF3 chemical laser

International Nuclear Information System (INIS)

1975-01-01

Stable, inert, non-corrosive nitrogen trifluoride gas and an inorganic source of hydrogen or deuterium gas are used as reactants in a compact combustion driven chemical laser. Nitrogen trifluoride is introduced into the combustion chamber of a chemical laser together with a hydrogen source selected from hydrogen, hydrazine, ammonia, acetylene, or benzene and the deuterated isotopes thereof and an optional inert diluent gas wherein the nitrogen trifluoride and the hydrogen- or deuterium-source gas hypergolically reacted upon heating to initiation temperature. Dissociated products from the reaction pass into a laser cavity at supersonic velocities where they are reacted with a source gas which is the isotopic opposite of the gas introduced into the combustor and which has been heated by regenerative cooling. Excited molecules of hydrogen fluoride or deuterium fluoride produce laser radiation which leaves the optical resonator cavity transversely to the flow of gases

Characterization of the designer drug deschloroketamine (2-methylamino-2-phenylcyclohexanone) by gas chromatography/mass spectrometry, liquid chromatography/high-resolution mass spectrometry, multistage mass spectrometry, and nuclear magnetic resonance.

Science.gov (United States)

Frison, Giampietro; Zamengo, Luca; Zancanaro, Flavio; Tisato, Francesco; Traldi, Pietro

2016-01-15

Clinical and forensic toxicology laboratories are challenged every day by the analytical aspects of the new psychoactive substances phenomenon. In this study we describe the analytical characterization of a new ketamine derivative, deschloroketamine (2-methylamino-2-phenylcyclohexanone), contained in seized powders. The analytical techniques employed include gas chromatography/mass spectrometry (GC/MS), liquid chromatography/electrospray ionization coupled with Orbitrap high-resolution/MS (LC/ESI-HRMS), multistage MS (ESI-MS(n)), and NMR. The LC/ESI-HRMS analyses consisted of accurate mass measurements of MH(+) ions in full-scan mode; comparison of experimental and calculated MH(+) isotopic patterns; and examination of the isotopic fine structure (IFS) of the M + 1, M + 2, M + 3 isotopic peaks relative to the monoisotopic M + 0 peak. The collision-induced product ions of the MH(+) ions were studied by both HRMS and MS(n). (1)H and (13)C NMR measurements were carried out to confirm the chemical structure of the analyte. The EI mass spectra obtained by GC/MS analysis showed the presence of molecular ions at m/z 203, and main fragment ions at m/z 175, 174, 160, 147, 146, and 132. The application of LC/ESI-HRMS allowed us to obtain: the accurate mass of deschloroketamine MH(+) ions with a mass accuracy of 1.47 ppm; fully superimposable experimental and calculated MH(+) isotopic patterns, with a relative isotopic abundance value of 3.69 %; and the IFS of the M + 1, M + 2, M + 3 isotopic peaks completely in accordance with theoretical values. Examination of the product ions of MH(+), as well as the study of both (1)H and (13)C NMR spectra, enabled the full characterization of the molecular structure of deschloroketamine. The combination of the employed analytical techniques allowed the characterization of the seized psychoactive substance, in spite of the lack of a reference standard. Deschloroketamine is a ketamine analogue considered to be

Gas chromatography-mass spectrometry and high-performance liquid chromatographic analyses of thermal degradation products of common plastics

OpenAIRE

Pacakova, V.; Leclercq, P.A.

1991-01-01

The thermo-oxidation of five commonly used materials, namely low-density polyethylene, retarded polyethylene, paper with a polyethylene foil, a milk package and filled polypropylene, was studied. Capillary gas chromatography and gas chromatography-mass spectrometry were used to analyze the volatile degradation products, while high-performance liquid chromatography was employed to measure polycyclic aromatic hydrocarbons. The results are discussed from the point of view of toxicity of the prod...

Gas chromatography analysisof organic compounds labelled with 14C and T

International Nuclear Information System (INIS)

Matukha, M.; Zhilka, L.; Khejze, K.-Kh.; Gehrner, Kh.

1982-01-01

Various methods of radio gas chromatography (RGC) including non-destructiveones are analyzed and compared as well as systems for their realization. The selected methods were verified in interlaboratory studies. The developed RGC-system produce a linear output signal proportional to the measured sample activity within 10 to 200 kBg. The system includes a nondestructive mass and radioactivity detector in series with combustion chamber of the effluent after TCD passage and 14 CO 2 absorber with ethanolamine. The activity of obtained solution is measured by means of liquid scintillation method [ru

Formation and Control of Sulfur Oxides in Sour Gas Oxy-Combustion: Prediction Using a Reactor Network Model

KAUST Repository

Bongartz, Dominik

2015-11-19

© 2015 American Chemical Society. Sour natural gas currently requires expensive gas cleanup before it can be used in power generation because it contains large amounts of hydrogen sulfide (H2S) and carbon dioxide (CO2) that entail a low heating value and highly corrosive combustion products. A potential alternative is to use the gas directly in a gas turbine process employing oxy-fuel combustion, which could eliminate the need for gas cleanup while also enabling the application of carbon capture and sequestration, possibly combined with enhanced oil recovery (EOR). However, the exact influence of an oxy-fuel environment on the combustion products of sour gas has not been quantified yet. In this work, we used a reactor network model for the combustor and the gas turbine together with our recently assembled and validated detailed chemical reaction mechanism for sour gas combustion to investigate the influence of some basic design parameters on the combustion products of natural gas and sour gas in CO2 or H2O diluted oxy-fuel combustion as well as in conventional air combustion. Our calculations show that oxy-fuel combustion produces up to 2 orders of magnitude less of the highly corrosive product sulfur trioxide (SO3) than air combustion, which clearly demonstrates its potential in handling sulfur containing fuels. Unlike in air combustion, in oxy-fuel combustion, SO3 is mainly formed in the flame zone of the combustor and is then consumed as the combustion products are cooled in the dilution zone of the combustor and the turbine. In oxy-fuel combustion, H2O dilution leads to a higher combustion efficiency than CO2 dilution. However, if the process is to be combined with EOR, CO2 dilution makes it easier to comply with the very low levels of oxygen (O2) required in the EOR stream. Our calculations also show that it might even be beneficial to operate slightly fuel-rich because this simultaneously decreases the O2 and SO3 concentration further. The flame zone

Determination of (BTEX) of the gasoline's combustion in Ecuador

International Nuclear Information System (INIS)

Garcia, Nelson; Insuasti, Alicia

1998-01-01

The contents of benzene, toluene, ethyl benzene and xylenes (BTEX) were determined and quantified in the gasoline's combustion on an internal combustion engine. Gas chromatography with flame ionization detector were used for chemical determinations

Nitrogen oxides in the combustion products of gas cookers

Energy Technology Data Exchange (ETDEWEB)

Benes, M.; Zahourek, J.

1981-07-01

The combustion of town gas and natural gas in two types of gas ranges manufactured in Czechoslovakia resulted in measurable amounts of NO/sub x/ in both the combustion products and the surrounding air. In all the cases tested, the amounts of NO/sub x/ given off exceeded levels permitted by current Czech standards. These results indicate that before the widespread use of any new gas ranges, their combustion products should be tested for NO/sub x/.

Nature of unresolved complex mixture in size-distributed emissions from residential wood combustion as measured by thermal desorption-gas chromatography-mass spectrometry

Science.gov (United States)

Hays, Michael D.; Smith, N. Dean; Dong, Yuanji

2004-08-01

Unresolved complex mixture (UCM) is an analytical artifact of gas chromatographs of combustion source-related fine aerosol extracts. In this study the UCM is examined in size-resolved fine aerosol emissions from residential wood combustion. The aerosols are sorted by size in an electrical low-pressure impactor (ELPI) and subsequently analyzed by thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). A semiquantitative system for predicting the branched alkane, cycloalkane, alkylbenzene, C3-, C4-, C5-alkylbenzene, methylnaphthalene, C3-, C4-, C5-alkylnaphthalene, methylphenanthrene C2-, C3-alkylphenanthrene, and dibenzothiophene concentrations in the UCM is introduced. Analysis by TD/GS/MS detects UCM on each ELPI stage for all six combustion tests. The UCM baseline among the different fuel types is variable. In particular, the UCM of Pseudotsuga sp. is enriched in later-eluting compounds of lower volatility. A high level of reproducibility is achieved in determining UCM areas. UCM fractions (UCM ion area/total extracted ion chromatograph area) by individual ELPI stage return a mean relative standard deviation of 19.1% over the entire combustion test set, indicating a highly consistent UCM fraction across the ELPI size boundaries. Among the molecular ions investigated, branched alkane (m/z 57) and dibenzothiophene (m/z 212 and 226) constituents are most abundant in UCM emissions from RWC, collectively accounting for 64-95% of the targeted chemical species. The total UCM emissions span 446-756 mg/kg of dry biomass burned and correspond to an upper limit of 7.1% of the PM2.5 mass. The UCM emissions are primarily accumulation mode (0.1 μm ≤ aerodynamic diameter (da) ≤ 1 μm), with a geometric mean diameter (dg) range of 120.3-518.4 nm. UCM in PM2.5 is chemically asymmetric (shifted to finer da), typically clustering at da ≤ 1 μm. Measurable shifts in dg and changes in distribution widths (σg) on an intratest basis suggest that the particle density

LabData database sub-systems for post-processing and quality control of stable isotope and gas chromatography measurements

Science.gov (United States)

Suckow, A. O.

2013-12-01

Measurements need post-processing to obtain results that are comparable between laboratories. Raw data may need to be corrected for blank, memory, drift (change of reference values with time), linearity (dependence of reference on signal height) and normalized to international reference materials. Post-processing parameters need to be stored for traceability of results. State of the art stable isotope correction schemes are available based on MS Excel (Geldern and Barth, 2012; Gröning, 2011) or MS Access (Coplen, 1998). These are specialized to stable isotope measurements only, often only to the post-processing of a special run. Embedding of algorithms into a multipurpose database system was missing. This is necessary to combine results of different tracers (3H, 3He, 2H, 18O, CFCs, SF6...) or geochronological tools (Sediment dating e.g. with 210Pb, 137Cs), to relate to attribute data (submitter, batch, project, geographical origin, depth in core, well information etc.) and for further interpretation tools (e.g. lumped parameter modelling). Database sub-systems to the LabData laboratory management system (Suckow and Dumke, 2001) are presented for stable isotopes and for gas chromatographic CFC and SF6 measurements. The sub-system for stable isotopes allows the following post-processing: 1. automated import from measurement software (Isodat, Picarro, LGR), 2. correction for sample-to sample memory, linearity, drift, and renormalization of the raw data. The sub-system for gas chromatography covers: 1. storage of all raw data 2. storage of peak integration parameters 3. correction for blank, efficiency and linearity The user interface allows interactive and graphical control of the post-processing and all corrections by export to and plot in MS Excel and is a valuable tool for quality control. The sub-databases are integrated into LabData, a multi-user client server architecture using MS SQL server as back-end and an MS Access front-end and installed in four

Calcium isotope fractionation in ion-exchange chromatography

International Nuclear Information System (INIS)

Russell, W.A.; Papanastassiou, D.A.

1978-01-01

Significant fractionation of the isotopes of calcium has been observed during elution through short ion-exchange columns packed with Dowex 50W-X8 resin. A double isotopic tracer was used to provide correction for instrumental fractionation effects. The absolute 40 Ca/ 44 Ca ratio is determined by this method to 0.05% and provides a measure of the fractionation of all Ca isotopes. It is found that the lighter isotopes are preferentially retained by the resin, with variations in 40 Ca/ 44 Ca between the first and last fractions of up to 1.1%. An estimate of the separation factor between batch solute and resin gives epsilon = 2.1 x 10 -4 . Details of the chemical or physical mechanisms causing isotope fractionation of Li, Na, Ca, and other elements during ion-exchange chromatography are not yet clear

Flow and Combustion in Advanced Gas Turbine Combustors

CERN Document Server

Janicka, Johannes; Schäfer, Michael; Heeger, Christof

2013-01-01

With regard to both the environmental sustainability and operating efficiency demands, modern combustion research has to face two main objectives, the optimization of combustion efficiency and the reduction of pollutants. This book reports on the combustion research activities carried out within the Collaborative Research Center (SFB) 568 “Flow and Combustion in Future Gas Turbine Combustion Chambers” funded by the German Research Foundation (DFG). This aimed at designing a completely integrated modeling and numerical simulation of the occurring very complex, coupled and interacting physico-chemical processes, such as turbulent heat and mass transport, single or multi-phase flows phenomena, chemical reactions/combustion and radiation, able to support the development of advanced gas turbine chamber concepts.

Boron isotope fractionation in column chromatography with glucamine type fibers

International Nuclear Information System (INIS)

Sonoda, Akinari; Makita, Yoji; Hirotsu, Takahiro

2008-01-01

Glucamine type polymers have specific affinity toward boric acid and borate ion. Among them, Chelest Fiber GRY-L showed larger fractionation for boron isotopes than other polymers in our previous study. For this study, we used Chelest Fibers with different fiber lengths (1.0 mm, 0.5 mm, and 0.3 mm) as column packing materials to perform chromatographic separation of boron isotopes. The shorter fiber has larger packing density when packed into the column using a dry method. The 0.3-mm-long fiber has a larger backpressure than fibers of other lengths. Boron adsorption capacities were measured using the breakthrough operation. At this time, the 0.5-mm-long fiber showed the highest capacity. When we measured the isotope ratio profile for fibers of different length using column chromatography, 0.5-mm-long fibers displayed the highest boron isotope fractionation. The 0.5-mm-long fiber is promising as a packing material of column chromatography for boron isotope separation. We also changed operation methods. The lower eluent concentration and the slower flow rate are suitable for boron isotope separation. (author)

Heater for Combustible-Gas Tanks

Science.gov (United States)

Ingle, Walter B.

1987-01-01

Proposed heater for pressurizing hydrogen, oxygen, or another combustible liquid or gas sealed in immersion cup in pressurized tank. Firmly supported in finned cup, coiled rod transfers heat through liquid metal to gas tank. Heater assembly welded or bolted to tank flange.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part II: 2-Methylfuran.

Science.gov (United States)

Tran, Luc-Sy; Togbé, Casimir; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2014-03-01

This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed.

Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

Science.gov (United States)

Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

2013-12-01

Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other

Development of a new method for hydrogen isotope analysis of trace hydrocarbons in natural gas samples

Directory of Open Access Journals (Sweden)

Xibin Wang

2016-12-01

Full Text Available A new method had been developed for the analysis of hydrogen isotopic composition of trace hydrocarbons in natural gas samples by using solid phase microextraction (SPME combined with gas chromatography-isotope ratio mass spectrometry (GC/IRMS. In this study, the SPME technique had been initially introduced to achieve the enrichment of trace content of hydrocarbons with low abundance and coupled to GC/IRMS for hydrogen isotopic analysis. The main parameters, including the equilibration time, extraction temperature, and the fiber type, were systematically optimized. The results not only demonstrated that high extraction yield was true but also shows that the hydrogen isotopic fractionation was not observed during the extraction process, when the SPME device fitted with polydimethylsiloxane/divinylbenzene/carbon molecular sieve (PDMS/DVB/CAR fiber. The applications of SPME-GC/IRMS method were evaluated by using natural gas samples collected from different sedimentary basins; the standard deviation (SD was better than 4‰ for reproducible measurements; and also, the hydrogen isotope values from C1 to C9 can be obtained with satisfying repeatability. The SPME-GC/IRMS method fitted with PDMS/DVB/CAR fiber is well suited for the preconcentration of trace hydrocarbons, and provides a reliable hydrogen isotopic analysis for trace hydrocarbons in natural gas samples.

Trends in the analysis of natural gas by capillary gas chromatography

NARCIS (Netherlands)

Cramers, C.A.M.G.; Rossum, van G.J.

1986-01-01

The importance of correct determination of physical and chemical properties of natural gas is evident. The calculation of calorific value or hydrocarbon dew point requires detailed analysis as can be provided by gas chromatography. Analysis by gas chromatography is a necessary complement to direct

Nitrogen enriched combustion of a natural gas internal combustion engine to reduce NO.sub.x emissions

Science.gov (United States)

Biruduganti, Munidhar S.; Gupta, Sreenath Borra; Sekar, R. Raj; McConnell, Steven S.

2008-11-25

A method and system for reducing nitrous oxide emissions from an internal combustion engine. An input gas stream of natural gas includes a nitrogen gas enrichment which reduces nitrous oxide emissions. In addition ignition timing for gas combustion is advanced to improve FCE while maintaining lower nitrous oxide emissions.

Determining the Levels of Volatile Organic Pollutants in Urban Air Using a Gas Chromatography-Mass Spectrometry Method

Science.gov (United States)

Nicoara, Simona; Tonidandel, Loris; Traldi, Pietro; Watson, Jonathan; Morgan, Geraint; Popa, Ovidiu

2009-01-01

The paper presents the application of a method based on coupled gas chromatography-mass spectrometry, using an isotopically labelled internal standard for the quantitative analysis of benzene (B), toluene (T), ethyl benzene (E), and o-, m-, p-xylenes (X). Their atmospheric concentrations were determined based on short-term sampling, in different sites of Cluj-Napoca, a highly populated urban centre in N-W Romania, with numerous and diversified road vehicles with internal combustion engines. The method is relatively inexpensive and simple and shows good precision and linearity in the ranges of 7–60 μg/m3 (B), 13–90 μg/m3 (T), 7–50 μg/m3 (E), 10–70 μg/m3 (X-m,p), and 20–130 μg/m3 (X-o). The limits of quantitation/detection of the method LOQ/LOD are of 10/5 μg/m3 (Xo), 5/3 μg/m3 (B, E, X-m,p), and of 3/1 μg/m3 (T), respectively. PMID:20168976

Determining the Levels of Volatile Organic Pollutants in Urban Air Using a Gas Chromatography-Mass Spectrometry Method

Directory of Open Access Journals (Sweden)

Simona Nicoara

2009-01-01

Full Text Available The paper presents the application of a method based on coupled gas chromatography-mass spectrometry, using an isotopically labelled internal standard for the quantitative analysis of benzene (B, toluene (T, ethyl benzene (E, and o-, m-, p-xylenes (X. Their atmospheric concentrations were determined based on short-term sampling, in different sites of Cluj-Napoca, a highly populated urban centre in N-W Romania, with numerous and diversified road vehicles with internal combustion engines. The method is relatively inexpensive and simple and shows good precision and linearity in the ranges of 7–60 μg/m3 (B, 13–90 μg/m3 (T, 7–50 μg/m3 (E, 10–70 μg/m3 (X-m,p, and 20–130 μg/m3 (X-o. The limits of quantitation/detection of the method LOQ/LOD are of 10/5 μg/m3 (Xo, 5/3 μg/m3 (B, E, X-m,p, and of 3/1 μg/m3 (T, respectively.

Analysis of pollutants in air and water using gas chromatography and headspace gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Stenner, H.

1980-01-01

The combination 'personal sampling' with headspace gas chromatography to determine traces of formaldehyde, phenol and benzene in air is investigated in this work, with the aim of developing maximum workplace concentration values (MWL values). Further possible applications of gas chromatography in trace analysis in the environmentally protected area. The analysis of chromium in waste waters (Cr III as acetyl acetonate complex) is investigated as further possible application, whereby optimum conditions are obtained. A modified flame ionization detector was used to increase the detection sensitivity.

Gas chromatography/ion trap mass spectrometry applied for the analysis of triazine herbicides in environmental waters by an isotope dilution technique

International Nuclear Information System (INIS)

Cai Zongwei; Wang Dongli; Ma, W.T.

2004-01-01

A gas chromatography/ion trap mass spectrometry method was developed for the analysis of simazine, atrazine, cyanazine, as well as the degradation products of atrazine, such as deethylatrazine and deisopropylatrazine in environmental water samples. Isotope dilution technique was applied for the quantitative analysis of atrazine in water at low ng/l levels. One liter of water sample spiked with stable isotope internal standard atrazine-d 5 was extracted with a C 18 solid-phase extraction cartridge. The analysis was performed on an ion trap mass spectrometer operated in MS/MS method. The extraction recoveries were in the range of 83-94% for the triazine herbicides in water at the concentrations of 24, 200, and 1000 ng/l, while poor recoveries were obtained for the degradation products of atrazine. The relative standard deviation (R.S.D.) were within the range of 3.2-16.1%. The detection limits of the method were between 0.75 and 12 ng/l when 1 l of water was analyzed. The method was successfully applied to analyze environmental water samples collected from a reservoir and a river in Hong Kong for atrazine detected at concentrations between 3.4 and 26 ng/l

Experimental and CFD investigation of gas phase freeboard combustion

DEFF Research Database (Denmark)

Andersen, Jimmy

Reliable and accurate modeling capabilities for combustion systems are valuable tools for optimization of the combustion process. This work concerns primary precautions for reducing NO emissions, thereby abating the detrimental effects known as “acid rain”, and minimizing cost for flue gas...... treatment. The aim of this project is to provide validation data for Computational Fluid Dynamic (CFD) models relevant for grate firing combustion conditions. CFD modeling is a mathematical tool capable of predicting fluid flow, mixing and chemical reaction with thermal conversion and transport. Prediction......, but under well-defined conditions. Comprehensive experimental data for velocity field, temperatures, and gas composition are obtained from a 50 kW axisymmetric non-swirling natural gas fired combustion setup under two different settings. Ammonia is added to the combustion setup in order to simulate fuel...

Continuous-flow isotope ratio mass spectrometry method for carbon and hydrogen isotope measurements on atmospheric methane

Directory of Open Access Journals (Sweden)

M. Brass

2010-12-01

Full Text Available We describe a continuous-flow isotope ratio mass spectrometry (CF-IRMS technique for high-precision δD and δ¹³C measurements of atmospheric methane on 40 mL air samples. CH₄ is separated from other air components by utilizing purely physical processes based on temperature, time and mechanical valve switching. Chemical agents are avoided. Trace amounts of interfering compounds can be separated by gas chromatography after pre-concentration of the CH₄ sample. The purified sample is then either combusted to CO₂ or pyrolyzed to H₂ for stable isotope measurement. Apart from connecting samples and refilling liquid nitrogen as coolant the system is fully automated and allows an unobserved, continuous analysis of samples. The analytical system has been used for analysis of air samples with CH₄ mixing ratios between ~100 and ~10 000 ppb, for higher mixing ratios samples usually have to be diluted.

[Poisoning by exhaust gas of the imperfect combustion of natural gas: 22 cases study].

Science.gov (United States)

Dong, Li-Min; Zhao, Hai; Zhang, Ming-Chang; He, Meng

2014-10-01

To analyze the case characteristics of poisoning by exhaust gas of the imperfect combustion of natural gas and provide references for forensic identification and prevention of such accidents. Twenty-two cases of poisoning by exhaust gas of the imperfect combustion of natural gas in Minhang District during 2004 to 2013 were collected. Some aspects such as general conditions of deaths, incidence time, weather, field investigation, and autopsy were retrospectively analyzed. In the 22 cases, there were 15 males and 16 females. The age range was between 2 and 82 years old. The major occurring time was in January or February (8 cases in each) and the cases almost occurred in small area room (21 cases). There was wide crack next to the exhaust port when the gas water heater was been used in all cases. There are more prone to occurrence of exhaust gas poisoning of imperfect combustion of natural gas in small area room with a ventilation window near the exhaust port of gas water heated. It shows that the scene of combustion exhaust gas poisoning should be more concerned in the cold season.

Process gas generator feeding internal combustion piston engines

Energy Technology Data Exchange (ETDEWEB)

Iwantscheff, G; Kostka, H; Henkel, H J

1978-10-26

The invention relates to a process gas generator feeding gaseous fuel to internal combustion piston engines. The cylinder linings of the internal combustion engine are enclosed by the catalytic reaction chamber of the process gas generator which contains perforated sintered nozzle bricks as carriers of the catalysts needed for the conversion. The reaction chamber is surrounded by the exhaust gas chamber around which a tube coil is ound which feeds the fuel charge to the reaction chamber after evaporation and mixing with exhaust gas and air. The fuel which may be used for this purpose, e.g., is low-octane gasoline or diesel fuel. In the reaction chamber the fuel is catalytically converted at temperatures above 200/sup 0/C, e.g., into low-molecular paraffins, carbon monoxide and hydrogen. Operation of the internal combustion engine with a process gas generator greatly reduces the pollutant content of the exhaust gases.

An improved reference measurement procedure for triglycerides and total glycerides in human serum by isotope dilution gas chromatography-mass spectrometry.

Science.gov (United States)

Chen, Yizhao; Liu, Qinde; Yong, Sharon; Teo, Hui Ling; Lee, Tong Kooi

2014-01-20

Triglycerides are widely tested in clinical laboratories using enzymatic methods for lipid profiling. As enzymatic methods can be affected by interferences from biological samples, this together with the non-specific nature of triglycerides measurement makes it necessary to verify the accuracy of the test results with a reference measurement procedure. Several such measurement procedures had been published. These procedures generally involved lengthy and laborious sample preparation steps. In this paper, an improved reference measurement procedure for triglycerides and total glycerides was reported which simplifies the sample preparation steps and greatly shortens the time taken. The procedure was based on isotope dilution gas chromatography-mass spectrometry (IDGC-MS)with tripalmitin as the calibration standard. Serum samples were first spiked with isotope-labeled tripalmitin. For the measurement of triglycerides, the serum samples were subjected to lipid extraction followed by separation of triglycerides from diglycerides and monoglycerides. Triglycerides were then hydrolyzed to glycerol, derivatized and injected into the GC–MS for quantification. For the measurement of total glycerides, the serum samples were hydrolyzed directly and derivatized before injection into the GC-MS for quantification. All measurement results showed good precision with CV triglycerides and total glycerides were well within the certified ranges of the CRM, with deviation triglycerides and total glycerides.

Decomposition of water into highly combustible hydroxyl gas used in ...

African Journals Online (AJOL)

The method proposed involves the decomposition of water into highly combustible hydroxyl gas via electrolysis, which is used in internal combustion engines of electrical generators for electricity generation. The by-product obtained from combustion of this gas is water vapour and oxygen to replenish the atmosphere.

Comparative determination of phenytoin by spectrophotometry, gas chromatography, liquid chromatography, enzyme immunoassay, and radioimmunoassay

International Nuclear Information System (INIS)

Castro, A.; Ibanez, J.; DiCesare, J.L.; Adams, R.F.; Malkus, H.

1978-01-01

Sera from patients being treated with phenytoin were analyzed for the drug by spectrophotometry, gas chromatography, radioimmunoasay, enzyme immunoassay, and liquid chromatography. The assay values obtained were intercompared statistically. Enzyme immunoassay and liquid chromatography appear to be attractive alternatives to the more traditional methods of spectrophotometry and gas chromatography. Our radioimmunoassay data correlated poorly with results by the four other methods

Automatic isotope gas analysis of tritium labelled organic materials Pt. 3

International Nuclear Information System (INIS)

Gacs, I.; Mlinko, S.; Payer, K.; Otvos, L.; Banfi, D.; Palagyi, T.

1978-01-01

An isotope analytical procedure and an automatic instrument developed for the determination of tritium in organic compounds and biological materials by internal gas counting are described. The sample is burnt in a stream of oxygen and the combustion products including water vapour carrying the tritium are led onto a column of molecular sieve-5A heated to 550 deg C. Tritium is retained temporarily on the column, then transferred into a stream of hydrogen by isotope exchange. After addition of butane, the tritiated hydrogen is led into an internal detector and enclosed there for radioactivity measurement. The procedure, providing quantitative recovery, is completed in five minutes. It is free of memory effect and suitable for the determination of tritium in a wide range of organic compounds and samples of biological origin. (author)

Feedlot lamb meat fatty acids profile characterization employing gas chromatography

Directory of Open Access Journals (Sweden)

M.I. Cruz-Gonzalez

2014-06-01

Full Text Available Fat is an important constituent in diet, not only as an energy source, but for its essential fatty acids associated to fats in foods, considering that some polyunsaturated fatty acids like linoleic, linolenic and arachidonic cannot be synthesized by superior animals like humans. Scientific evidence show that the fatty acids ingest can affect the thrombotic tendency, cardiac rhythm, endothelial function systematic inflammation, insulin sensibility and oxidative stress. Samples from 21 ovine crossbreds from Pelibuey, Blackbelly, Dorper and Katahadin (40 kg average weight feed with corn based balanced diets were taken from loin area 18 h after refrigeration. Saturated and polyunsaturated fatty acids levels were analyzed by gas chromatography. Results in this work showed that the healthy fatty acids levels are higher as compared to saturated fatty acids levels, indicating that this meat can influence consumer’s buying choice decision regarded to their health.

Complementary stable carbon isotope ratio and amount of substance measurements in sports anti-doping.

Science.gov (United States)

Cawley, Adam T; George, Adrian V

2012-12-01

The detection of steroids originating from synthetic precursors against a background of their chemically identical natural analogues has proven to be a significant challenge for doping control laboratories accredited by the World Anti-Doping Agency (WADA). The complementary application of gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) has been demonstrated to provide specific detection of endogenous steroid misuse for improved anti-doping analysis. Markers of synthetically derived steroids are reviewed on the basis of abnormal urinary excretions and low (13)C content. A combinatorial approach is presented for the interpretation of GC-MS and GC-C-IRMS data in the anti-doping context. This methodology can allow all relevant information concerning an individual's metabolism to be assessed in order to make an informed decision with respect to a doping violation. Copyright © 2012 John Wiley & Sons, Ltd.

Contribution to high-temperature chromatography and high-temperature-gas-chromatography-mass spectrometry of lipids

International Nuclear Information System (INIS)

Aichholz, R.

1998-04-01

additional structure information of unseparated compounds could be obtained. In this report for the first time the combination of high temperature gas chromatography / tandem mass spectrometry was employed for the analysis of neutral lipids. The three dimensional analytical system leads to a selectivity enhancement and enables, for example, the assignment of the regiospecific distribution of the fatty acid acyl groups of individual triacylglycerols. (author)

XII All-Russian conference on gas chromatography. Program. Summary of reports

International Nuclear Information System (INIS)

2002-01-01

Program and summary of reports of the XII All-Russian conference on gas chromatography are performed. The conference took place in Samara, 10-14 June, 2002. Reports on physicochemical regularities of gas chromatography, application of chromatographic methods in atomic energetics are included in the program of the conference. Part of the reports are deleted to the analytical application of the gas chromatography. Adsorbents for the gas chromatography, complex methods, mathematic methods in chromatography, ecological aspects of the gas chromatography [ru

Ionic liquid stationary phases for gas chromatography.

Science.gov (United States)

Poole, Colin F; Poole, Salwa K

2011-04-01

This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fuel Flexible Combustion Systems for High-Efficiency Utilization of Opportunity Fuels in Gas Turbines

Energy Technology Data Exchange (ETDEWEB)

Venkatesan, Krishna

2011-11-30

The purpose of this program was to develop low-emissions, efficient fuel-flexible combustion technology which enables operation of a given gas turbine on a wider range of opportunity fuels that lie outside of current natural gas-centered fuel specifications. The program encompasses a selection of important, representative fuels of opportunity for gas turbines with widely varying fundamental properties of combustion. The research program covers conceptual and detailed combustor design, fabrication, and testing of retrofitable and/or novel fuel-flexible gas turbine combustor hardware, specifically advanced fuel nozzle technology, at full-scale gas turbine combustor conditions. This project was performed over the period of October 2008 through September 2011 under Cooperative Agreement DE-FC26-08NT05868 for the U.S. Department of Energy/National Energy Technology Laboratory (USDOE/NETL) entitled "Fuel Flexible Combustion Systems for High-Efficiency Utilization of Opportunity Fuels in Gas Turbines". The overall objective of this program was met with great success. GE was able to successfully demonstrate the operability of two fuel-flexible combustion nozzles over a wide range of opportunity fuels at heavy-duty gas turbine conditions while meeting emissions goals. The GE MS6000B ("6B") gas turbine engine was chosen as the target platform for new fuel-flexible premixer development. Comprehensive conceptual design and analysis of new fuel-flexible premixing nozzles were undertaken. Gas turbine cycle models and detailed flow network models of the combustor provide the premixer conditions (temperature, pressure, pressure drops, velocities, and air flow splits) and illustrate the impact of widely varying fuel flow rates on the combustor. Detailed chemical kinetic mechanisms were employed to compare some fundamental combustion characteristics of the target fuels, including flame speeds and lean blow-out behavior. Perfectly premixed combustion experiments were conducted to

Applications of the gas chromatography in the nuclear science and technology; Aplicaciones de la cromatografia de gases a la ciencia y tecnologia nuclear

Energy Technology Data Exchange (ETDEWEB)

Gasco Sanchez, L

1972-07-01

This paper is a review on the applications of the gas chromatography in the nuclear science and technology published up to December 1971. Its contents has been classified under the following heads; I) Radiogaschromatography, II) Isotope separation, III) Preparation of labelled molecules, IV) Nuclear fuel cycle, V) Nuclear reactor technology, VI) Irradiation chemistry, VIl) Separation of me tal compounds in gas phase, VIII) Applications of the gas chromatography carried out at the Junta de Energia Nuclear, Spain. Arapter VIII only includes the investigations carried out from January 1969 to December 1971. Previous investigations in this field has been published elsewhere. (Author)

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part II: 2-Methylfuran

Science.gov (United States)

Tran, Luc-Sy; Togbé, Casimir; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2013-01-01

This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed. PMID:24518895

Optimization of combustion chamber geometry for natural gas engines with diesel micro-pilot-induced ignition

International Nuclear Information System (INIS)

Wang, Bin; Li, Tie; Ge, Linlin; Ogawa, Hideyuki

2016-01-01

Highlights: • Combustion chamber geometry is optimized to reduce the HC/CO emissions. • CFD model is calibrated against the spray visualization and engine bench test data. • Design space is explored by the multi-objective NSGA-II with Kriging meta-model. • HC and CO emissions are respectively reduced by 56.47% and 33.55%. - Abstract: Smokeless, low nitrogen oxides (NOx), and high thermal efficiency have been achieved through the lean-burn concept for natural gas engine with diesel micro-pilot-induced ignition (MPII). However, the combustion chamber is usually not specialized for natural gas combustion, and increases in the unburned hydrocarbon (HC) and carbon monoxide (CO) emissions are still a challenge for this type of engines. This paper describes optimization of the combustion chamber geometry to reduce the HC and CO emissions and improve the combustion efficiency in the MPII natural gas engine. The 3-D computational fluid dynamics (CFD) simulation model coupled with a chemical reaction mechanism is described. The temporal development of the short-pulsed diesel spray in a high pressure constant-volume vessel is measured and used to calibrate the spray model in the CFD simulation. The simulation models are validated by the experimental data of the in-cylinder pressure trace, apparent heat release rate (AHRR) and exhaust gas emissions from a single-cylinder MPII natural gas engine. To generate the various combustion chamber geometries, the bowl outline is parameterized by the two cubic Bezier curves while keeping the compression ratio constant. The available design space is explored by the multi-objective non-dominated sorting genetic algorithm II (NSGA-II) with Kriging-based meta-model. With the optimization, the HC and CO emissions are reduced by 56.47% and 33.55%, respectively, while the NOx emissions, the maximum rate of pressure rise and the gross indicated thermal efficiency that are employed as the constraints are slightly improved. Finally, the

In situ high-temperature gas sensors: continuous monitoring of the combustion quality of different wood combustion systems and optimization of combustion process

Directory of Open Access Journals (Sweden)

H. Kohler

2018-03-01

Full Text Available The sensing characteristics and long-term stability of different kinds of CO ∕ HC gas sensors (non-Nernstian mixed potential type during in situ operation in flue gas from different types of low-power combustion systems (wood-log- and wood-chip-fuelled were investigated. The sensors showed representative but individual sensing behaviour with respect to characteristically varying flue gas composition over the combustion process. The long-term sensor signal stability evaluated by repeated exposure to CO ∕ H2 ∕ N2 ∕ synthetic air mixtures showed no sensitivity loss after operation in the flue gas. Particularly for one of the sensors (Heraeus GmbH, this high signal stability was observed in a field test experiment even during continuous operation in the flue gas of the wood-chip firing system over 4 months. Furthermore, it was experimentally shown that the signals of these CO ∕ HC sensing elements yield important additional information about the wood combustion process. This was demonstrated by the adaptation of an advanced combustion airstream control algorithm on a wood-log-fed fireplace and by the development of a combustion quality monitoring system for wood-chip-fed central heaters.

Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

Science.gov (United States)

Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

2009-01-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N

Collaborative trial validation study of two methods, one based on high performance liquid chromatography-tandem mass spectrometry and on gas chromatography-mass spectrometry for the determination of acrylamide in bakery and potato products.

Science.gov (United States)

Wenzl, Thomas; Karasek, Lubomir; Rosen, Johan; Hellenaes, Karl-Erik; Crews, Colin; Castle, Laurence; Anklam, Elke

2006-11-03

A European inter-laboratory study was conducted to validate two analytical procedures for the determination of acrylamide in bakery ware (crispbreads, biscuits) and potato products (chips), within a concentration range from about 20 microg/kg to about 9000 microgg/kg. The methods are based on gas chromatography-mass spectrometry (GC-MS) of the derivatised analyte and on high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) of native acrylamide. Isotope dilution with isotopically labelled acrylamide was an integral part of both methods. The study was evaluated according to internationally accepted guidelines. The performance of the HPLC-MS/MS method was found to be superior to that of the GC-MS method and to be fit-for-the-purpose.

Measuring the exhaust gas dew point of continuously operated combustion plants

Energy Technology Data Exchange (ETDEWEB)

Fehler, D.

1985-07-16

Low waste-gas temperatures represent one means of minimizing the energy consumption of combustion facilities. However, condensation should be prevented to occur in the waste gas since this could result in a destruction of parts. Measuring the waste-gas dew point allows to control combustion parameters in such a way as to be able to operate at low temperatures without danger of condensation. Dew point sensors will provide an important signal for optimizing combustion facilities.

Radiation energy devaluation in diffusion combusting flows of natural gas

International Nuclear Information System (INIS)

Makhanlall, Deodat; Munda, Josiah L.; Jiang, Peixue

2013-01-01

Abstract: CFD (Computational fluid dynamics) is used to evaluate the thermodynamic second-law effects of thermal radiation in turbulent diffusion natural gas flames. Radiative heat transfer processes in gas and at solid walls are identified as important causes of energy devaluation in the combusting flows. The thermodynamic role of thermal radiation cannot be neglected when compared to that of heat conduction and convection, mass diffusion, chemical reactions, and viscous dissipation. An energy devaluation number is also defined, with which the optimum fuel–air equivalence for combusting flows can be determined. The optimum fuel–air equivalence ratio for a natural gas flame is determined to be 0.7. The CFD model is validated against experimental measurements. - Highlights: • Thermodynamic effects of thermal radiation in combusting flows analyzed. • General equation for second-law analyses of combusting flows extended. • Optimum fuel–air equivalence ratio determined for natural gas flame

Mixed-mode chromatography/isotope ratio mass spectrometry.

Science.gov (United States)

McCullagh, James S O

2010-03-15

Liquid chromatography coupled to molecular mass spectrometry (LC/MS) has been a standard technique since the early 1970s but liquid chromatography coupled to high-precision isotope ratio mass spectrometry (LC/IRMS) has only been available commercially since 2004. This development has, for the first time, enabled natural abundance and low enrichment delta(13)C measurements to be applied to individual analytes in aqueous mixtures creating new opportunities for IRMS applications, particularly for the isotopic study of biological molecules. A growing number of applications have been published in a range of areas including amino acid metabolism, carbohydrates studies, quantification of cellular and plasma metabolites, dietary tracer and nucleic acid studies. There is strong potential to extend these to new compounds and complex matrices but several challenges face the development of LC/IRMS methods. To achieve accurate isotopic measurements, HPLC separations must provide baseline-resolution between analyte peaks; however, the design of current liquid interfaces places severe restrictions on compatible flow rates and in particular mobile phase compositions. These create a significant challenge on which reports associated with LC/IRMS have not previously focused. Accordingly, this paper will address aspects of chromatography in the context of LC/IRMS, in particular focusing on mixed-mode separations and their benefits in light of these restrictions. It aims to provide an overview of mixed-mode stationary phases and of ways to improve high aqueous separations through manipulation of parameters such as column length, temperature and mobile phase pH. The results of several practical experiments are given using proteogenic amino acids and nucleosides both of which are of noted importance in the LC/IRMS literature. This communication aims to demonstrate that mixed-mode stationary phases provide a flexible approach given the constraints of LC/IRMS interface design and acts as a

Modelling of EAF off-gas post combustion in dedusting systems using CFD methods

Energy Technology Data Exchange (ETDEWEB)

Tang, X.; Kirschen, M.; Pfeifer, H. [Inst. for Industrial Furnaces and Heat Engineering in Metallurgy, RWTH Aachen, Aachen (Germany); Abel, M. [VAI-Fuchs GmbH, Willstaett (Germany)

2003-04-01

To comply with the increasingly strict environmental regulations, the poisonous off-gas species, e.g. carbon monoxide (CO), produced in the electric arc furnace (EAF) must be treated in the dedusting system. In this work, gas flow patterns of the off-gas post combustion in three different dedusting system units were simulated with a computational fluid dynamics (CFD) code: (1) post combustion in a horizontal off-gas duct, (2) post combustion in a water cooled post combustion chamber without additional energy supply (no gas or air/oxygen injectors) and (3) post combustion in a post combustion chamber with additional energy input (gas, air injectors and ignition burner, case study of VAI-Fuchs GmbH). All computational results are illustrated with gas velocity, temperature distribution and chemical species concentration fields for the above three cases. In case 1, the effect of different false air volume flow rates at the gap between EAF elbow and exhaust gas duct on the external post combustion of the off-gas was investigated. For case 2, the computed temperature and chemical composition (CO, CO{sub 2} and O{sub 2}) of the off-gas at the post chamber exit are in good agreement with additional measurements. Various operating conditions for case 3 have been studied, including different EAF off-gas temperatures and compositions, i. e. CO content, in order to optimize oxygen and burner gas flow rates. Residence time distributions in the external post combustion chambers have been calculated for cases 2 and 3. Derived temperature fields of the water cooled walls yield valuable information on thermally stressed parts of post combustion units. The results obtained in this work may also gain insight to future investigation of combustion of volatile organic components (VOC) or formation of nitrogen oxide (NO{sub x}) and permit the optimization of the operation and design of the off-gas dedusting system units. (orig.)

Low-Emission combustion of fuel in aeroderivative gas turbines

Science.gov (United States)

Bulysova, L. A.; Vasil'ev, V. D.; Berne, A. L.

2017-12-01

The paper is the first of a planned set of papers devoted to the world experience in development of Low Emission combustors (LEC) for industrial Gas Turbines (GT). The purpose of the article is to summarize and analyze the most successful experience of introducing the principles of low-emission combustion of the so-called "poor" (low fuel concentration in air when the excess air ratio is about 1.9-2.1) well mixed fuelair mixtures in the LEC for GTs and ways to reduce the instability of combustion. The consideration examples are the most successful and widely used aero-derivative GT. The GT development meets problems related to the difference in requirements and operation conditions between the aero, industrial, and power production GT. One of the main problems to be solved is the LEC development to mitigate emissions of the harmful products first of all the Nitrogen oxides NOx. The ways to modify or convert the initial combustors to the LEC are shown. This development may follow location of multiburner mixers within the initial axial envelope dimensions or conversion of circular combustor to the can type one. The most interesting are Natural Gas firing GT without water injection into the operating process or Dry Low emission (DLE) combustors. The current GT efficiency requirement may be satisfied at compressor exit pressure above 3 MPa and Turbine Entry temperature (TET) above 1500°C. The paper describes LEC examples based on the concept of preliminary prepared air-fuel mixtures' combustion. Each combustor employs its own fuel supply control concept based on the fuel flow-power output relation. In the case of multiburner combustors, the burners are started subsequently under a specific scheme. The can type combustors have combustion zones gradually ignited following the GT power change. The combustion noise problem experienced in lean mixtures' combustion is also considered, and the problem solutions are described. The GT test results show wide ranges of stable

On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

Directory of Open Access Journals (Sweden)

J. Schmitt

2013-05-01

Full Text Available Stable carbon isotope analysis of methane (δ13C of CH4 on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC isotope ratio mass spectrometry (IRMS coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr can severely interfere during the mass spectrometric measurement, leading to significant biases in δ13C of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged 86Kr peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in δ13C. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

Internal combustion engine for natural gas compressor operation

Energy Technology Data Exchange (ETDEWEB)

Hagen, Christopher; Babbitt, Guy

2016-12-27

This application concerns systems and methods for compressing natural gas with an internal combustion engine. In a representative embodiment, a method is featured which includes placing a first cylinder of an internal combustion engine in a compressor mode, and compressing a gas within the first cylinder, using the cylinder as a reciprocating compressor. In some embodiments a compression check valve system is used to regulate pressure and flow within cylinders of the engine during a compression process.

Flame kernel characterization of laser ignition of natural gas-air mixture in a constant volume combustion chamber

Science.gov (United States)

Srivastava, Dhananjay Kumar; Dharamshi, Kewal; Agarwal, Avinash Kumar

2011-09-01

In this paper, laser-induced ignition was investigated for compressed natural gas-air mixtures. Experiments were performed in a constant volume combustion chamber, which simulate end of the compression stroke conditions of a SI engine. This chamber simulates the engine combustion chamber conditions except turbulence of air-fuel mixture. It has four optical windows at diametrically opposite locations, which are used for laser ignition and optical diagnostics simultaneously. All experiments were conducted at 10 bar chamber pressure and 373 K chamber temperature. Initial stage of combustion phenomena was visualized by employing Shadowgraphy technique using a high speed CMOS camera. Flame kernel development of the combustible fuel-air mixture was investigated under different relative air-fuel ratios ( λ=1.2-1.7) and the images were interrogated for temporal propagation of flame front. Pressure-time history inside the combustion chamber was recorded and analyzed. This data is useful in characterizing the laser ignition of natural gas-air mixture and can be used in developing an appropriate laser ignition system for commercial use in SI engines.

Quantitative characterization of urban sources of organic aerosol by high-resolution gas chromatography

International Nuclear Information System (INIS)

Hildemann, L.M.; Mazurek, M.A.; Cass, G.R.; Simoneit, B.R.T.

1991-01-01

Fine aerosol emissions have been collected from a variety of urban combustion sources, including an industrial boiler, a fireplace, automobiles, diesel trucks, gas-fired home appliances, and meat cooking operations, by use of a dilution sampling system. Other sampling techniques have been utilized to collect fine aerosol samples of paved road dust, brake wear, tire wear, cigarette smoke, tar pot emissions, and vegetative detritus. The organic matter contained in each of these samples has been analyzed via high-resolution gas chromatography. By use of a simple computational approach, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type has been determined. The organic mass distribution fingerprints obtained by this approach are shown to differ significantly from each other for most of the source types tested, using hierarchical cluster analysis

15N/14N isotopic ratio and statistical analysis: an efficient way of linking seized Ecstasy tablets

International Nuclear Information System (INIS)

Palhol, Fabien; Lamoureux, Catherine; Chabrillat, Martine; Naulet, Norbert

2004-01-01

In this study, the 15 N/ 14 N isotopic ratios of 106 samples of 3,4-methylenedioxymethamphetamine (MDMA) extracted from Ecstasy tablets are presented. These ratios, measured using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), show a large discrimination between samples with a range of δ 15 N values between -17 and +19%o, depending on the precursors and the method used in clandestine laboratories. Thus, δ 15 N values can be used in a statistical analysis carried out in order to link Ecstasy tablets prepared with the same precursors and synthetic pathway. The similarity index obtained after principal component analysis and hierarchical cluster analysis appears to be an efficient way to group tablets seized in different places

Experimental and numerical investigation of gas phase freeboard combustion

DEFF Research Database (Denmark)

Andersen, J.; Jensen, Peter Arendt; Meyer, K.E.

2009-01-01

Experimental data for velocity field, temperatures, and gas composition have been obtained from a 50 kW axisymmetric non-swirling natural gas fired combustion setup under two different settings. The reactor was constructed to simulate the conditions in the freeboard of a grate-fired boiler...... but under well-defined conditions. The experimental results are compared to computational fluid dynamics (CFD) modeling predictions, using the eddy dissipation model (EDM) its well as the eddy dissipation concept (EDC). The use of EDC allows for implementation of more advanced combustion schemes; we have...... tested the four-step global mechanism by Jones and Lindstedt (Combust. Flame 1988, 73, 233-249), and the 16 species and 41 reaction skeletal mechanism by Yang and Pope (Combust. Flame 1998, 112 16-32). The CFD model captured the main features of the combustion process and flow patterns. The application...

Normalization of natural gas composition data measured by gas chromatography

International Nuclear Information System (INIS)

Milton, Martin J T; Harris, Peter M; Brown, Andrew S; Cowper, Chris J

2009-01-01

The composition of natural gas determined by gas chromatography is routinely used as the basis for calculating physico-chemical properties of the gas. Since the data measured by gas chromatography have particular statistical properties, the methods used to determine the composition can make use of a priori assumptions about the statistical model for the data. We discuss a generalized approach to determining the composition, and show that there are particular statistical models for the data for which the generalized approach reduces to the widely used method of post-normalization. We also show that the post-normalization approach provides reasonable estimates of the composition for cases where it cannot be shown to arise rigorously from the statistical structure of the data

Combustion Dynamics and Control for Ultra Low Emissions in Aircraft Gas-Turbine Engines

Science.gov (United States)

DeLaat, John C.

2011-01-01

Future aircraft engines must provide ultra-low emissions and high efficiency at low cost while maintaining the reliability and operability of present day engines. The demands for increased performance and decreased emissions have resulted in advanced combustor designs that are critically dependent on efficient fuel/air mixing and lean operation. However, all combustors, but most notably lean-burning low-emissions combustors, are susceptible to combustion instabilities. These instabilities are typically caused by the interaction of the fluctuating heat release of the combustion process with naturally occurring acoustic resonances. These interactions can produce large pressure oscillations within the combustor and can reduce component life and potentially lead to premature mechanical failures. Active Combustion Control which consists of feedback-based control of the fuel-air mixing process can provide an approach to achieving acceptable combustor dynamic behavior while minimizing emissions, and thus can provide flexibility during the combustor design process. The NASA Glenn Active Combustion Control Technology activity aims to demonstrate active control in a realistic environment relevant to aircraft engines by providing experiments tied to aircraft gas turbine combustors. The intent is to allow the technology maturity of active combustion control to advance to eventual demonstration in an engine environment. Work at NASA Glenn has shown that active combustion control, utilizing advanced algorithms working through high frequency fuel actuation, can effectively suppress instabilities in a combustor which emulates the instabilities found in an aircraft gas turbine engine. Current efforts are aimed at extending these active control technologies to advanced ultra-low-emissions combustors such as those employing multi-point lean direct injection.

Online Stable Isotope Analysis of Dissolved Organic Carbon Size Classes Using Size Exclusion Chromatography Coupled to an Isotope Ratio Mass Spectrometer

Digital Repository Service at National Institute of Oceanography (India)

Malik, A.; Scheibe, A.; LokaBharathi, P.A.; Gleixner, G.

size classes by coupling high-performance liquid chromatography (HPLC) - size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface...

Modelling combustion reactions for gas flaring and its resulting emissions

Directory of Open Access Journals (Sweden)

O. Saheed Ismail

2016-07-01

Full Text Available Flaring of associated petroleum gas is an age long environmental concern which remains unabated. Flaring of gas maybe a very efficient combustion process especially steam/air assisted flare and more economical than utilization in some oil fields. However, it has serious implications for the environment. This study considered different reaction types and operating conditions for gas flaring. Six combustion equations were generated using the mass balance concept with varying air and combustion efficiency. These equations were coded with a computer program using 12 natural gas samples of different chemical composition and origin to predict the pattern of emission species from gas flaring. The effect of key parameters on the emission output is also shown. CO2, CO, NO, NO2 and SO2 are the anticipated non-hydrocarbon emissions of environmental concern. Results show that the quantity and pattern of these chemical species depended on percentage excess/deficiency of stoichiometric air, natural gas type, reaction type, carbon mass content, impurities, combustion efficiency of the flare system etc. These emissions degrade the environment and human life, so knowing the emission types, pattern and flaring conditions that this study predicts is of paramount importance to governments, environmental agencies and the oil and gas industry.

Gas Phase Sulfur, Chlorine and Potassium Chemistry in Biomass Combustion

DEFF Research Database (Denmark)

Løj, Lusi Hindiyarti

2007-01-01

Gas Phase Sulfur, Chlorine and Alkali Metal Chemistry in Biomass Combustion Concern about aerosols formation, deposits, corrosion, and gaseous emissions during biomass combustion, especially straw, continues to be a driving force for investigation on S, Cl, K-containing species under combustions...... conditions. These trace species contained in the biomass structure will be released to the gas phase during combustion and contribute to the problems generated during the process. The investigation during this PhD project is done to stepwise improve the understanding in the chemistry and reduce...... the uncertainties. In the present work, the detailed kinetic model for gas phase sulfur, chlorine, alkali metal, and their interaction has been updated. The K/O/H/Cl chemistry, S chemistry, and their interaction can reasonably predict a range of experimental data. In general, understanding of the interaction...

Dioxin and furan emissions from landfill gas-fired combustion units

International Nuclear Information System (INIS)

Caponi, F.R.; Wheless, E.; Frediani, D.

1998-01-01

The 1990 Federal Clean Air Act Amendments require the development of maximum achievable control technology standards (MACT) for sources of hazardous air pollutants, including landfill gas-fired combustion sources. The Industrial Combustion Coordinated Rulemaking (ICCR) Federal Advisory Committee is a group of stakeholders from the public and private sector whose charge is to develop recommendations for a unified set of federal toxic air emissions regulations. Specifically, the group will establish MACT standards for industrial-commercial-institutional combustion sources. The ICCR proceedings have given rise to considerable interest in potential dioxin and furan emissions from landfill gas-fired combustion units. In order to establish the potential of dioxin and furan emissions from this group of combustion sources, a world-wide literature search was conducted. A total of 22 references were evaluated. The references covered a wide range of test programs, testing methodologies and combustion equipment type. The most abundant data were for landfill gas-fired flares (shrouded and afterburners) and I.C. engines. Because of limitations in obtaining actual test reports with complete lab data and QA/QC results, and a lack of knowledge as to the exact types of waste received at the European landfills, the test data from these sources, for the purposes of this paper, are considered qualitative. The conclusion reached from review of the test data is that there is a potential for dioxin and furan emissions from landfill gas-fired combustion units, but at very low levels for well operated systems

PARs for combustible gas control in advanced light water reactors

International Nuclear Information System (INIS)

Hosler, J.; Sliter, G.

1997-01-01

This paper discusses the progress being made in the United States to introduce passive autocatalytic recombiner (PAR) technology as a cost-effective alternative to electric recombiners for controlling combustible gas produced in postulated accidents in both future Advanced Light Water Reactors (ALWRs) and certain U. S. operating nuclear plants. PARs catalytically recombine hydrogen and oxygen, gradually producing heat and water vapor. They have no moving parts and are self-starting and self-feeding, even under relatively cold and wet containment conditions. Buoyancy of the hot gases they create sets up natural convective flow that promotes mixing of combustible gases in a containment. In a non-inerted ALWR containment, two approaches each employing a combination of PARs and igniters are being considered to control hydrogen in design basis and severe accidents. In pre-inerted ALWRs, PARs alone control radiolytic oxygen produced in either accident type. The paper also discusses regulatory feedback regarding these combustible gas control approaches and describes a test program being conducted by the Electric Power Research Institute (EPRI) and Electricite de France (EdF) to supplement the existing PAR test database with performance data under conditions of interest to U.S. plants. Preliminary findings from the EPRI/EdF PAR model test program are included. Successful completion of this test program and confirmatory tests being sponsored by the U. S. NRC are expected to pave the way for use of PARs in ALWRs and operating plants. (author)

Recent applications of gas chromatography with high-resolution mass spectrometry.

Science.gov (United States)

Špánik, Ivan; Machyňáková, Andrea

2018-01-01

Gas chromatography coupled to high-resolution mass spectrometry is a powerful analytical method that combines excellent separation power of gas chromatography with improved identification based on an accurate mass measurement. These features designate gas chromatography with high-resolution mass spectrometry as the first choice for identification and structure elucidation of unknown volatile and semi-volatile organic compounds. Gas chromatography with high-resolution mass spectrometry quantitative analyses was previously focused on the determination of dioxins and related compounds using magnetic sector type analyzers, a standing requirement of many international standards. The introduction of a quadrupole high-resolution time-of-flight mass analyzer broadened interest in this method and novel applications were developed, especially for multi-target screening purposes. This review is focused on the development and the most interesting applications of gas chromatography coupled to high-resolution mass spectrometry towards analysis of environmental matrices, biological fluids, and food safety since 2010. The main attention is paid to various approaches and applications of gas chromatography coupled to high-resolution mass spectrometry for non-target screening to identify contaminants and to characterize the chemical composition of environmental, food, and biological samples. The most interesting quantitative applications, where a significant contribution of gas chromatography with high-resolution mass spectrometry over the currently used methods is expected, will be discussed as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas turbines with complete continuous combustion of the fuels

Energy Technology Data Exchange (ETDEWEB)

Koch, C

1976-10-21

The invention concerns a gas turbine plant with complete continuous combustion of the fuel. The fuel is taken to a gas generator in which the preheated fuel is catalytically converted at high temperature in a fuel mixture using an oxygen carrier. Heating of the fuel takes place in a heat exchanger which is situated in the outlet pipe of the turbine. The efficiency is increased and the emission of noxious gas is kept as low as possible using the heat exchanger as a fuel evaporator and by using part of the waste formed in the combustion chamber to carry oxygen to the gas generator via an outlet pipe.

Isotope dilution analysis for urinary fentanyl and its main metabolite, norfentanyl, in patients by isotopic fractionation using capillary gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Sera, Shoji; Goromaru, Tsuyoshi [Fukuyama Univ., Hiroshima (Japan). Faculty of Pharmacy and Pharmaceutical Sciences; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

1998-07-01

Isotope dilution analysis was applied to determine urinary excretion of fentanyl (FT) and its main metabolite, norfentanyl (Nor-FT), by isotopic fractionation using a capillary gas chromatograph equipped with a surface ionization detector (SID). Urinary FT was determined quantitatively in the range of 0.4-40 ng/ml using deuterium labeled FT (FT-{sup 2}H{sub 19}), as an internal standard. We also performed isotope dilution analysis of Nor-FT in urine. N-Alkylation was necessary to sensitively detect Nor-FT with SID. Methyl derivative was selected from 3 kinds of N-alkyl derivatives to increase sensitivity and peak resolution, and to prevent interference with urinary compound. Nor-FT concentration was quantitatively determined in the range of 10-400 ng/ml using deuterium labeled Nor-FT (Nor-FT-{sup 2}H{sub 10}). No endogenous compounds or concomitant drugs interfered with the detection of FT and Nor-FT in the urine of patients. The present method will be useful for pharmacokinetic studies and the evaluation of drug interactions in FT metabolism. (author)

Isotope dilution analysis for urinary fentanyl and its main metabolite, norfentanyl, in patients by isotopic fractionation using capillary gas chromatography

International Nuclear Information System (INIS)

Sera, Shoji; Goromaru, Tsuyoshi; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

1998-01-01

Isotope dilution analysis was applied to determine urinary excretion of fentanyl (FT) and its main metabolite, norfentanyl (Nor-FT), by isotopic fractionation using a capillary gas chromatograph equipped with a surface ionization detector (SID). Urinary FT was determined quantitatively in the range of 0.4-40 ng/ml using deuterium labeled FT (FT- 2 H 19 ), as an internal standard. We also performed isotope dilution analysis of Nor-FT in urine. N-Alkylation was necessary to sensitively detect Nor-FT with SID. Methyl derivative was selected from 3 kinds of N-alkyl derivatives to increase sensitivity and peak resolution, and to prevent interference with urinary compound. Nor-FT concentration was quantitatively determined in the range of 10-400 ng/ml using deuterium labeled Nor-FT (Nor-FT- 2 H 10 ). No endogenous compounds or concomitant drugs interfered with the detection of FT and Nor-FT in the urine of patients. The present method will be useful for pharmacokinetic studies and the evaluation of drug interactions in FT metabolism. (author)

Comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones.

Science.gov (United States)

Carnes, Stephanie; O'Brien, Stacey; Szewczak, Angelica; Tremeau-Cayel, Lauriane; Rowe, Walter F; McCord, Bruce; Lurie, Ira S

2017-09-01

A comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones has been conducted. Nine different mixtures of bath salts were analyzed in this study. The three different chromatographic techniques were examined using a general set of controlled synthetic cathinones as well as a variety of other synthetic cathinones that exist as positional isomers. Overall 35 different synthetic cathinones were analyzed. A variety of column types and chromatographic modes were examined for developing each separation. For the ultra high performance supercritical fluid chromatography separations, analyses were performed using a series of Torus and Trefoil columns with either ammonium formate or ammonium hydroxide as additives, and methanol, ethanol or isopropanol organic solvents as modifiers. Ultra high performance liquid chromatographic separations were performed in both reversed phase and hydrophilic interaction chromatographic modes using SPP C18 and SPP HILIC columns. Gas chromatography separations were performed using an Elite-5MS capillary column. The orthogonality of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography was examined using principal component analysis. For the best overall separation of synthetic cathinones, the use of ultra high performance supercritical fluid chromatography in combination with gas chromatography is recommended. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

{sup 15}N/{sup 14}N isotopic ratio and statistical analysis: an efficient way of linking seized Ecstasy tablets

Energy Technology Data Exchange (ETDEWEB)

Palhol, Fabien; Lamoureux, Catherine; Chabrillat, Martine; Naulet, Norbert

2004-05-10

In this study, the {sup 15}N/{sup 14}N isotopic ratios of 106 samples of 3,4-methylenedioxymethamphetamine (MDMA) extracted from Ecstasy tablets are presented. These ratios, measured using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), show a large discrimination between samples with a range of {delta}{sup 15}N values between -17 and +19%o, depending on the precursors and the method used in clandestine laboratories. Thus, {delta}{sup 15}N values can be used in a statistical analysis carried out in order to link Ecstasy tablets prepared with the same precursors and synthetic pathway. The similarity index obtained after principal component analysis and hierarchical cluster analysis appears to be an efficient way to group tablets seized in different places.

Gas Chromatography-Mass Spectroscopic (GC-MS) Analysis of n ...

African Journals Online (AJOL)

tuber-regium (synonym Pleurotus tuber regium) using gas chromatography-mass spectroscopic (GC-. MS) techniques. Methods: The n-hexane extract of the sclerotia ... Soxhlet extraction and analysed using gas chromatography-mass spectroscopic (MS) techniques. ..... Phytochemical composition of Pleurotus tuber regium.

Determination of the hydrogen isotopic compositions of organic materials and hydrous minerals using thermal combustion laser spectroscopy.

Science.gov (United States)

Koehler, Geoff; Wassenaar, Leonard I

2012-04-17

Hydrogen isotopic compositions of hydrous minerals and organic materials were measured by combustion to water, followed by optical isotopic analysis of the water vapor by off-axis integrated cavity output spectroscopy. Hydrogen and oxygen isotopic compositions were calculated by numerical integration of the individual isotopologue concentrations measured by the optical spectrometer. Rapid oxygen isotope exchange occurs within the combustion reactor between water vapor and molecular oxygen so that only hydrogen isotope compositions may be determined. Over a wide range in sample sizes, precisions were ±3-4 per mil. This is comparable but worse than continuous flow-isotope ratio mass spectroscopy (CF-IRMS) methods owing to memory effects inherent in water vapor transfer. Nevertheless, the simplicity and reduced cost of this analysis compared to classical IRMS or CF-IRMS methods make this an attractive option to determine the hydrogen isotopic composition of organic materials where the utmost precision or small sample sizes are not needed.

Stable carbon isotope ratios of lipid biomarkers and their applications in the marine environment

International Nuclear Information System (INIS)

Tolosa, I.; Mora, S. de

2001-01-01

Studies on the distribution of lipid biomarkers in the environment help elucidate biogeochemical processes, but recent findings have significantly reduced the specificity of some biomarkers. The analytical development of Gas Chromatography-Combustion-IRMS (GC-C-IRMS) allows the determination of the δ 13 C of specific biomarkers, thereby improving the veracity of source apportionment. In this report, we present a brief description of the analytical approach for sample preparation and carbon isotope measurements of individual biomarkers. Selected examples of the applications in the use of GC-C-IRMS for biomarker source elucidation in the marine environment and potential applications to paleoclimatological studies are reviewed. (author)

Gas chromatography: mass selective detector

International Nuclear Information System (INIS)

Lapinskas, R.

1988-01-01

The mechanism of mass spectrometry technique directed for detecting molecular structures is described, with some considerations about its operational features. This mass spectrometer is used as a gas chromatography detector. (author)

Measurement of natural carbon isotopic composition of acetone in human urine.

Science.gov (United States)

Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

2016-02-01

The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease.

Simultaneous analysis of polychlorinated biphenyls and polychlorinated naphthalenes by isotope dilution comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry

International Nuclear Information System (INIS)

Xia, Dan; Gao, Lirong; Zheng, Minghui; Wang, Shasha; Liu, Guorui

2016-01-01

Polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Because they have similar physical and chemical properties, they are coeluted and are usually analyzed separately by different gas chromatography high-resolution mass spectrometry (GC-HRMS) methods. In this study, a novel method was developed for simultaneous analysis of six indicator PCBs, 12 dioxin-like PCBs, and 16 PCNs using isotope dilution comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS). The method parameters, including the type of GC column, oven temperature program, and modulation period, were systematically optimized. Complete separation of all target analytes and the matrix was achieved with a DB-XLB column in the first dimension and a BPX-70 column in the second dimension. The isotope dilution method was used for quantification of the PCBs and PCNs by GC × GC-HRTOF-MS. The method showed good linearity from 5 to 500 pg μL"−"1 for all the target compounds. The instrumental limit of detection ranged from 0.03 to 0.3 pg μL"−"1 for the 18 PCB congeners and from 0.09 to 0.6 pg μL"−"1 for the 16 PCN congeners. Repeatability for triplicate injections was always lower than 20%. The method was successfully applied to the determination of 18 PCBs present at 0.9–2054 pg g"−"1 and 16 PCNs present at 0.2–15.7 pg g"−"1 in three species of fish. The GC × GC-HRTOF-MS results agreed with those obtained by GC-HRMS. The GC × GC-HRTOF-MS method proved to be a sensitive and accurate technique for simultaneous analysis of the selected PCBs and PCNs. With the excellent chromatographic separation offered by GC × GC and accurate mass measurements offered by HRTOF-MS, this method allowed identification of non-target contaminants in the fish samples, including organochlorine pesticides and polycyclic aromatic

Simultaneous analysis of polychlorinated biphenyls and polychlorinated naphthalenes by isotope dilution comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Xia, Dan [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); University of Chinese Academy of Sciences, Beijing 100085 (China); Gao, Lirong, E-mail: gaolr@rcees.ac.cn [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Zheng, Minghui; Wang, Shasha; Liu, Guorui [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China)

2016-09-21

Polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Because they have similar physical and chemical properties, they are coeluted and are usually analyzed separately by different gas chromatography high-resolution mass spectrometry (GC-HRMS) methods. In this study, a novel method was developed for simultaneous analysis of six indicator PCBs, 12 dioxin-like PCBs, and 16 PCNs using isotope dilution comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS). The method parameters, including the type of GC column, oven temperature program, and modulation period, were systematically optimized. Complete separation of all target analytes and the matrix was achieved with a DB-XLB column in the first dimension and a BPX-70 column in the second dimension. The isotope dilution method was used for quantification of the PCBs and PCNs by GC × GC-HRTOF-MS. The method showed good linearity from 5 to 500 pg μL{sup −1} for all the target compounds. The instrumental limit of detection ranged from 0.03 to 0.3 pg μL{sup −1} for the 18 PCB congeners and from 0.09 to 0.6 pg μL{sup −1} for the 16 PCN congeners. Repeatability for triplicate injections was always lower than 20%. The method was successfully applied to the determination of 18 PCBs present at 0.9–2054 pg g{sup −1} and 16 PCNs present at 0.2–15.7 pg g{sup −1} in three species of fish. The GC × GC-HRTOF-MS results agreed with those obtained by GC-HRMS. The GC × GC-HRTOF-MS method proved to be a sensitive and accurate technique for simultaneous analysis of the selected PCBs and PCNs. With the excellent chromatographic separation offered by GC × GC and accurate mass measurements offered by HRTOF-MS, this method allowed identification of non-target contaminants in the fish samples, including organochlorine pesticides and

Stable carbon isotope analyses of nanogram quantities of particulate organic carbon (pollen) with laser ablation nano combustion gas chromatography/isotope ratio mass spectrometry

NARCIS (Netherlands)

van Roij, Linda; Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert-Jan

2017-01-01

Rationale: Analyses of stable carbon isotope ratios (δ13C values) of organic and inorganic matter remains have been instrumental for much of our understanding of present and past environmental and biological processes. Until recently, the analytical window of such analyses has been limited to

Gas-centrifuge unit and centrifugal process for isotope separation

International Nuclear Information System (INIS)

Stark, T.M.

1979-01-01

An invention involving a process and apparatus for isotope-separation applications such as uranium-isotope enrichment is disclosed which employs cascades of gas centrifuges. A preferred apparatus relates to an isotope-enrichment unit which includes a first group of cascades of gas centrifuges and an auxiliary cascade. Each cascade has an input, a light-fraction output, and a heavy-fraction output for separating a gaseous-mixture feed including a compound of a light nuclear isotope and a compound of a heavy nuclear isotope into light and heavy fractions respectively enriched and depleted in the light isotope. The cascades of the first group have at least one enriching stage and at least one stripping stage. The unit further includes means for introducing a gaseous-mixture feedstock into each input of the first group of cascades, means for withdrawing at least a portion of a product fraction from the light-fraction outputs of the first group of cascades, and means for withdrawing at least a portion of a waste fraction from the heavy-fraction outputs of the first group of cascades. The isotope-enrichment unit also includes a means for conveying a gaseous-mixture from a light-fraction output of a first cascade included in the first group to the input of the auxiliary cascade so that at least a portion of a light gaseous-mixture fraction produced by the first group of cascades is further separated into a light and a heavy fraction by the auxiliary cascade. At least a portion of a product fraction is withdrawn from the light fraction output of the auxiliary cascade. If the light-fraction output of the first cascade and the heavy-fraction output of the auxiliary cascade are reciprocal outputs, the concentraton of the light isotope in the heavy fraction produced by the auxiliary cascade essentially equals the concentration of the light isotope in the gaseous-mixture feedstock

Gas chromatography

International Nuclear Information System (INIS)

Cram, S.P.; Risby, T.H.; Field, L.R.; Yu, W.L.

1980-01-01

In addition to the published literature for the years 1978 - 79, this review of developments in the field of gas chromatography includes earlier articles of particular significance appearing in foreign journals and the patent literature which was not available at the time of the previous review. The articles cited were selected as presenting the most fundamental developments in theory, methodology, and instrumentation. Some applications are cited if they reflect an advance in the state-of-the-art or have particular relevance to new developments. 1149 references are cited

Evaluation of catalytic combustion of actual coal-derived gas

Science.gov (United States)

Blanton, J. C.; Shisler, R. A.

1982-01-01

The combustion characteristics of a Pt-Pl catalytic reactor burning coal-derived, low-Btu gas were investigated. A large matrix of test conditions was explored involving variations in fuel/air inlet temperature and velocity, reactor pressure, and combustor exit temperature. Other data recorded included fuel gas composition, reactor temperatures, and exhaust emissions. Operating experience with the reactor was satisfactory. Combustion efficiencies were quite high (over 95 percent) over most of the operating range. Emissions of NOx were quite high (up to 500 ppm V and greater), owing to the high ammonia content of the fuel gas.

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid chromatography system for clinical use is a device intended to separate one or more drugs or compounds from a...

The development of an electrochemical technique for in situ calibrating of combustible gas detectors

Science.gov (United States)

Shumar, J. W.; Lantz, J. B.; Schubert, F. H.

1976-01-01

A program to determine the feasibility of performing in situ calibration of combustible gas detectors was successfully completed. Several possible techniques for performing the in situ calibration were proposed. The approach that showed the most promise involved the use of a miniature water vapor electrolysis cell for the generation of hydrogen within the flame arrestor of a combustible gas detector to be used for the purpose of calibrating the combustible gas detectors. A preliminary breadboard of the in situ calibration hardware was designed, fabricated and assembled. The breadboard equipment consisted of a commercially available combustible gas detector, modified to incorporate a water vapor electrolysis cell, and the instrumentation required for controlling the water vapor electrolysis and controlling and calibrating the combustible gas detector. The results showed that operation of the water vapor electrolysis at a given current density for a specific time period resulted in the attainment of a hydrogen concentration plateau within the flame arrestor of the combustible gas detector.

Measurement of the isotope ratio of acetic acid in vinegar by HS-SPME-GC-TC/C-IRMS.

Science.gov (United States)

Hattori, Ryota; Yamada, Keita; Shibata, Hiroki; Hirano, Satoshi; Tajima, Osamu; Yoshida, Naohiro

2010-06-23

Acetic acid is the main ingredient of vinegar, and the worth of vinegar often depends on the fermentation of raw materials. In this study, we have developed a simple and rapid method for discriminating the fermentation of the raw materials of vinegar by measuring the hydrogen and carbon isotope ratio of acetic acid using head space solid-phase microextraction (HS-SPME) combined with gas chromatography-high temperature conversion or combustion-isotope ratio mass spectrometry (GC-TC/C-IRMS). The measurement of acetic acid in vinegar by this method was possible with repeatabilities (1sigma) of +/-5.0 per thousand for hydrogen and +/-0.4 per thousand for carbon, which are sufficient to discriminate the origin of acetic acid. The fermentation of raw materials of several vinegars was evaluated by this method.

Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

Science.gov (United States)

Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

2015-12-01

Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

Science.gov (United States)

Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

2009-11-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the delta values of these reference materials should bracket the isotopic range of samples with unknown delta values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for delta13C and delta15N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as

Isotope separations using chromatographic methods

International Nuclear Information System (INIS)

Leseticky, L.

1985-01-01

A survey is given of chromatographic separations of compounds only differing in isotope composition. Isotope effects on physical properties which allow chromatographic separation (vapour tension, adsorption heat, partition coefficient) are very small, with the exception of the simplest molecules. Therefore, separation factors only assume the value of several per cent. From this ensues the necessity of using columns which are specially and very carefully prepared and have a separation efficiency of the order of 10 4 theoretical plates. Briefly discussed is liquid chromatography on ion exchangers which with a varied degree of success was used for separating simple inorganic compounds or ions. Ion exchange chromatography of amino acids labelled with tritium, and chromatography of tritium labelled steroids also provided only a certain degree of separation. A detailed analysis is presented of gas chromatography separation of various deuterium and tritium labelled low-molecular compounds, to which a number of studies has been devoted in the literature. Very promising is the method of complexation gas chromatography based on the reversible formation of a complex of the ligand (the compound being separated) and the compound of the (transition) metal as the steady-state phase. (author)

Internal combustion engine for natural gas compressor operation

Energy Technology Data Exchange (ETDEWEB)

Hagen, Christopher L.; Babbitt, Guy; Turner, Christopher; Echter, Nick; Weyer-Geigel, Kristina

2016-04-19

This application concerns systems and methods for compressing natural gas with an internal combustion engine. In a representative embodiment, a system for compressing a gas comprises a reciprocating internal combustion engine including at least one piston-cylinder assembly comprising a piston configured to travel in a cylinder and to compress gas in the cylinder in multiple compression stages. The system can further comprise a first pressure tank in fluid communication with the piston-cylinder assembly to receive compressed gas from the piston-cylinder assembly until the first pressure tank reaches a predetermined pressure, and a second pressure tank in fluid communication with the piston-cylinder assembly and the first pressure tank. The second pressure tank can be configured to receive compressed gas from the piston-cylinder assembly until the second pressure tank reaches a predetermined pressure. When the first and second pressure tanks have reached the predetermined pressures, the first pressure tank can be configured to supply gas to the piston-cylinder assembly, and the piston can be configured to compress the gas supplied by the first pressure tank such that the compressed gas flows into the second pressure tank.

Frontal and band displacement chromatography of the hydrogen isotopes on palladium; Chromatographies frontale et de deplacement de bande des isotopes de l'hydrogene sur palladium

Energy Technology Data Exchange (ETDEWEB)

Botter, F; Menes, J; Tistchenko, S; Dirian, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1964-07-01

As a result of hydrogen isotope separations which we have carried out on supports containing palladium, we believe that we can now make a double contribution, theoretical and experimental, to the work which has already been published in this field. From the fundamental point of view we have developed and studied the validity of a simple model, in our particular case of a separation coefficient {alpha} which is very different to unity. This model, which is of a counter-current isotopic exchange, neglects the longitudinal diffusion in the gas phase and the lateral diffusion in the adsorbed phase and only takes into account the surface resistance to exchange between the phases. It is therefore possible to estimate the efficiency of a chromatography column in terms of the height equivalent of a theoretical plate (HETP). The slight differences observed between the actual chromatograms and the simple model justify both the research undertaken into a more complex model taking into account the diffusion, and the adoption of a simple model for comparing the efficiency of several columns. We describe also a new and simple graphical method for deducing the number of theoretical plates of a column in chromatograms of the frontal and band displacement types. Experimentally we give in particular the criteria for the validity of the model used, the law as a function of the {sup {alpha}}H{sub 2}-HD temperature, the study of the HETP as a function of the various parameters on several palladium containing supports, and the possibilities of an application to preparative chromatography. (authors) [French] Grace aux separations des isotopes de l'hydrogene que nous avons realisees sur masses palladiees, nous pensons apporter aux etudes precedemment publiees dans ce domaine, une double contribution, theorique et experimentale. Du point de vue fondamental, on a developpe et etudie la validite d'un modele simple, dans notre cas particulier d'un coefficient de separation {alpha} tres

A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

NARCIS (Netherlands)

Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

2014-01-01

RATIONALELiquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (C-13/C-12) in biological metabolites, at their natural abundance. However, until now this technique

On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

NARCIS (Netherlands)

Schmitt, J.; Seth, B.; Bock, M; van der Veen, C.; Möller, L.; Sapart, C.J.; Prokopiou, M.; Sowers, T.; Röckmann, T.; Fischer, H

2013-01-01

Stable carbon isotope analysis of methane ( 13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a

Prediction of Non-Equilibrium Kinetics of Fuel-Rich Kerosene/LOX Combustion in Gas Generator

International Nuclear Information System (INIS)

Yu, Jung Min; Lee, Chang Jin

2007-01-01

Gas generator is the device to produce high enthalpy gases needed to drive turbo-pump system in liquid rocket engine. And, the combustion temperature in gas generator should be controlled below around 1,000K to avoid any possible thermal damages to turbine blade by using either fuel rich combustion or oxidizer rich combustion. Thus, nonequilibrium chemical reaction dominates in fuel-rich combustion of gas generator. Meanwhile, kerosene is a compounded fuel with various types of hydrocarbon elements and difficult to model the chemical kinetics. This study focuses on the prediction of the non-equilibrium reaction of fuel rich kerosene/LOX combustion with detailed kinetics developed by Dagaut using PSR (Perfectly Stirred Reactor) assumption. In Dagaut's surrogate model for kerosene, chemical kinetics of kerosene consists of 1,592 reaction steps with 207 chemical species. Also, droplet evaporation time is taken into account in the PSR calculation by changing the residence time of droplet in the gas generator. Frenklach's soot model was implemented along with detailed kinetics to calculate the gas properties of fuel rich combustion efflux. The results could provide very reliable and accurate numbers in the prediction of combustion gas temperature,species fraction and material properties

Suitability of selected free-gas and dissolved-gas sampling containers for carbon isotopic analysis.

Science.gov (United States)

Eby, P; Gibson, J J; Yi, Y

2015-07-15

Storage trials were conducted for 2 to 3 months using a hydrocarbon and carbon dioxide gas mixture with known carbon isotopic composition to simulate typical hold times for gas samples prior to isotopic analysis. A range of containers (both pierced and unpierced) was periodically sampled to test for δ(13)C isotopic fractionation. Seventeen containers were tested for free-gas storage (20°C, 1 atm pressure) and 7 containers were tested for dissolved-gas storage, the latter prepared by bubbling free gas through tap water until saturated (20°C, 1 atm) and then preserved to avoid biological activity by acidifying to pH 2 with phosphoric acid and stored in the dark at 5°C. Samples were extracted using valves or by piercing septa, and then introduced into an isotope ratio mass spectrometer for compound-specific δ(13)C measurements. For free gas, stainless steel canisters and crimp-top glass serum bottles with butyl septa were most effective at preventing isotopic fractionation (pierced and unpierced), whereas silicone and PTFE-butyl septa allowed significant isotopic fractionation. FlexFoil and Tedlar bags were found to be effective only for storage of up to 1 month. For dissolved gas, crimp-top glass serum bottles with butyl septa were again effective, whereas silicone and PTFE-butyl were not. FlexFoil bags were reliable for up to 2 months. Our results suggest a range of preferred containers as well as several that did not perform very well for isotopic analysis. Overall, the results help establish better QA/QC procedures to avoid isotopic fractionation when storing environmental gas samples. Recommended containers for air transportation include steel canisters and glass serum bottles with butyl septa (pierced and unpierced). Copyright © 2015 John Wiley & Sons, Ltd.

Investigation of the feeding effect on the 13C/12C isotope ratio of the hormones in bovine urine using gas chromatography/combustion isotope ratio mass spectrometry

NARCIS (Netherlands)

Balizs, Gabor; Jainz, Annett; Horvatovich, Peter

2005-01-01

The effect of the feeding on the 13C/12C isotope ratio of four endogenous steroid hormones testosterone (T), epi-testosterone (epi-T), dehydroepiandrosterone (DHEA) and etiocholanolone (ETIO) in bovine urine was investigated. An analytical method to determine the accurate isotope ratio was developed

Real gas CFD simulations of hydrogen/oxygen supercritical combustion

Science.gov (United States)

Pohl, S.; Jarczyk, M.; Pfitzner, M.; Rogg, B.

2013-03-01

A comprehensive numerical framework has been established to simulate reacting flows under conditions typically encountered in rocket combustion chambers. The model implemented into the commercial CFD Code ANSYS CFX includes appropriate real gas relations based on the volume-corrected Peng-Robinson (PR) equation of state (EOS) for the flow field and a real gas extension of the laminar flamelet combustion model. The results indicate that the real gas relations have a considerably larger impact on the flow field than on the detailed flame structure. Generally, a realistic flame shape could be achieved for the real gas approach compared to experimental data from the Mascotte test rig V03 operated at ONERA when the differential diffusion processes were only considered within the flame zone.

Comparing the greenhouse gas emissions from three alternative waste combustion concepts.

Science.gov (United States)

Vainikka, Pasi; Tsupari, Eemeli; Sipilä, Kai; Hupa, Mikko

2012-03-01

Three alternative condensing mode power and combined heat and power (CHP) waste-to-energy concepts were compared in terms of their impacts on the greenhouse gas (GHG) emissions from a heat and power generation system. The concepts included (i) grate, (ii) bubbling fluidised bed (BFB) and (iii) circulating fluidised bed (CFB) combustion of waste. The BFB and CFB take advantage of advanced combustion technology which enabled them to reach electric efficiency up to 35% and 41% in condensing mode, respectively, whereas 28% (based on the lower heating value) was applied for the grate fired unit. A simple energy system model was applied in calculating the GHG emissions in different scenarios where coal or natural gas was substituted in power generation and mix of fuel oil and natural gas in heat generation by waste combustion. Landfilling and waste transportation were not considered in the model. GHG emissions were reduced significantly in all of the considered scenarios where the waste combustion concepts substituted coal based power generation. With the exception of condensing mode grate incinerator the different waste combustion scenarios resulted approximately in 1 Mton of fossil CO(2)-eq. emission reduction per 1 Mton of municipal solid waste (MSW) incinerated. When natural gas based power generation was substituted by electricity from the waste combustion significant GHG emission reductions were not achieved. Copyright © 2011 Elsevier Ltd. All rights reserved.

CFD simulation of gas and particles combustion in biomass furnaces

Energy Technology Data Exchange (ETDEWEB)

Griselin, Nicolas

2000-11-01

In this thesis, gas and particle combustion in biomass furnaces is investigated numerically. The aim of this thesis is to use Computational Fluid Dynamics (CFD) technology as an effective computer based simulation tool to study and develop the combustion processes in biomass furnaces. A detailed model for the numerical simulation of biomass combustion in a furnace, including fixed-bed modeling, gas-phase calculation (species distribution, temperature field, flow field) and gas-solid two-phase interaction for flying burning particles is presented. This model is used to understand the mechanisms of combustion and pollutant emissions under different conditions in small scale and large scale furnaces. The code used in the computations was developed at the Division of Fluid Mechanics, LTH. The flow field in the combustion enclosure is calculated by solving the Favre-averaged Navier-Stokes equations, with standard {kappa} - {epsilon} turbulence closure, together with the energy conservation equation and species transport equations. Discrete transfer method is used for calculating the radiation source term in the energy conservation equation. Finite difference is used to solve the general form of the equation yielding solutions for gas-phase temperatures, velocities, turbulence intensities and species concentrations. The code has been extended through this work in order to include two-phase flow simulation of particles and gas combustion. The Favre-averaged gas equations are solved in a Eulerian framework while the submodels for particle motion and combustion are used in the framework of a Lagrangian approach. Numerical simulations and measurement data of unburned hydrocarbons (UHC), CO, H{sub 2}, O{sub 2} and temperature on the top of the fixed bed are used to model the amount of tar and char formed during pyrolysis and combustion of biomass fuel in the bed. Different operating conditions are examined. Numerical calculations are compared with the measured data. It is

[Gas chromatography in quantitative analysis of hydrocyanic acid and its salts in cadaveric blood].

Science.gov (United States)

Iablochkin, V D

2003-01-01

A direct gas chromatography method was designed for the quantitative determination of cyanides (prussic acid) in cadaveric blood. Its sensitivity is 0.05 mg/ml. The routine volatile products, including substances, which emerge due to putrefaction of organic matters, do not affect the accuracy and reproducibility of the method; the exception is H-propanol that was used as the internal standard. The method was used in legal chemical expertise related with acute cyanide poisoning (suicide) as well as with poisoning of products of combustion of nonmetals (foam-rubber). The absolute error does not exceed 10% with a mean quadratic deviation of 0.0029-0.0033 mg.

Multi-column chromatography and the use of isotopes in the study of steroid metabolism

International Nuclear Information System (INIS)

Sayegh, J.F.; Vestergaard, P.

1978-01-01

Multi-column liquid chromatography is demonstrated to be a technique well suited for isotope experiments involving administration of labelled cortisol. It has potential for secretion rate determinations, for dynamic studies of cortisol metabolism and for work with stable isotopes. (author)

Use of micro gas chromatography in the fuel cycle of fusion reactors

International Nuclear Information System (INIS)

Laesser, R.; Gruenhagen, S.; Kawamura, Y.

2003-01-01

Various analytical techniques exist to determine the compositions of gases handled in the fuel cycle of future fusion machines. Gas chromatography was found to be the most appropriate method. The main disadvantages of conventional gas chromatography were the long retention times for the heavy hydrogen species of >30 min. Recent progress in the development of micro-gas chromatography has reduced these retention times to ∼3 min. The usefulness of micro-gas chromatography for the analysis of hydrogen and impurity gas mixtures in the fuel cycle of future fusion machines is presented and the advantages and drawbacks are discussed

Comparing the greenhouse gas emissions from three alternative waste combustion concepts

International Nuclear Information System (INIS)

Vainikka, Pasi; Tsupari, Eemeli; Sipilä, Kai; Hupa, Mikko

2012-01-01

Highlights: ► Significant GHG reductions are possible by efficient WtE technologies. ► CHP and high power-to-heat ratio provide significant GHG savings. ► N 2 O and coal mine type are important in LCA GHG emissions of FBC co-combustion. ► Substituting coal and fuel oil by waste is beneficial in electricity and heat production. ► Substituting natural gas by waste may not be reasonable in CHP generation. - Abstract: Three alternative condensing mode power and combined heat and power (CHP) waste-to-energy concepts were compared in terms of their impacts on the greenhouse gas (GHG) emissions from a heat and power generation system. The concepts included (i) grate, (ii) bubbling fluidised bed (BFB) and (iii) circulating fluidised bed (CFB) combustion of waste. The BFB and CFB take advantage of advanced combustion technology which enabled them to reach electric efficiency up to 35% and 41% in condensing mode, respectively, whereas 28% (based on the lower heating value) was applied for the grate fired unit. A simple energy system model was applied in calculating the GHG emissions in different scenarios where coal or natural gas was substituted in power generation and mix of fuel oil and natural gas in heat generation by waste combustion. Landfilling and waste transportation were not considered in the model. GHG emissions were reduced significantly in all of the considered scenarios where the waste combustion concepts substituted coal based power generation. With the exception of condensing mode grate incinerator the different waste combustion scenarios resulted approximately in 1 Mton of fossil CO 2 -eq. emission reduction per 1 Mton of municipal solid waste (MSW) incinerated. When natural gas based power generation was substituted by electricity from the waste combustion significant GHG emission reductions were not achieved.

Contact heating of water products of combustion of natural gas

Energy Technology Data Exchange (ETDEWEB)

Aronov, I Z

1978-01-01

The USSR's NIIST examined the processes and equipment for heating water by submerged combustion using natural gas. Written for engineers involved with the design and application of thermal engineering equipment operating with natural gas, the book emphasizes equipment, test results, and methods of calculating heat transfer for contact gas economizers developed by Scientific Research Institute of Sanitary Engineering and other Soviet organizations. The economic effectiveness of submerged-combustion heating depends on several factors, including equipment design. Recommendations cover cost-effective designs and applications of contact economizers and boilers.

Data acquisition and quantitative analysis of stable hydrogen isotope in liquid and gas in the liquid phase catalytic exchange process

International Nuclear Information System (INIS)

Choi, H. J.; Lee, H. S.; Kim, K. R.; Cheong, H. S.; Ahn, D. H.; Lee, S. H.; Paek, S. W.; Kang, H. S.; Kim, J. G.

2001-01-01

A pilot plant for the Liquid Phase Catalytic Exchange process was built and has been operating to test the hydrophobic catalyst developed to remove the tritium generated at the CANDU nuclear power plants. The methods of quantitative analysis of hydrogen stable isotope were compared. Infrared spectroscopy was used for the liquid samples, and gas chromatography with hydrogen carrier gas showed the best result for gas samples. Also, a data acquisition system was developed to record the operation parameters. This record was very useful to investigate the causes of the system trip

Optimization of an online heart-cutting multidimensional gas chromatography clean-up step for isotopic ratio mass spectrometry and simultaneous quadrupole mass spectrometry measurements of endogenous anabolic steroid in urine.

Science.gov (United States)

Casilli, Alessandro; Piper, Thomas; de Oliveira, Fábio Azamor; Padilha, Monica Costa; Pereira, Henrique Marcelo; Thevis, Mario; de Aquino Neto, Francisco Radler

2016-11-01

Measuring carbon isotope ratios (CIRs) of urinary analytes represents a cornerstone of doping control analysis and has been particularly optimized for the detection of the misuse of endogenous steroids. Isotope ratio mass spectrometry (IRMS) of appropriate quality, however, necessitates adequate purities of the investigated steroids, which requires extensive pre-analytical sample clean-up steps due to both the natural presence of the target analytes and the high complexity of the matrix. In order to accelerate the sample preparation and increase the automation of the process, the use of multidimensional gas chromatography (MDGC) prior to IRMS experiments, was investigated. A well-established instrumental configuration based on two independent GC ovens and one heart-cutting device was optimized. The first dimension (1D) separation was obtained by a non-polar column which assured high efficiency and good loading capacity, while the second dimension (2D), based on a mid-polar stationary phase, provided good selectivity. A flame ionization detector monitored the 1D, and the 2D was simultaneously recorded by isotope ratio and quadrupole mass spectrometry. The assembled MDGC set-up was applied for measuring testosterone, 5α- and 5β-androstanediol, androsterone, and etiocholanolone as target compounds and pregnanediol as endogenous reference compound. The urine sample were pretreated by conventional sample preparation steps comprising solid-phase extraction, hydrolysis, and liquid-liquid extraction. The extract obtained was acetylated and different aliquots were injected into the MDGC system. Two high performance liquid chromatography steps, conventionally adopted prior to CIR measurements, were replaced by the MDGC approach. The obtained values were consistent with the conventional ones. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

CFD analysis of combustion of natural gas and syngas from biomass pyrolysis in the combustion chamber of a micro gas turbine

Energy Technology Data Exchange (ETDEWEB)

Fantozzi, Francesco; Laranci, Paolo; D' Alessandro, Bruno [University of Perugia (DII/UNIPG) (Italy). Dept. of Industrial Engineering], Emails: fanto@unipg.it, paolo.laranci@unipg.it, dalessandro@bio-net.it

2009-07-01

Micro gas turbines (MGT) can be profitably used for the production of distributed energy (DE), with the possibility to use gaseous fuels with low BTU derived from biomass or waste through the pyrolysis or gasification processes. These synthesis gases (SG) show significant differences with respect to natural gas (NG), in terms of composition, calorific value, content of hydrogen, tar and particulate matter content; such differences can be turn into problems of ignition, instability burning, difficulties in controlling the emissions and fouling. CFD analysis of the combustion process is an essential tool for identifying the main critical arising in using these gases, in order to modify existing geometries and to develop new generation of combustor for use with low BTU gases. This paper describes the activities of experimental and numerical analysis carried out to study the combustion process occurring inside an existing annular Rich-Quench-Lean (RQL) Combustion Chamber (CC) of a 80 kW MGT. In the paper some results of a CFD study of the combustion process performed with an original developed chemical models are reported in terms of temperature and velocity distributions inside the CC and in terms of compositions of turbine inlet gas and of its thermodynamic parameters (mass flow, temperature, pressure). An evaluation of pollutant emissions of CO, CO{sub 2} and NOx and a comparison with the available experimental data relating to the case of combustion of NG is also provided in the paper. Moreover, the carried out investigation concerns the case of operation with a SG fuel derived from biomass in an Integrated Pyrolysis Regenerated Plant (IPRP). (author)

Development and test of combustion chamber for Stirling engine heated by natural gas

Science.gov (United States)

Li, Tie; Song, Xiange; Gui, Xiaohong; Tang, Dawei; Li, Zhigang; Cao, Wenyu

2014-04-01

The combustion chamber is an important component for the Stirling engine heated by natural gas. In the paper, we develop a combustion chamber for the Stirling engine which aims to generate 3˜5 kWe electric power. The combustion chamber includes three main components: combustion module, heat exchange cavity and thermal head. Its feature is that the structure can divide "combustion" process and "heat transfer" process into two apparent individual steps and make them happen one by one. Since natural gas can mix with air fully before burning, the combustion process can be easily completed without the second wind. The flame can avoid contacting the thermal head of Stirling engine, and the temperature fields can be easily controlled. The designed combustion chamber is manufactured and its performance is tested by an experiment which includes two steps. The experimental result of the first step proves that the mixture of air and natural gas can be easily ignited and the flame burns stably. In the second step of experiment, the combustion heat flux can reach 20 kW, and the energy utilization efficiency of thermal head has exceeded 0.5. These test results show that the thermal performance of combustion chamber has reached the design goal. The designed combustion chamber can be applied to a real Stirling engine heated by natural gas which is to generate 3˜5 kWe electric power.

Evaluation of gas radiation models in CFD modeling of oxy-combustion

International Nuclear Information System (INIS)

Rajhi, M.A.; Ben-Mansour, R.; Habib, M.A.; Nemitallah, M.A.; Andersson, K.

2014-01-01

Highlights: • CFD modeling of a typical industrial water tube boiler is conducted. • Different combustion processes were considered including air and oxy-fuel combustion. • SGG, EWBM, Leckner, Perry and WSGG radiation models were considered in the study. • EWBM is the most accurate model and it’s considered to be the benchmark model. • Characteristics of oxy-fuel combustion are compared to those of air–fuel combustion. - Abstract: Proper determination of the radiation energy is very important for proper predictions of the combustion characteristics inside combustion devices using CFD modeling. For this purpose, different gas radiation models were developed and applied in the present work. These radiation models vary in their accuracy and complexity according to the application. In this work, a CFD model for a typical industrial water tube boiler was developed, considering three different combustion environments. The combustion environments are air–fuel combustion (21% O 2 and 79% N 2 ), oxy-fuel combustion (21% O 2 and 79% CO 2 ) and oxy-fuel combustion (27% O 2 and 73% CO 2 ). Simple grey gas (SGG), exponential wide band model (EWBM), Leckner, Perry and weighted sum of grey gases (WSGG) radiation models were examined and their influences on the combustion characteristics were evaluated. Among those radiation models, the EWBM was found to provide close results to the experimental data for the present boiler combustion application. The oxy-fuel combustion characteristics were analyzed and compared with those of air–fuel combustion

Multiplex gas chromatography

Science.gov (United States)

Valentin, Jose R.

1990-01-01

The principles of the multiplex gas chromatography (GC) technique, which is a possible candidate for chemical analysis of planetary atmospheres, are discussed. Particular attention is given to the chemical modulators developed by present investigators for multiplex GC, namely, the thermal-desorption, thermal-decomposition, and catalytic modulators, as well as to mechanical modulators. The basic technique of multiplex GC using chemical modulators and a mechanical modulator is demonstrated. It is shown that, with the chemical modulators, only one gas stream consisting of the carrier in combination with the components is being analyzed, resulting in a simplified instrument that requires relatively few consumables. The mechanical modulator demonstrated a direct application of multiplex GC for the analysis of gases in atmosphere of Titan at very low pressures.

Combustion Sensors: Gas Turbine Applications

Science.gov (United States)

Human, Mel

2002-01-01

This report documents efforts to survey the current research directions in sensor technology for gas turbine systems. The work is driven by the current and future requirements on system performance and optimization. Accurate real time measurements of velocities, pressure, temperatures, and species concentrations will be required for objectives such as combustion instability attenuation, pollutant reduction, engine health management, exhaust profile control via active control, etc. Changing combustor conditions - engine aging, flow path slagging, or rapid maneuvering - will require adaptive responses; the effectiveness of such will be only as good as the dynamic information available for processing. All of these issues point toward the importance of continued sensor development. For adequate control of the combustion process, sensor data must include information about the above mentioned quantities along with equivalence ratios and radical concentrations, and also include both temporal and spatial velocity resolution. Ultimately these devices must transfer from the laboratory to field installations, and thus must become low weight and cost, reliable and maintainable. A primary conclusion from this study is that the optics-based sensor science will be the primary diagnostic in future gas turbine technologies.

Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks

Science.gov (United States)

Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C.-Y.; Fujitani, T.; Okano, O.

2011-01-01

Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

Mercury stable isotope signatures of world coal deposits and historical coal combustion emissions.

Science.gov (United States)

Sun, Ruoyu; Sonke, Jeroen E; Heimbürger, Lars-Eric; Belkin, Harvey E; Liu, Guijian; Shome, Debasish; Cukrowska, Ewa; Liousse, Catherine; Pokrovsky, Oleg S; Streets, David G

2014-07-01

Mercury (Hg) emissions from coal combustion contribute approximately half of anthropogenic Hg emissions to the atmosphere. With the implementation of the first legally binding UNEP treaty aimed at reducing anthropogenic Hg emissions, the identification and traceability of Hg emissions from different countries/regions are critically important. Here, we present a comprehensive world coal Hg stable isotope database including 108 new coal samples from major coal-producing deposits in South Africa, China, Europe, India, Indonesia, Mongolia, former USSR, and the U.S. A 4.7‰ range in δ(202)Hg (-3.9 to 0.8‰) and a 1‰ range in Δ(199)Hg (-0.6 to 0.4‰) are observed. Fourteen (p coal Hg emissions tracing. A revised coal combustion Hg isotope fractionation model is presented, and suggests that gaseous elemental coal Hg emissions are enriched in the heavier Hg isotopes relative to oxidized forms of emitted Hg. The model explains to first order the published δ(202)Hg observations on near-field Hg deposition from a power plant and global scale atmospheric gaseous Hg. Yet, model uncertainties appear too large at present to permit straightforward Hg isotope source identification of atmospheric forms of Hg. Finally, global historical (1850-2008) coal Hg isotope emission curves were modeled and indicate modern-day mean δ(202)Hg and Δ(199)Hg values for bulk coal emissions of -1.2 ± 0.5‰ (1SD) and 0.05 ± 0.06‰ (1SD).

New method for GC/FID and GC-C-IRMS analysis of plasma free fatty acid concentration and isotopic enrichment.

Science.gov (United States)

Kangani, Cyrous O; Kelley, David E; Delany, James P

2008-09-15

A simple, direct and accurate method for the determination of concentration and enrichment of free fatty acids (FFAs) in human plasma was developed. The validation and comparison to a conventional method are reported. Three amide derivatives, dimethyl, diethyl and pyrrolidide, were investigated in order to achieve optimal resolution of the individual fatty acids. This method involves the use of dimethylamine/Deoxo-Fluor to derivatize plasma free fatty acids to their dimethylamides. This derivatization method is very mild and efficient, and is selective only towards FFAs so that no separation from a total lipid extract is required. The direct method gave lower concentrations for palmitic acid and stearic acid and increased concentrations for oleic acid and linoleic acid in plasma as compared to methyl ester derivative after thin-layer chromatography. The [(13)C]palmitate isotope enrichment measured using direct method was significantly higher than that observed with the BF(3)/MeOH-TLC method. The present method provided accurate and precise measures of concentration as well as enrichment when analyzed with gas chromatography combustion-isotope ratio-mass spectrometry.

Combustion modeling in advanced gas turbine systems

Energy Technology Data Exchange (ETDEWEB)

Smoot, L.D.; Hedman, P.O.; Fletcher, T.H. [Brigham Young Univ., Provo, UT (United States)] [and others

1995-10-01

The goal of the U.S. Department of Energy`s Advanced Turbine Systems (ATS) program is to help develop and commercialize ultra-high efficiency, environmentally superior, and cost competitive gas turbine systems for base-load applications in the utility, independent power producer, and industrial markets. Combustion modeling, including emission characteristics, has been identified as a needed, high-priority technology by key professionals in the gas turbine industry.

Sourcing methane and carbon dioxide emissions from a small city: Influence of natural gas leakage and combustion.

Science.gov (United States)

Chamberlain, Samuel D; Ingraffea, Anthony R; Sparks, Jed P

2016-11-01

Natural gas leakage and combustion are major sources of methane (CH 4 ) and carbon dioxide (CO 2 ), respectively; however, our understanding of emissions from cities is limited. We mapped distribution pipeline leakage using a mobile CH 4 detection system, and continuously monitored atmospheric CO 2 and CH 4 concentrations and carbon isotopes (δ 13 C-CO 2 and δ 13 C-CH 4 ) for one-year above Ithaca, New York. Pipeline leakage rates were low (emission source in that wind sector. Our results demonstrate pipeline leakage rates are low in cities with a low extent of leak prone pipe, and natural gas power facilities may be an important source of urban and suburban emissions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characteristics of stable carbon isotopic composition of shale gas

Directory of Open Access Journals (Sweden)

Zhenya Qu

2016-04-01

Full Text Available A type Ⅱ kerogen with low thermal maturity was adopted to perform hydrocarbon generation pyrolysis experiments in a vacuum (Micro-Scale Sealed Vessel system at the heating rates of 2 °C/h and 20 °C/h. The stable carbon isotopic compositions of gas hydrocarbons were measured to investigate their evolving characteristics and the possible reasons for isotope reversal. The δ13C values of methane became more negative with the increasing pyrolysis temperatures until it reached the lightest point, after which they became more positive. Meanwhile, the δ13C values of ethane and propane showed a positive trend with elevating pyrolysis temperatures. The carbon isotopic compositions of shale gasses were mainly determined by the type of parent organic matter, thermal evolutionary extent, and gas migration in shale systems. Our experiments and study proved that the isotope reversal shouldn't occur in a pure thermogenic gas reservoir, it must be involved with some other geochemical process/es; although mechanisms responsible for the reversal are still vague. Carbon isotopic composition of the Fayetteville and Barnett shale gas demonstrated that the isotope reversal was likely involved with water–gas reaction and Fischer-Tropsch synthesis during its generation.

Stable isotope ratiometer-multiple ion detector (SIRMID) unit for quantitative and qualitative stable isotope studies by gas chromatography-mass spectrometry

International Nuclear Information System (INIS)

Klein, P.D.; Haumann, J.R.; Hachey, D.L.

1975-01-01

A stable isotope ratiometer-multiple ion detector (SIRMID) unit which can drive existing gas chromatograph-quadrupole or magnetic sector mass spectrometers to monitor up to six ions in turn is described. Each of the three pairs of ions can be selected for quantitation; thus three different or successive components can be analyzed in a single GC run. A background subtraction option permits the ion intensity in the absence of sample to be subtracted automatically during sample measurement. Displays of accumulated counts and isotope ratio are updated twice per second during the measurement and can be printed out at its conclusion. All six ions can be monitored in the analog mode by parallel outputs to a multipen recorder. Experience gained in the construction of this prototype indicates that SIRMID units could be commercially available for $10K, or about 1 / 3 rd to 1 / 6 th of the cost of even an inexpensive computer system. (U.S.)

Optical backscatter probe for sensing particulate in a combustion gas stream

Science.gov (United States)

Parks, James E; Partridge, William P

2013-05-28

A system for sensing particulate in a combustion gas stream is disclosed. The system transmits light into a combustion gas stream, and thereafter detects a portion of the transmitted light as scattered light in an amount corresponding to the amount of particulates in the emissions. Purge gas may be supplied adjacent the light supply and the detector to reduce particles in the emissions from coating or otherwise compromising the transmission of light into the emissions and recovery of scattered light from the emissions.

Quantification of fentanyl in serum by isotope dilution analysis using capillary gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Sera, Shoji; Goromaru, Tsuyoshi [Fukuyama Univ., Hiroshima (Japan); Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

1998-06-01

The quantitative determination of fentanyl (FT) in serum was examined by isotope dilution analysis using a capillary gas chromatograph equipped with a surface ionization detector. The separation of FT and its deuterated analogue, FT-{sup 2}H{sub 19}, was achieved within 15 min a column temperature of 260degC by using a 25 m column. Measurement of the samples prepared by the addition of a known amount of FT in the range of 0.2 to 40 ng/ml with 20 ng/ml of FT-{sup 2}H{sub 19} to human control serum allowed observation of a linear relationship between the peak area ratio and the added amount ratio. The correlation coefficient obtained by regression analysis was 0.999. The advantage of the present isotope dilution method was demonstrated by comparison with other FT analogues which substituted a propionyl group with an acetyl group or a phenethyl group with a benzyl group as the internal standard. The present method was used to determine the serum level of FT in surgical patients after i.v. administration. No endogenous compounds and concomitant drugs interfered with the detection of FT or FT-{sup 2}H{sub 19}. This method was considered to be useful for the pharmacokinetic study of FT in patients. (author)

Quantification of fentanyl in serum by isotope dilution analysis using capillary gas chromatography

International Nuclear Information System (INIS)

Sera, Shoji; Goromaru, Tsuyoshi; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

1998-01-01

The quantitative determination of fentanyl (FT) in serum was examined by isotope dilution analysis using a capillary gas chromatograph equipped with a surface ionization detector. The separation of FT and its deuterated analogue, FT- 2 H 19 , was achieved within 15 min a column temperature of 260degC by using a 25 m column. Measurement of the samples prepared by the addition of a known amount of FT in the range of 0.2 to 40 ng/ml with 20 ng/ml of FT- 2 H 19 to human control serum allowed observation of a linear relationship between the peak area ratio and the added amount ratio. The correlation coefficient obtained by regression analysis was 0.999. The advantage of the present isotope dilution method was demonstrated by comparison with other FT analogues which substituted a propionyl group with an acetyl group or a phenethyl group with a benzyl group as the internal standard. The present method was used to determine the serum level of FT in surgical patients after i.v. administration. No endogenous compounds and concomitant drugs interfered with the detection of FT or FT- 2 H 19 . This method was considered to be useful for the pharmacokinetic study of FT in patients. (author)

Internal Combustion Engine Powered by Synthesis Gas from Pyrolysed Plastics

Directory of Open Access Journals (Sweden)

Chríbik Andrej

2016-07-01

Full Text Available The article discusses the application of synthesis gas from pyrolysis of plastics in petrol engine. The appropriate experimental measurements were performed on a combustion engine LGW 702 designated for micro-cogeneration unit. The power parameters, economic parameters in term of brake specific fuel consumption, and internal parameters of the engine were compared to the engine running on the reference fuel - natural gas and synthesis gas. Burning synthesis gas leads to decreased performance by about 5% and to increased mass hourly consumption by 120 %. In terms of burning, synthesis gas has similar properties as natural gas. Compared with [5] a more detailed study has been prepared on the effects of angle of spark advance on the engine torque, giving more detailed assessment of engine cycle variability and considering specification of start and end of combustion in the logarithm p-V diagram.

Towards Control-Oriented Modeling of Natural Gas-Diesel RCCI Combustion

NARCIS (Netherlands)

Bekdemir, C.; Baert, R.; Willems, F.; Somers, B.

2015-01-01

For natural gas (NG)-diesel RCCI, a multi-zonal, detailed chemistry modeling approach is presented. This dual fuel combustion process requires further understanding of the ignition and combustion processes to maximize thermal efficiency and minimize (partially) unburned fuel emissions. The

Towards control-oriented modeling of natural gas-diesel RCCI combustion

NARCIS (Netherlands)

Bekdemir, C.; Baert, R.S.G.; Willems, F.P.T.; Somers, L.M.T.

2015-01-01

For natural gas (NG)-diesel RCCI, a multi-zonal, detailed chemistry modeling approach is presented. This dual fuel combustion process requires further understanding of the ignition and combustion processes to maximize thermal efficiency and minimize (partially) unburned fuel emissions. The

Combustible gas recombining method and processing facility for gas waste

International Nuclear Information System (INIS)

Watabe, Atsushi; Murakami, Kazuo

1998-01-01

Combustible gases (hydrogen, oxygen) generated by radiation decomposition of reactor water in the vicinity of a reactor core in a reactor pressure vessel of a BWR type nuclear power plant pass, together with flow of steams, through a gas/water separator and a steam dryer disposed at the upper portion of a reactor core. A catalyst for allowing hydrogen and oxygen to react efficiently and recombine them into water is plated on the surface of the steam dryer. The catalyst comprises palladium (Pd) or platinum (Pt) or a Pd-Pt alloy. The combustible gases passing through the steam dryer are recombined and formed into steams by the catalyst. A slight amount of hydrogen and oxygen which are not recombined transfers, together with main steams, from a main steam pipe to a main condensator by way of a turbine. Then they are released, together with air from an air extraction device, from an activated carbon-type rare gas hold up tower. (I.N.)

Early stages in the history of gas chromatography.

Science.gov (United States)

Kolomnikov, Ivan G; Efremov, Alexander M; Tikhomirova, Tatyana I; Sorokina, Nadezhda M; Zolotov, Yury A

2018-02-16

The creation of gas chromatography is traditionally associated with the names of Nobel Prize winner Archer Martin and his colleagues Richard Synge and Anthony James. However, sometimes references to their predecessors can be found. An investigation conducted by the authors of this article not only confirmed the reliability of these references; but in fact led to the conclusion that by 1952, which is commonly believed to be the year when gas chromatography was born, many research papers had already been devoted to this method, mainly, in its gas-solid version. These papers are considered in this article. Copyright © 2018. Published by Elsevier B.V.

Effect of exhaust gas recirculation on some combustion characteristics of dual fuel engine

Energy Technology Data Exchange (ETDEWEB)

Selim, Mohamed Y.E. [United Arab Emirates Univ., Dept. of Mechanical Engineering, Al-Ain (United Arab Emirates)

2003-03-01

Combustion pressure rise rate and thermal efficiency data are measured and presented for a dual fuel engine running on a dual fuel of Diesel and compressed natural gas and utilizing exhaust gas recirculation (EGR). The maximum pressure rise rate during combustion is presented as a measure of combustion noise. The experimental investigation on the dual fuel engine revealed the noise generated from combustion and the thermal efficiency at different EGR ratios. A Ricardo E6 Diesel version engine is converted to run on a dual fuel of Diesel and compressed natural gas and having an exhaust gas recycling system is used throughout the work. The engine is fully computerized, and the cylinder pressure data and crank angle data are stored in a PC for offline analysis. The effects of EGR ratio, engine speeds, loads, temperature of recycled exhaust gases, intake charge pressure and engine compression ratio on combustion noise and thermal efficiency are examined for the dual fuel engine. The combustion noise and thermal efficiency of the dual fuel engine are found to be affected when EGR is used in the dual fuel engine. (Author)

Characterisation of uremic "Middle molecular"fractions by gas chromatography mass spectrometry, isotachophoresis, and liquid chromatography

NARCIS (Netherlands)

Schoots, A.C.; Mikkers, F.E.P.; Claessens, H.A.; Smet, de R.; Landschoot, van N.; Ringoir, S.M.G.

1982-01-01

Uremic ultrafiltrates (and normal serum, for comparison) were fractionated by means of gel filtration. The collected fractions were further investigated by combined analytical techniques: "high- performance" liquid chromatography, gas chromatography, mass spectrometry, and isotachophoresis.

Isotopic and molecular fractionation in combustion; three routes to molecular marker validation, including direct molecular 'dating' (GC/AMS)

Science.gov (United States)

Currie, L. A.; Klouda, G. A.; Benner, B. A.; Garrity, K.; Eglinton, T. I.

The identification of unique isotopic, elemental, and molecular markers for sources of combustion aerosol has growing practical importance because of the potential effects of fine particle aerosol on health, visibility and global climate. It is urgent, therefore, that substantial efforts be directed toward the validation of assumptions involving the use of such tracers for source apportionment. We describe here three independent routes toward carbonaceous aerosol molecular marker identification and validation: (1) tracer regression and multivariate statistical techniques applied to field measurements of mixed source, carbonaceous aerosols; (2) a new development in aerosol 14C metrology: direct, pure compound accelerator mass spectrometry (AMS) by off-line GC/AMS ('molecular dating'); and (3) direct observation of isotopic and molecular source emissions during controlled laboratory combustion of specific fuels. Findings from the combined studies include: independent support for benzo( ghi)perylene as a motor vehicle tracer from the first (statistical) and second (direct 'dating') studies; a new indication, from the third (controlled combustion) study, of a relation between 13C isotopic fractionation and PAH molecular fractionation, also linked with fuel and stage of combustion; and quantitative data showing the influence of both fuel type and combustion conditions on the yields of such species as elemental carbon and PAH, reinforcing the importance of exercising caution when applying presumed conservative elemental or organic tracers to fossil or biomass burning field data as in the first study.

Flow Rates in Liquid Chromatography, Gas Chromatography and Supercritical Fluid Chromatography: A Tool for Optimization

Directory of Open Access Journals (Sweden)

Joris Meurs

2016-08-01

Full Text Available This paper aimed to develop a standalone application for optimizing flow rates in liquid chromatography (LC, gas chromatography (GC and supercritical fluid chromatography (SFC. To do so, Van Deemter’s equation, Knox’ equation and Golay’s equation were implemented in a MATLAB script and subsequently a graphical user interface (GUI was created. The application will show the optimal flow rate or linear velocity and the corresponding plate height for the set input parameters. Furthermore, a plot will be shown in which the plate height is plotted against the linear flow velocity. Hence, this application will give optimized flow rates for any set conditions with minimal effort.

Scaling of the flow field in a combustion chamber with a gas–gas injector

International Nuclear Information System (INIS)

Xiao-Wei, Wang; Guo-Biao, Cai; Ping, Jin

2010-01-01

The scaling of the flow field in a gas–gas combustion chamber is investigated theoretically, numerically and experimentally. To obtain the scaling criterion of the gas–gas combustion flowfield, formulation analysis of the three-dimensional (3D) Navier–Stokes equations for a gaseous multi-component mixing reaction flow is conducted and dimensional analysis on the gas–gas combustion phenomena is also carried out. The criterion implies that the size and the pressure of the gas–gas combustion chamber can be changed. Based on the criterion, multi-element injector chambers with different geometric sizes and at different chamber pressures ranging from 3 MPa to 20 MPa are numerically simulated. A multi-element injector chamber is designed and hot-fire tested at five chamber pressures from 1.64 MPa to 3.68 MPa. Wall temperature measurements are used to understand the similarity of combustion flowfields in the tests. The results have verified the similarities between combustion flowfields under different chamber pressures and geometries, with the criterion applied. (geophysics, astronomy and astrophysics)

Device to lower NOx in a gas turbine engine combustion system

Science.gov (United States)

Laster, Walter R; Schilp, Reinhard; Wiebe, David J

2015-02-24

An emissions control system for a gas turbine engine including a flow-directing structure (24) that delivers combustion gases (22) from a burner (32) to a turbine. The emissions control system includes: a conduit (48) configured to establish fluid communication between compressed air (22) and the combustion gases within the flow-directing structure (24). The compressed air (22) is disposed at a location upstream of a combustor head-end and exhibits an intermediate static pressure less than a static pressure of the combustion gases within the combustor (14). During operation of the gas turbine engine a pressure difference between the intermediate static pressure and a static pressure of the combustion gases within the flow-directing structure (24) is effective to generate a fluid flow through the conduit (48).

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

Science.gov (United States)

Kawamura, Kimitaka; Barrie, Leonard A.; Toom-Sauntry, Desiree

2010-12-01

Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (oxalic acid by GC ranged from 6.5-59.1 ng m -3 (av. 26.0 ng m -3, median 26.2 ng m -3) whereas those by IC ranged from 6.6-52.1 ng m -3 (av. 26.6 ng m -3, median 25.4 ng m -3). They showed a good correlation ( r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.

Pico-CSIA: Picomolar Scale Compound-Specific Isotope Analyses

Science.gov (United States)

Baczynski, A. A.; Polissar, P. J.; Juchelka, D.; Schwieters, J. B.; Hilkert, A.; Freeman, K. H.

2016-12-01

The basic approach to analyzing molecular isotopes has remained largely unchanged since the late 1990s. Conventional compound-specific isotope analyses (CSIA) are conducted using capillary gas chromatography (GC), a combustion interface, and an isotope-ratio mass spectrometer (IRMS). Commercially available GC-IRMS systems are comprised of components with inner diameters ≥0.25 mm and employ helium flow rates of 1-4 mL/min. These flow rates are an order of magnitude larger than what the IRMS can accept. Consequently, ≥90% of the sample is lost through the open split, and 1-10s of nanomoles of carbon are required for analysis. These sample requirements are prohibitive for many biomarkers, which are often present in picomolar concentrations. We utilize the resolving power and low flows of narrow-bore capillary GC to improve the sensitivity of CSIA. Narrow bore capillary columns (<0.25 mm ID) allow low helium flow rates of ≤0.5mL/min for more efficient sample transfer to the ion source of the IRMS while maintaining the high linear flow rates necessary to preserve narrow peak widths ( 250 ms). The IRMS has been fitted with collector amplifiers configured to 25 ms response times for rapid data acquisition across narrow peaks. Previous authors (e.g., Sacks et al., 2007) successfully demonstrated improved sensitivity afforded by narrow-bore GC columns. They reported an accuracy and precision of 1.4‰ for peaks with an average width at half maximum of 720 ms for 100 picomoles of carbon on column. Our method builds on their advances and further reduces peak widths ( 600 ms) and the amount of sample lost prior to isotopic analysis. Preliminary experiments with 100 picomoles of carbon on column show an accuracy and standard deviation <1‰. With further improvement, we hope to demonstrate robust isotopic analysis of 10s of picomoles of carbon, more than 2 orders of magnitude lower than commercial systems. The pico-CSIA method affords high-precision isotopic analyses for

ANALYSIS AND IDENTIFICATION SPIKING CHEMICAL COMPOUNDS RELATED TO CHEMICAL WEAPON CONVENTION IN UNKNOWN WATER SAMPLES USING GAS CHROMATOGRAPHY AND GAS CHROMATOGRAPHY ELECTRON IONIZATION MASS SPECTROMETRY

Directory of Open Access Journals (Sweden)

Harry Budiman

2010-06-01

Full Text Available The identification and analysis of chemical warfare agents and their degradation products is one of important component for the implementation of the convention. Nowadays, the analytical method for determination chemical warfare agent and their degradation products has been developing and improving. In order to get the sufficient analytical data as recommended by OPCW especially in Proficiency Testing, the spiking chemical compounds related to Chemical Weapon Convention in unknown water sample were determined using two different techniques such as gas chromatography and gas chromatography electron-impact ionization mass spectrometry. Neutral organic extraction, pH 11 organic extraction, cation exchanged-methylation, triethylamine/methanol-silylation were performed to extract the chemical warfare agents from the sample, before analyzing with gas chromatography. The identification of chemical warfare agents was carried out by comparing the mass spectrum of chemicals with mass spectrum reference from the OPCW Central Analytical Database (OCAD library while the retention indices calculation obtained from gas chromatography analysis was used to get the confirmation and supported data of  the chemical warfare agents. Diisopropyl methylphosphonate, 2,2-diphenyl-2-hydroacetic acid and 3-quinuclidinol were found in unknown water sample. Those chemicals were classified in schedule 2 as precursor or reactant of chemical weapons compound in schedule list of Chemical Weapon Convention.   Keywords: gas chromatography, mass spectrometry, retention indices, OCAD library, chemical warfare agents

Frontal and band displacement chromatography of the hydrogen isotopes on palladium; Chromatographies frontale et de deplacement de bande des isotopes de l'hydrogene sur palladium

Energy Technology Data Exchange (ETDEWEB)

Botter, F.; Menes, J.; Tistchenko, S.; Dirian, G. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1964-07-01

As a result of hydrogen isotope separations which we have carried out on supports containing palladium, we believe that we can now make a double contribution, theoretical and experimental, to the work which has already been published in this field. From the fundamental point of view we have developed and studied the validity of a simple model, in our particular case of a separation coefficient {alpha} which is very different to unity. This model, which is of a counter-current isotopic exchange, neglects the longitudinal diffusion in the gas phase and the lateral diffusion in the adsorbed phase and only takes into account the surface resistance to exchange between the phases. It is therefore possible to estimate the efficiency of a chromatography column in terms of the height equivalent of a theoretical plate (HETP). The slight differences observed between the actual chromatograms and the simple model justify both the research undertaken into a more complex model taking into account the diffusion, and the adoption of a simple model for comparing the efficiency of several columns. We describe also a new and simple graphical method for deducing the number of theoretical plates of a column in chromatograms of the frontal and band displacement types. Experimentally we give in particular the criteria for the validity of the model used, the law as a function of the {sup {alpha}}H{sub 2}-HD temperature, the study of the HETP as a function of the various parameters on several palladium containing supports, and the possibilities of an application to preparative chromatography. (authors) [French] Grace aux separations des isotopes de l'hydrogene que nous avons realisees sur masses palladiees, nous pensons apporter aux etudes precedemment publiees dans ce domaine, une double contribution, theorique et experimentale. Du point de vue fondamental, on a developpe et etudie la validite d'un modele simple, dans notre cas particulier d'un coefficient de separation

Simplified simulation of multicomponent isotope separation by gas centrifuge

International Nuclear Information System (INIS)

Guo Zhixiong; Ying Chuntong

1995-01-01

The expressions of diffusion equation for multicomponent isotope separation by gas centrifuge are derived by utilizing the simplified diffusion transport vector. A method of radial averaging which was restricted to a binary mixture is extended to multicomponent isotope mixtures by using an iterative scheme. A numerical analysis of tetradic UF 6 or SF 6 gas isotope separation by centrifuge is discussed when a special model of velocity distribution is given. The dependence of mutual separation factor for the components on their molecular weights' difference is obtained. Some aspects of the given model of gas fluid are also discussed

The isotopic record of Northern Hemisphere atmospheric carbon monoxide since 1950: implications for the CO budget

Directory of Open Access Journals (Sweden)

Z. Wang

2012-05-01

Full Text Available We present a 60-year record of the stable isotopes of atmospheric carbon monoxide (CO from firn air samples collected under the framework of the North Greenland Eemian Ice Drilling (NEEM project. CO concentration, δ¹³C, and δ¹⁸O of CO were measured by gas chromatography/isotope ratio mass spectrometry (gc-IRMS from trapped gases in the firn. We applied LGGE-GIPSA firn air models (Witrant et al., 2011 to correlate gas age with firn air depth and then reconstructed the trend of atmospheric CO and its stable isotopic composition at high northern latitudes since 1950. The most probable firn air model scenarios show that δ¹³C decreased slightly from −25.8‰ in 1950 to −26.4‰ in 2000, then decreased more significantly to −27.2‰ in 2008. δ¹⁸O decreased more regularly from 9.8‰ in 1950 to 7.1‰ in 2008. Those same scenarios show CO concentration increased gradually from 1950 and peaked in the late 1970s, followed by a gradual decrease to present day values (Petrenko et al., 2012. Results from an isotope mass balance model indicate that a slight increase, followed by a large reduction, in CO derived from fossil fuel combustion has occurred since 1950. The reduction of CO emission from fossil fuel combustion after the mid-1970s is the most plausible mechanism for the drop of CO concentration during this time. Fossil fuel CO emissions decreased as a result of the implementation of catalytic converters and the relative growth of diesel engines, in spite of the global vehicle fleet size having grown several fold over the same time period.

Potential of using stable nitrogen isotope ratio measurements to resolve fuel and thermal NOx in coal combustion

Energy Technology Data Exchange (ETDEWEB)

Chenggong Sun; Janos Lakatos; Colin E. Snape; Tony Fallick [University of Nottingham, Nottingham (United Kingdom). School of Chemical, Environmental and Mining Engineering (SChEME)

2003-07-01

In order to examine the potential of applying isotopic analysis to apportion NOx formation from different mechanisms, stable nitrogen isotope ratio measurements have been conducted on a number of thermal/prompt (diesel) and actual (coal) PF NO samples generated from a 1MW test facility at Powergen (UK), together with measurements on a range of pyrolysis and combustion chars obtained from a drop-tube reactor. A highly effective nitrogen-free sorbent, derived from white sugar with Mn as promoter, has been developed using an innovative procedure. This adsorbent has facilitated, for the first time, the determination of {delta}{sup 15}N values without background corrections. The isotopic data indicate that the thermal/prompt NOx collected during start-up with diesel as fuel has a {delta}{sup 15}N of close to 6.5(per thousand) compared to +15(per thousand) for the actual PF sample analysed. Thus, differences of up to ca. 20(per thousand) have been found to exist between thermal and PF fuel (char) NOx isotopic values. This augurs very well for the further development of the approach in order to help quantify the extent of thermal/prompt NOx formation in PF combustion. Measurements on chars have indicated that the extent of isotopic fractionation that occurs between coal-N and NOx from char is related to the reactivity of coals. Further, it would appear that much of the isotopic fractionation that occurs between coal nitrogen and fuel NO arises in the formation of char, although further fractionation can be inferred to occur during char combustion. In contrast, a lesser degree of isotopic fractionation is associated with the formation of thermal NO (ca. 6(per thousand)), atmospheric nitrogen having a value of 0(per thousand). 4 refs., 6 tabs.

Natural gas reburning technology for NOx reduction from MSW combustion systems

International Nuclear Information System (INIS)

Penterson, C.A.; Abbasi, H.; Khinkis, M.J.; Wakamura, Y.; Linz, D.G.

1990-01-01

A technology for reducing emissions from municipal solid waste combustion systems through advanced combustion techniques is being developed. Pilot testing of natural gas reburning was first performed in the Institute of Gas Technology's pilot-scale furnace under conditions simulating the firing of 1.7 x 10 6 Btu/hr (0.5 MWth) of MSW. Pilot testing then continued in Riley Stoker Corporation's 3 x 10 6 Btu/hr (0.88 MWth), 7 ton/day, pilot-scale MSW combustor using actual MSW in both test series, injection of up to 15% (HHV basis) natural gas reduced NO, by 50--70% while maintaining or improving combustion efficiency as measured by CO and hydrocarbon emissions and temperature stability. This paper will review the test results and discuss the status of the full-scale field demonstration testing that is planned for 1990

Carbon and hydrogen isotopic evidence for the origin of combustible gases in water-supply wells in north-central Pennsylvania

Science.gov (United States)

Révész, K. M.; Breen, K.J.; Baldassare, A.J.; Burruss, R.C.

2010-01-01

The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH4) and ethane (C2H6) and microbial CH4 were found. Microbial CH4 is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ13C values of CH4 and C2H6 for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C2H6 with microbial CH4 and a range of C and H isotopic compositions of CH4 indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.

Study of radiolysis products of natural organic materials by means of gas chromatography

International Nuclear Information System (INIS)

Pogocki, D.

1994-01-01

Analytical methods based on gas chromatography for identification determination of products arising during food irradiation have been presented. Behind the classics version of the methods one has shown also combined methods being the on-line connection of gas chromatography with mass spectroscopy as well as gas chromatography with liquid chromatography and mass spectroscopy. The applicability as well as weakness and advantages of each version have been discussed on the context of food irradiation. 11 refs, 7 figs

Analysis of oxygen-enhanced combustion of gas power cycle

Energy Technology Data Exchange (ETDEWEB)

Maidana, Cristiano Frandalozo; Carotenuto, Adriano; Schneider, Paulo Smith [Universidade Federal do Rio Grande do Sul (GESTE/UFRGS), Porto Alegre, RS (Brazil). Grupo de Estudos Termicos e Energeticos], E-mails: cristiano.maidana@ufrgs.br, pss@mecanica.ufrgs.br

2010-07-01

The majority of combustion processes use air as oxidant, roughly taken as 21% O{sub 2} and 79% N{sub 2}, by volume. In many cases, these processes can be enhanced by using an oxidant that contains higher proportion of O{sub 2} than in air. This is known as oxygen-enhanced combustion or OEC, and can bring important benefits like higher thermal efficiencies, lower exhaust gas volumes, higher heat transfer efficiency, reduction fuel consumption, reduced equipment costs and substantially pollutant emissions reduction. Within this scenario, this paper aims to investigate the influence of 21-30% oxygen concentration on the performance of a air-fired natural gas fueled power plant. This power plant operates under a Brayton cycle with models with the help of an air flow splitter after the compressor output in order to dose the oxygen rate of combustion and to keep the flue gas intake of the turbine at a prescribed temperature. Simulations shows that the enhancing of the oxidant stream reduced fuel consumption of about 10%, driven by higher adiabatic flame temperatures, which improves thermal and heat transfer efficiencies. A conclusion obtained is that the use of oxygen in higher proportions can be a challenge to retrofit existing air-fired natural gas power turbine cycles, because of the technological limitation of its materials with higher flame temperatures. (author)

The Combination of Internal-Combustion Engine and Gas Turbine

Science.gov (United States)

Zinner, K.

1947-01-01

While the gas turbine by itself has been applied in particular cases for power generation and is in a state of promising development in this field, it has already met with considerable success in two cases when used as an exhaust turbine in connection with a centrifugal compressor, namely, in the supercharging of combustion engines and in the Velox process, which is of particular application for furnaces. In the present paper the most important possibilities of combining a combustion engine with a gas turbine are considered. These "combination engines " are compared with the simple gas turbine on whose state of development a brief review will first be given. The critical evaluation of the possibilities of development and fields of application of the various combustion engine systems, wherever it is not clearly expressed in the publications referred to, represents the opinion of the author. The state of development of the internal-combustion engine is in its main features generally known. It is used predominantly at the present time for the propulsion of aircraft and road vehicles and, except for certain restrictions due to war conditions, has been used to an increasing extent in ships and rail cars and in some fields applied as stationary power generators. In the Diesel engine a most economical heat engine with a useful efficiency of about 40 percent exists and in the Otto aircraft engine a heat engine of greatest power per unit weight of about 0.5 kilogram per horsepower.

Device for flame combustion of liquid or solid samples in radioactive isotope trace indication

International Nuclear Information System (INIS)

Kaartinen, N.H.

1979-01-01

The plant or animal tissue containing T and/or 14 C isotope indicator is in a small ignition cage within the combustion chamber. The ignition cage consists of Nichrome which supports the ignition procedure. The combustion chamber is maintained at a temperature above the condensation temperature of the vapours escaping from the tissue (e.g. H 2 O). The thimble type ignition cage burns uniformly together with the sample. It is no longer necessary to make pellets of the sample. (DG) [de

Determination of gamma-aminobutyric acid in food matrices by isotope dilution hydrophilic interaction chromatography coupled to mass spectrometry.

Science.gov (United States)

Zazzeroni, Raniero; Homan, Andrew; Thain, Emma

2009-08-01

The estimation of the dietary intake of gamma-aminobutyric acid (GABA) is dependent upon the knowledge of its concentration values in food matrices. To this end, an isotope dilution liquid chromatography-mass spectrometry method has been developed employing the hydrophilic interaction chromatography technique for analyte separation. This approach enabled accurate quantification of GABA in apple, potato, soybeans, and orange juice without the need of a pre- or post-column derivatization reaction. A selective and precise analytical measurement has been obtained with a triple quadrupole mass spectrometer operating in multiple reaction monitoring using the method of standard additions and GABA-d(6) as an internal standard. The concentrations of GABA found in the matrices tested are 7 microg/g of apple, 342 microg/g of potatoes, 211 microg/g of soybeans, and 344 microg/mL of orange juice.

A novel methylation derivatization method for δ(18)O analysis of individual carbohydrates by gas chromatography/pyrolysis-isotope ratio mass spectrometry.

Science.gov (United States)

Lehmann, Marco M; Fischer, Maria; Blees, Jan; Zech, Michael; Siegwolf, Rolf T W; Saurer, Matthias

2016-01-15

The oxygen isotope ratio (δ(18)O) of carbohydrates derived from animals, plants, sediments, and soils provides important information about biochemical and physiological processes, past environmental conditions, and geographical origins, which are otherwise not available. Nowadays, δ(18)O analyses are often performed on carbohydrate bulk material, while compound-specific δ(18)O analyses remain challenging and methods for a wide range of individual carbohydrates are rare. To improve the δ(18)O analysis of individual carbohydrates by gas chromatography/pyrolysis-isotope ratio mass spectrometry (GC/Pyr-IRMS) we developed a new methylation derivatization method. Carbohydrates were fully methylated within 24 h in an easy-to-handle one-pot reaction in acetonitrile, using silver oxide as proton acceptor, methyl iodide as methyl group carrier, and dimethyl sulfide as catalyst. The precision of the method ranged between 0.12 and 1.09‰ for the δ(18)O values of various individual carbohydrates of different classes (mono-, di-, and trisaccharides, alditols), with an accuracy of a similar order of magnitude, despite high variation in peak areas. Based on the δ(18)O values of the main isomers, important monosaccharides such as glucose and fructose could also be precisely analyzed for the first time. We tested the method on standard mixtures, honey samples, and leaf carbohydrates extracted from Pinus sylvestris, showing that the method is also applicable to different carbohydrate mixtures. The new methylation method shows unrivalled accuracy and precision for δ(18)O analysis of various individual carbohydrates; it is fast and easy-to-handle, and may therefore find wide-spread application. Copyright © 2015 John Wiley & Sons, Ltd.

A reliable compound-specific nitrogen isotope analysis of amino acids by GC-C-IRMS following derivatisation into N-pivaloyl-iso-propyl (NPIP)esters for high-resolution food webs estimation.

Science.gov (United States)

Zhang, Zhongyi; Tian, Jing; Xiao, Hongwei; Zheng, Nengjian; Gao, Xiaofei; Zhu, Renguo; Xiao, Huayun

2016-10-15

The signatures of natural stable nitrogen isotopic composition (δ(15)N) of individual amino acid (AA) have been confirmed to be a potentially effective tool for elucidating nitrogen cycling and trophic position of various organisms in food webs. In the present study, a two-stage derivatisation approach of esterification followed by acylation was evaluated. The biological samples underwent acid hydrolysis and the released individual AA was derivatived into corresponding N-pivaloyl-isopropyl (NPIP) esters for nitrogen isotopic analysis in gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Usually, 13 individual AA derivatives were separated with fine baseline resolution based on a nonpolar gas chromatography column (DB-5ms). The minimum sample amount required under the presented conditions is larger than 20ngN on column in order to accurately determine the δ(15)N values. The δ(15)N values determined by GC-C-IRMS with a precision of better than 1‰, were within 1‰ after empirical correction compared to the corresponding measured by element analysis (EA)-IRMS. Bland-Altman plot showed highly consistency of the δ(15)N values determined by the two measurement techniques. Cation-exchange chromatography was applied to remove interfering fraction from the extracts of plant and animal samples and without nitrogen isotope fractionation during the treatment procedure. Moreover, this approach was carried out to estimate the trophic level of various natural organisms in a natural lake environment. Results highly proved that the trophic level estimated via the presented AA method well reflected the actual food web structure in natural environments. Copyright © 2016 Elsevier B.V. All rights reserved.

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part III: 2,5-Dimethylfuran.

Science.gov (United States)

Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2014-03-01

This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model.

Device to remove hydrogen isotopes from a gas phase

International Nuclear Information System (INIS)

Morlock, G.; Wiesemes, J.; Bachner, D.

1977-01-01

The device described here guarantees the selective removal of hydrogen isotopes from gas phases in order to prevent the occurence of explosive H 2 gas mixtures, or to separate off radioactive tritium in nuclear plants from the gas phase. It consists of a closed container whose walls are selectively penetrable by hydrogen isotopes. It is simultaneously filled compactly and presssure-resistant with a metal bulk (e.g. powder, sponges or the like of titanium or other hydrogen isotope binding metal). Walling and bulk are maintained at suitable working temperatures by means of a system according to the Peltier effect. The whole thing is safeguarded by protective walling. (RB) [de

Computational fluid dynamics (CFD) analysis of the combustion process of a leather residuals gasification fuel gas: influence of fuel moisture content

Energy Technology Data Exchange (ETDEWEB)

Antonietti, Anderson Jose; Beskow, Arthur Bortolin; Silva, Cristiano Vitorino da [Universidade Regional Integrada do Alto Uruguai e das Missoes (URI), Erechim, RS (Brazil)], E-mails: arthur@uricer.edu.br, mlsperb@unisinos.br; Indrusiak, Maria Luiza Sperb [Universidade do Vale do Rio dos Sinos (UNISINOS), Sao Leopoldo, RS (Brazil)], E-mail: cristiano@uricer.edu.br

2010-07-01

This work presents a numerical study of the combustion process of leather residuals gasification gas, aiming the improvement of the process efficiency, considering different concentrations of water on the gas. The heating produced in this combustion process can be used to generation of thermal and/or electrical energy, for use at the leather industrial plant. However, the direct burning of this leather-residual-gas into the chambers is not straightforward. The alternative in development consists in processing this leather residuals by gasification or pyrolysis, separating the volatiles and products of incomplete combustion, for after use as fuel in a boiler. At these processes, different quantities of water can be used, resulting at different levels of moisture content in this fuel gas. This humidity can affect significantly the burning of this fuel, producing unburnt gases, as the carbon monoxide, or toxic gases as NOx, which must have their production minimized on the process, with the purpose of reducing the emission of pollutants to the atmosphere. Other environment-harmful-gases, remaining of the chemical treatment employed at leather manufacture, as cyanide, and hydrocarbons as toluene, must burn too, and the moisture content has influence on it. At this way, to increase understanding of the influence of moisture in the combustion process, it was made a numerical investigation study of reacting flow in the furnace, evaluating the temperature field, the chemical species concentration fields, flow mechanics and heat transfer at the process. The commercial CFD code CFX Ansys Inc. was used. Considering different moisture contents in the fuel used on the combustion process, with this study was possible to achieve the most efficient burning operation parameters, with improvement of combustion efficiency, and reduction of environmental harmful gases emissions. It was verified that the different moisture contents in the fuel gas demand different operation conditions

Gas phase adsorption technology for nitrogen isotope separation and its feasibility for highly enriched nitrogen gas production

International Nuclear Information System (INIS)

Inoue, Masaki; Asaga, Takeo

2000-04-01

Highly enriched nitrogen-15 gas is favorable to reduce radioactive carbon-14 production in reactor. The cost of highly enriched nitrogen-15 gas in mass production is one of the most important subject in nitride fuel option in 'Feasibility Study for FBR and Related Fuel Cycle'. In this work gas phase adsorption technology was verified to be applicable for nitrogen isotope separation and feasible to produce highly enriched nitrogen-15 gas in commercial. Nitrogen isotopes were separated while ammonia gas flows through sodium-A type zeolite column using pressure swing adsorption process. The isotopic ratio of eight samples were measured by high resolution mass spectrometry and Fourier transform microwave spectroscopy. Gas phase adsorption technology was verified to be applicable for nitrogen isotope separation, since the isotopic ratio of nitrogen-15 and nitrogen-14 in samples were more than six times as high as in natural. The cost of highly enriched nitrogen-15 gas in mass production were estimated by the factor method. It revealed that highly enriched nitrogen-15 gas could be supplied in a few hundred yen per gram in mass production. (author)

Separation of uranium isotopes by gas centrifugation

International Nuclear Information System (INIS)

Jordan, I.

1980-05-01

The uranium isotope enrichment is studied by means of the countercurrent gas centrifuge driven by thermal convection. A description is given of (a) the transfer and purification of the uranium hexafluoride used as process gas in the present investigation; (b) the countercurrent centrifuge ZG3; (c) the system designed for the introduction and extraction of the process gas from the centrifuge; (d) the measurement of the process gas flow rate through the centrifuge; (e) the determination of the uranium isotopic abundance by mass spectrometry; (f) the operation and mechanical behavior of the centrifuge and (g) the isotope separation experiments, performed, respectively, at total reflux and with production of enriched material. The results from the separation experiments at total reflux are discussed in terms of the enrichment factor variation with the magnitude and flow profile of the countercurrent given by the temperature difference between the rotor covers. As far as the separation experiments with production are concerned, the discussion of their results is presented through the variation of the enrichment factor as a function of the flow rate, the observed asymmetry of the process and the calculated separative power of the centrifuge. (Author) [pt

Evaluation technology for burnup and generated amount of plutonium by measurement of Xenon isotopic ratio in dissolver off-gas at reprocessing facility (Joint research)

International Nuclear Information System (INIS)

Okano, Masanori; Kuno, Takehiko; Shirouzu, Hidetomo; Yamada, Keiji; Sakai, Toshio; Takahashi, Ichiro; Charlton, William S.; Wells, Cyndi A.; Hemberger, Philip H.

2006-12-01

The amount of Pu in the spent fuel was evaluated from Xe isotopic ratio in off-gas in reprocessing facility, is related to burnup. Six batches of dissolver off-gas (DOG) at spent fuel dissolution process were sampled from the main stack in Tokai Reprocessing Plant (TRP) during BWR fuel (approx. 30GWD/MTU) reprocessing campaign. Xenon isotopic ratio was determined with Gas Chromatography/Mass Spectrometry. Burnup and generated amount of Pu were evaluated with Noble Gas Environmental Monitoring Application code (NOVA), developed by Los Alamos National Laboratory. Inferred burnup evaluated by Xe isotopic measurements and NOVA were in good agreement with those of the declared burnup in the range from -3.8% to 7.1%. Also, the inferred amount of Pu in spent fuel was in good agreed with those of the declared amount of Pu calculated by ORIGEN code in the range from -0.9% to 4.7%. The evaluation technique is applicable for both burnup credit to achieve efficient criticality safety control and a new measurement method for safeguards inspection. (author)

Gas permeation process for post combustion CO2 capture

International Nuclear Information System (INIS)

Pfister, Marc

2017-01-01

CO 2 Capture and Storage (CCS) is a promising solution to separate CO 2 from flue gas, to reduce the CO 2 emissions in the atmosphere, and hence to reduce global warming. In CCS, one important constraint is the high additional energy requirement of the different capture processes. That statement is partly explained by the low CO 2 fraction in the inlet flue gas and the high output targets in terms of CO 2 capture and purity (≥90%). Gas permeation across dense membrane can be used in post combustion CO 2 capture. Gas permeation in a dense membrane is ruled by a mass transfer mechanism and separation performance in a dense membrane are characterized by component's effective permeability and selectivity. One of the newest and encouraging type of membrane in terms of separation performance is the facilitated transport membrane. Each particular type of membrane is defined by a specific mass transfer law. The most important difference to the mass transfer behavior in a dense membrane is related to the facilitated transport mechanism and the solution diffusion mechanism and its restrictions and limitations. Permeation flux modelling across a dense membrane is required to perform a post combustion CO 2 capture process simulation. A CO 2 gas permeation separation process is composed of a two-steps membrane process, one drying step and a compression unit. Simulation on the energy requirement and surface area of the different membrane modules in the global system are useful to determine the benefits of using dense membranes in a post combustion CO 2 capture technology. (author)

Isotope-dilution gas chromatography-mass spectrometry coupled with injection-port butylation for the determination of 4-t-octylphenol, 4-nonylphenols and bisphenol A in human urine.

Science.gov (United States)

Chung, Shuang-Hung; Ding, Wang-Hsien

2018-02-05

An analytical method that utilizes isotope-dilution gas chromatography-mass spectrometry (ID-GC-MS) coupled with injection-port butylation was developed. The method was validated, and confirmed to be able to determine the presence of three commonly detected endocrine-disrupting chemicals (EDCs: 4-tert-octylphenol (4-t-OP), 4-nonylphenols (4-NPs) and bisphenol A (BPA)) in human urine with high precision and accuracy. After sample preparation by solid-phase extraction, the extract was introduced into GC-MS via injection-port butylation. The butylated target analytes were identified and quantified by using ion-trap mass spectrometry operating in the selected-ion-storage mode, and employing the measurement of peak area ratios of the butylated target analytes and labeled-analogues in the samples and calibration standards. The labeled-analogues were also used to correct the variations associated with the analysis and matrix effect. The limits of quantitation (LOQs) ranged from 0.1 to 0.3ng/mL. High precisions for both intra- and inter-day analysis ranged from 1 to 6%, and excellent accuracy (mean recovery) ranged from 92 to 105% on two concentration levels. In human urine, the total concentrations of three selected EDCs varied from 1.28 to 7.14ng/mL. 4-NPs were detected within all collected samples. The developed method allows accurate analysis of trace-level of EDCs in urine, and these target EDCs could act as useful biomarkers to assess exposure in biomonitoring studies and programs. Copyright © 2017 Elsevier B.V. All rights reserved.

Iodine release from sodium pool combustion

International Nuclear Information System (INIS)

Sagawa, N.; Fukushima, Y.; Yokota, N.; Akagane, K.; Mochizuki, K.

1979-01-01

Iodine release associated with sodium pool combustion was determined by heating 20 gr sodium containing sodium iodide, which was labelled with 131 I and dissolved in the sodium in concentration of 1∼1,000 ppm, to burn on a nickel crucible in conditioned atmosphere in a closed vessel of 0.4 m 3 . Oxygen concentration was changed in 5∼21% and humidity in 0∼89% by mixing nitrogen gas and air. Combustion products were trapped by a Maypack filter composed of particle filters, copper screens and activated charcoal beds and by a glass beads pack cooled by liquid argon. Iodine collected on these filter elements was determined by radio-gas chromatography. When the sodium sample burned in the atmosphere of air at room temperature, the release fractions observed were 6∼33% for sodium and 1∼20% for iodine added in the sodium. The release iodine was present in aerosol at a ratio of 98%, and the remainder in the gas form. The release fraction of iodine trended to decrease as oxygen concentration and humidity in the atmosphere increased. No organic iodide was detected in the combustion products. (author)

Effluents of toxic and corrosion-active components at coke-oven gas combustion

International Nuclear Information System (INIS)

Mikhajlov, G.S.; Afanas'ev, Yu.O.; Plotnikov, V.A.; Iskhakov, Kh.A.; Tikhov, S.D.; Gaus, A.I.; Nagibin, P.D.

1996-01-01

Various modes of coke-coal gas combustion are studied and dependence of concentration of nitrogen sulfur oxides and carbon monoxides originating in smoke gases on the air excess delivered to the combustion chamber is determined. The lowest summary releases of hazardous substances are achieved by the excess air coefficients α > 1.2 relative to modes of coke-coal gas combustion with smoke gases recirculation. The quantity of sulfur does not depend on the mode of fuel combustion and is determined by the total sulfur content in the fuel. To prevent the corrosion of low-temperature heat exchange surfaces it is necessary to heat up the feed-water up to the temperature exceeding the temperature of the coal gases dew point by 10-15 deg C. 10 refs

Evaluation of the Discriminative Potential of a Novel Biomarker for Estradiol Treatments in Bovine Animals

NARCIS (Netherlands)

Regal, P.; Blokland, M.H.; Fente, C.A.; Sterk, S.S.; Cepeda, A.; Ginkel, van L.A.

2015-01-01

The endogenous occurrence of natural hormones obstructs the application of classical targeted methods as confirmatory options. In the case of estradiol, the ultimate confirmation of its exogenous administration relies on gas chromatography coupled to combustion/isotope ratio mass spectrometry

Bacteria and fungi respond differently to multifactorial climate change in a temperate heathland, traced with ¹³C-Glycine and FACE CO₂

DEFF Research Database (Denmark)

Andresen, Louise C.; Dungait, Jennifer A.J.; Bol, Roland

2014-01-01

PLFAs for specific microbial groups (Gram positive bacteria, Gram negative bacteria, actinobacteria and fungi) was quantified using gas chromatography-combustion-stable isotope ratio mass spectrometry (GC-C-IRMS). Gram positive bacteria opportunistically utilized the freshly added glycine substrate, i...

Exhaust gas recirculation for advanced diesel combustion cycles

International Nuclear Information System (INIS)

Asad, Usman; Zheng, Ming

2014-01-01

Highlights: • Analysis of the incremental (cycle-by-cycle) build-up of EGR. • Proposed one-step equations for transient/steady-state gas concentration estimation. • Defined an in-cylinder excess-air ratio to account for the recycled oxygen with EGR. • Demonstrated the use of intake oxygen as a reliable measure of EGR effectiveness. • Demonstrated the impact of engine load and intake pressure on EGR effectiveness. - Abstract: Modern diesel engines tend to utilize significantly large quantities of exhaust gas recirculation (EGR) and high intake pressures across the engine load range to meet NOx targets. At such high EGR rates, the combustion process and exhaust emissions tend to exhibit a marked sensitivity to small changes in the EGR quantity, resulting in unintended deviations from the desired engine performance characteristics (energy efficiency, emissions, stability). An accurate estimation of EGR and its effect on the intake dilution are, therefore, necessary to enable its application during transient engine operation or unstable combustion regimes. In this research, a detailed analysis that includes estimation of the transient (cycle-by-cycle) build-up of EGR and the time (engine cycles) required to reach the steady-state EGR operation has been carried out. One-step global equations to calculate the transient and steady-state gas concentrations in the intake and exhaust are proposed. The effects of engine load and intake pressure on EGR have been examined and explained in terms of intake charge dilution and in-cylinder excess-air ratio. The EGR analysis is validated against a wide range of empirical data that include low temperature combustion cycles, intake pressure and load sweeps. This research intends to not only formulate a clear understanding of EGR application for advanced diesel combustion but also to set forth guidelines for transient analysis of EGR

New regulations, combustion, environment: responses for natural gas; Nouvelles reglementations, combustion, environnement: les reponses pour le gaz naturel

Energy Technology Data Exchange (ETDEWEB)

Le Peltier-Marc, A. [Gaz de France (GDF), 75 - Paris (France). Direction Commerciale

1997-12-31

The impacts of the new French regulations concerning low- to medium-power combustion equipment with regards to their energy sources, energy efficiency and pollution control, on natural gas fired boilers, are discussed: lower pollutant emission limits are set for SO{sub 2}, NO{sub x} and ashes. The decree gives new regulations concerning plant location, combustion control systems, plant monitoring and maintenance, and air pollution control measures such as chimney stack height and emission limits. The French national gas utility promotes environmental high performance boilers

Gas Chromatography-Mass Spectrometric Analysis and Insecticidal ...

African Journals Online (AJOL)

HP

Original Research Article. Gas Chromatography-Mass Spectrometric Analysis and ... into a natural fumigant/insecticide for the control of stored product insects. Keywords: Mallotus ..... stability as well as reduce cost. ACKNOWLEDGEMENT.

Environmental application of elemental speciation analysis based on liquid or gas chromatography hyphenated to inductively coupled plasma mass spectrometry-A review

International Nuclear Information System (INIS)

Popp, Maximilian; Hann, Stephan; Koellensperger, Gunda

2010-01-01

In recent years the number of environmental applications of elemental speciation analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. The analytical characteristics, such as extremely low detection limits (LOD) for almost all elements, the wide linear range, the possibility for multi-elemental analysis and the possibility to apply isotope dilution mass spectrometry (IDMS) make ICP-MS an attractive tool for elemental speciation analysis. Two methodological approaches, i.e. the combination of ICP-MS with high performance liquid chromatography (HPLC) and gas chromatography (GC), dominate the field. Besides the investigation of metals and metalloids and their species (e.g. Sn, Hg, As), representing 'classic' elements in environmental science, more recently other elements (e.g. P, S, Br, I) amenable to ICP-MS determination were addressed. In addition, the introduction of isotope dilution analysis and the development of isotopically labeled species-specific standards have contributed to the success of ICP-MS in the field. The aim of this review is to summarize these developments and to highlight recent trends in the environmental application of ICP-MS coupled to GC and HPLC.

Method and apparatus for isotope separation from a gas stream

International Nuclear Information System (INIS)

Szoke, A.

1978-01-01

A method and apparatus are described for isotope separation and in particular for separating the desired isotope from the gas in which it is contained by irradiating it with a laser. The laser selectively provides kinetic energy to the isotope through inelastic events, monomolecular or bimolecular, in order to cause it to segregate within or fly out of the gas stream in which it is contained

Biomass utilization for green environment: Co-combustion of diesel fuel and producer gas in thermal application

International Nuclear Information System (INIS)

Hussain, A.; Ani, F.N.; Mehamed, A.F.

2007-01-01

Study of co-combustion of diesel oil and producer gas from a gasifier, individually as well as combined, in an experimental combustion chamber revealed that the producer gas can be co-combusted with liquid fuel. The process produced more CO, NO/sub x/, SO/sub 2/ and CO/sub 2/ as compared to the combustion of diesel oil alone; the exhaust temperature for the process was higher than the diesel combustion alone. (author)

Combustion engineering

CERN Document Server

Ragland, Kenneth W

2011-01-01

Introduction to Combustion Engineering The Nature of Combustion Combustion Emissions Global Climate Change Sustainability World Energy Production Structure of the Book   Section I: Basic Concepts Fuels Gaseous Fuels Liquid Fuels Solid Fuels Problems Thermodynamics of Combustion Review of First Law Concepts Properties of Mixtures Combustion StoichiometryChemical EnergyChemical EquilibriumAdiabatic Flame TemperatureChemical Kinetics of CombustionElementary ReactionsChain ReactionsGlobal ReactionsNitric Oxide KineticsReactions at a Solid SurfaceProblemsReferences  Section II: Combustion of Gaseous and Vaporized FuelsFlamesLaminar Premixed FlamesLaminar Flame TheoryTurbulent Premixed FlamesExplosion LimitsDiffusion FlamesGas-Fired Furnaces and BoilersEnergy Balance and EfficiencyFuel SubstitutionResidential Gas BurnersIndustrial Gas BurnersUtility Gas BurnersLow Swirl Gas BurnersPremixed-Charge Engine CombustionIntroduction to the Spark Ignition EngineEngine EfficiencyOne-Zone Model of Combustion in a Piston-...

Impact of comprehensive two-dimensional gas chromatography with mass spectrometry on food analysis.

Science.gov (United States)

Tranchida, Peter Q; Purcaro, Giorgia; Maimone, Mariarosa; Mondello, Luigi

2016-01-01

Comprehensive two-dimensional gas chromatography with mass spectrometry has been on the separation-science scene for about 15 years. This three-dimensional method has made a great positive impact on various fields of research, and among these that related to food analysis is certainly at the forefront. The present critical review is based on the use of comprehensive two-dimensional gas chromatography with mass spectrometry in the untargeted (general qualitative profiling and fingerprinting) and targeted analysis of food volatiles; attention is focused not only on its potential in such applications, but also on how recent advances in comprehensive two-dimensional gas chromatography with mass spectrometry will potentially be important for food analysis. Additionally, emphasis is devoted to the many instances in which straightforward gas chromatography with mass spectrometry is a sufficiently-powerful analytical tool. Finally, possible future scenarios in the comprehensive two-dimensional gas chromatography with mass spectrometry food analysis field are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

10 CFR 50.44 - Combustible gas control for nuclear power reactors.

Science.gov (United States)

2010-01-01

... with Mark III type containments and all pressurized water reactors with ice condenser containments must... condenser containments that do not rely upon an inerted atmosphere inside containment to control combustible... containment atmosphere following a significant beyond design-basis accident for combustible gas control and...

Computational fluid dynamics (CFD) analysis of an industrial gas turbine combustion chamber

Energy Technology Data Exchange (ETDEWEB)

Anzai, Thiago Koichi; Fontes, Carlo Eduardo; Ropelato, Karolline [Engineering Simulation and Scientic Software Ltda. (ESSS), Rio de Janeiro, RJ (Brazil)], E-mails: anzai, carlos.fontes, ropelato@esss.com.br; Silva, Luis Fernando Figueira da; Huapaya, Luis Enrique Alva [Pontificia Universidade Catolica do Rio de Janeiro (PUC-Rio), RJ (Brazil). Dept. of Mechanical Engineering], E-mail: luisfer.luisalva@esp.puc-rio.br

2010-07-01

The accurate determination of pollutant emission from gas turbine combustors is a crucial problem in situations when such equipment is subject to long periods of operation away from the design point. In such operating conditions, the flow field structure may also drastically differ from the design point one, leading to the presence of undesirable hot spots or combustion instabilities, for instance. A priori experiments on all possible operation conditions is economically unfeasible, therefore, models that allow for the prediction of combustion behavior in the full operation range could be used to instruct power plant operators on the best strategies to be adopted. Since the direct numerical simulation of industrial combustors is beyond reach of the foreseeable computational resources, simplified models should be used for such purpose. This works presents the results of the application to an industrial gas turbine combustion chamber of the CFD technique to the prediction of the reactive flow field. This is the first step on the coupling of reactive CFD results with detailed chemical kinetics modeling using chemical reactor networks, toward the goal of accurately predicting pollutant emissions. The CFD model considers the detailed geometrical information of such a combustion chamber and uses actual operating conditions, calibrated via an overall gas turbine thermodynamical simulation, as boundary conditions. This model retains the basic information on combustion staging, which occurs both in diffusion and lean premixed modes. The turbulence has been modeled using the SST-CC model, which is characterized by a well established regime of accurate predictive capability. Combustion and turbulence interaction is accounted for by using the Zimont et al. model, which makes use of on empirical expression for the turbulent combustion velocity for the closure of the progress variable transport equation. A high resolution scheme is used to solve the advection terms of the

Gas Chromatography-Mass Spectrometric Analysis of Nematicidal ...

African Journals Online (AJOL)

Gas Chromatography-Mass Spectrometric Analysis of Nematicidal Essential Oil of Valeriana ... Tropical Journal of Pharmaceutical Research ... have a potential to be developed to natural nematicides for the control of cereal cyst nematodes.

13 C analysis of aromas and perfumes by a coupled GC-IRMS technique. The case of vanillin and leaf alcohol extracts

International Nuclear Information System (INIS)

Breas, O.; Fourel, F.; Martin, G.J.

1994-01-01

The determination of stable isotope ratios is a precious tool to establish the natural status of flavors and fragrances. Results are presented concerning δ 13 C measurements using gas chromatography-combustion interface-isotope ratio mass spectrometry (GC-C- 13 C IRMS). This technique allows to measure carbon isotope ratios on pure compounds separated by capillary gas chromatography and injected on-line into an isotopic mass spectrometer. δ 13 C measurements carried out on vanilla extracts require only very small quantities of compounds ( 13 C measurements performed on cis-3-hexanol extracted from mint, the difference between natural and synthetic cis-3-hexanol is underlined and it is demonstrated that reproducible isotope ratios may be measured for cis-3-hexanol on mint extracts without purification even if this compound only represents 0.5% of the extract. (authors). 17 refs., 1 fig., 3 tabs

Accuracy improvement of the modified EDM model for non-premixed turbulent combustion in gas turbine

Directory of Open Access Journals (Sweden)

Qiong Li

2015-09-01

Full Text Available Eight bluff body and swirl turbulent diffusion flames resembling the flow field and combustion inside gas turbine combustors are simulated and the simulation results are compared with experimental data. It is revealed that the original modified EDM model could not predict the temperature profile accurately. A more accurate model is developed and validated for gas turbine combustion application. However, this model under predicts the flame temperature for the regular round jet flames indicating that no universal form of the modified EDM model could be achieved for the combustion simulation of both gas furnaces and gas turbines.

Utilization and mitigation of VAM/CMM emissions by a catalytic combustion gas turbine

Energy Technology Data Exchange (ETDEWEB)

Tanaka, K.; Yoshino, Y.; Kashihara, H. [Kawasaki Heavy Industries Ltd., Hyougo (Japan); Kajita, S.

2013-07-01

A system configured with a catalytic combustion gas turbine generator unit is introduced. The system has been developed using technologies produced by Kawasaki Heavy Industries, Ltd., such as small gas turbines, recuperators and catalytic combustors, and catalytic oxidation units which use exhaust heat from gas turbines. The system combusts (oxidizes) ventilation air methane (less than 1% concentration) and low concentration coal mine methane (30% concentration or less) discharged as waste from coal mines. Thus, it cannot only reduce the consumption of high- quality fuel for power generation, but also mitigate greenhouse gas emissions.

Evaluation of reduced chemical kinetic mechanisms used for modeling mild combustion for natural gas

Directory of Open Access Journals (Sweden)

Hamdi Mohamed

2009-01-01

Full Text Available A numerical and parametric study was performed to evaluate the potential of reduced chemistry mechanisms to model natural gas chemistry including NOx chemistry under mild combustion mode. Two reduced mechanisms, 5-step and 9-step, were tested against the GRI-Mech3.0 by comparing key species, such as NOx, CO2 and CO, and gas temperature predictions in idealized reactors codes under mild combustion conditions. It is thus concluded that the 9-step mechanism appears to be a promising reduced mechanism that can be used in multi-dimensional codes for modeling mild combustion of natural gas.

Single-run determination of polybrominated diphenyl ethers (PBDEs) di- to deca-brominated in fish meal, fish oil and fish feed by isotope dilution: Application of automated sample purification and gas chromatography/ion trap tandem mass spectrometry (GC/ITMS)

International Nuclear Information System (INIS)

Blanco, Sonia Lucia; Vieites, Juan M.

2010-01-01

The present paper describes the application of automated cleanup and fractionation procedures of the Power Prep system (Fluid Management Systems) for the determination of polybrominated diphenyl ethers (PBDEs) in feeding stuffs and fish meal and oil. Gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITMS) allowed the analysis of di- to deca-BDEs in the samples matrices used in fish aquaculture. The method developed enabled the determination of 26 native PBDE congeners and 11 13 C 12 -labelled congeners, including deca-BDE 209, in a single-run analysis, using isotope dilution. The automated cleanup, consisting of a succession of multilayer silica and basic alumina columns previously applied by Wyrzykowska et al. (2009) in combustion flue gas, was succesfully applied in our complex matrices. The method allowed an increase in productivity, i.e. lower time was required to process samples, and simultaneous purification of several samples was achieved at a time, reducing analyst dedication and human error input. Average recoveries of 43-96% were obtained. GC/ITMS can overcome the complexity originating from the sample matrix, eliminating matrix effects by tandem MS, to enable the detection of congeners penta- to nona-BDEs where interferent masses were present. The provisional detection limits, estimated in the samples, were 5-30 pg for di-, tri-, tetra-, and penta-BDEs, 20-65 pg for hexa-, hepta-, octa- and nona-BDEs, and 105 pg for deca-BDE. Reduction of deca-BDE 209 blank values is of concern to ongoing research. Good accuracy was obtained by application of the whole procedure, representing an efficient, low-cost and fast alternative for routine analyses.

Gas Chromatography-Mass Spectrometric Analysis and Insecticidal ...

African Journals Online (AJOL)

Tropical Journal of Pharmaceutical Research ... apelta aerial parts was analyzed by gas chromatography/mass spectrometric (GC/MS) to determine its composition. ... into a natural fumigant/insecticide for the control of stored product insects.

Test plan for measuring ventilation rates and combustible gas levels in TWRS active catch tanks

Energy Technology Data Exchange (ETDEWEB)

NGUYEN, D.M.

1999-05-20

The purpose of this test is to provide an initial screening of combustible gas concentrations in catch tanks that currently are operated by Tank Waste Remediation System (TWRS). The data will be used to determine whether or not additional data will be needed for closure of the flammable gas unreviewed safety question for these facilities. This test will involve field measurements of ammonia, organic vapor, and total combustible gas levels in the headspace of the catch tanks. If combustible gas level in a tank exceeds an established threshold, gas samples will be collected in SUMMA canisters for more extensive laboratory analysis. In addition, ventilation rates of some catch tanks will be measured to evaluate removal of flammable gas by air flow through the tanks.

Test plan for measuring ventilation rates and combustible gas levels in RPP active catch tanks

Energy Technology Data Exchange (ETDEWEB)

NGUYEN, D.M.

1999-06-03

The purpose of this test is to provide an initial screening of combustible gas concentrations in catch tanks that currently are operated by River Protection Project (RPP). The data will be used to determine whether or not additional data will be needed for closure of the flammable gas unreviewed safety question for these facilities. This test will involve field measurements of ammonia, organic vapor, and total combustible gas levels in the headspace of the catch tanks. If combustible gas level in a tank exceeds an established threshold, gas samples will be collected in SUMMA canisters for more extensive laboratory analysis. In addition, ventilation rates of some catch tanks will be measured to evaluate removal of flammable gas by air flow through the tanks.

Numerical investigation of high temperature synthesis gas premixed combustion via ANSYS Fluent

Directory of Open Access Journals (Sweden)

Pashchenko Dmitry

2018-01-01

Full Text Available A numerical model of the synthesis gas pre-mixed combustion is developed. The research was carried out via ANSYS Fluent software. Verification of the numerical results was carried out using experimental data. A visual comparison of the flame contours that obtained by the synthesis gas combustion for Re = 600; 800; 1000 was performed. A comparison of the wall temperature of the combustion chamber, obtained with the help of the developed model, with the results of a physical experiment was also presented. For all cases, good convergence of the results is observed. It is established that a change in the temperature of the syngas/air mixture at the inlet to the combustion chamber does not significantly affect the temperature of the combustion products due to the dissipation of the H2O and CO2 molecules. The obtained results are of practical importance for the design of heat engineering plants with thermochemical heat recovery.

Hydrogen isotope exchange in a metal hydride tube

Energy Technology Data Exchange (ETDEWEB)

Robinson, David B. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

2014-09-01

This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

Isotopic mass-dependence of noble gas diffusion coefficients inwater

Energy Technology Data Exchange (ETDEWEB)

Bourg, I.C.; Sposito, G.

2007-06-25

Noble gas isotopes are used extensively as tracers inhydrologic and paleoclimatic studies. These applications requireknowledge of the isotopic mass (m) dependence of noble gas diffusioncoefficients in water (D), which has not been measured but is estimatedusing experimental D-values for the major isotopes along with an untestedrelationship from kinetic theory, D prop m-0.5. We applied moleculardynamics methods to determine the mass dependence of D for four noblegases at 298 K, finding that D prop m-beta with beta<0.2, whichrefutes the kinetic theory model underlying all currentapplications.

Investigation of Methane Oxy-Fuel Combustion in a Swirl-Stabilised Gas Turbine Model Combustor

Directory of Open Access Journals (Sweden)

Mao Li

2017-05-01

Full Text Available CO2 has a strong impact on both operability and emission behaviours in gas turbine combustors. In the present study, an atmospheric, preheated, swirl-stabilised optical gas turbine model combustor rig was employed. The primary objectives were to analyse the influence of CO2 on the fundamental characteristics of combustion, lean blowout (LBO limits, CO emission and flame structures. CO2 dilution effects were examined with three preheating temperatures (396.15, 431.15, and 466.15 K. The fundamental combustion characteristics were studied utilising chemical kinetic simulations. To study the influence of CO2 on the operational range of the combustor, equivalence ratio (Ф was varied from stoichiometric conditions to the LBO limits. CO emissions were measured at the exit of the combustor using a water-cooled probe over the entire operational range. The flame structures and locations were characterised by performing CH chemiluminescence imaging. The inverse Abel transformation was used to analyse the CH distribution on the axisymmetric plane of the combustor. Chemical kinetic modelling indicated that the CO2 resulted in a lower reaction rate compared with the CH4/air flame. Fundamental combustion properties such as laminar flame speed, ignition delay time and blowout residence time were found to be affected by CO2. The experimental results revealed that CO2 dilution resulted in a narrower operational range for the equivalence ratio. It was also found that CO2 had a strong inhibiting effect on CO burnout, which led to a higher concentration of CO in the combustion exhaust. CH chemiluminescence showed that the CO2 dilution did not have a significant impact on the flame structure.

Identification of Cyclopentenyl Fatty Acids by Gas Liquid Chromatography and Mass Spectrometry

DEFF Research Database (Denmark)

Shukla, V. K. S.; Abdel-Moety, E. M.; Larsen, Elfinn

1979-01-01

The straight chain fatty acids and the cyclopentenyl fatty acids present in the lipids of Hydnocarpus wightiana seeds were separated as their pyrrolidides by means of gas chromatography. A gas chromatography-mass spectrometry system confirmed the complete separation and permitted the identification...

Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part III: 2,5-Dimethylfuran

Science.gov (United States)

Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

2013-01-01

This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model. PMID:24518851

Quantitative analysis of deuterium by gas chromatography

International Nuclear Information System (INIS)

Isomura, Shohei; Kaetsu, Hayato

1981-01-01

An analytical method for the determination of deuterium concentration in water and hydrogen gas by gas chromatography is described. HD and D 2 in a hydrogen gas sample were separated from H 2 by a column packed with Molecular Sieve 13X, using extra pure hydrogen gas as carrier. A thermal conductivity detector was used. Concentrations of deuterium were determined by comparison with standard samples. The error inherent to the present method was less a 1% on the basis of the calibration curves obtained with the standard samples. The average time required for the analysis was about 3 minutes. (author)

Exhaust gas afterburner for internal combustion engines

Energy Technology Data Exchange (ETDEWEB)

Haertel, G

1977-05-12

The invention pertains to an exhaust gas afterburner for internal combustion engines, with an auxiliary fuel device arranged upstream from the afterburner proper and controlled by the rotational speed of the engine, which is additionally controlled by an oxygen or carbon monoxide sensor. The catalytic part of the afterburner, together with a rotochamber, is a separate unit.

Three-step approach for prediction of limit cycle pressure oscillations in combustion chambers of gas turbines

Science.gov (United States)

Iurashev, Dmytro; Campa, Giovanni; Anisimov, Vyacheslav V.; Cosatto, Ezio

2017-11-01

Currently, gas turbine manufacturers frequently face the problem of strong acoustic combustion driven oscillations inside combustion chambers. These combustion instabilities can cause extensive wear and sometimes even catastrophic damages to combustion hardware. This requires prevention of combustion instabilities, which, in turn, requires reliable and fast predictive tools. This work presents a three-step method to find stability margins within which gas turbines can be operated without going into self-excited pressure oscillations. As a first step, a set of unsteady Reynolds-averaged Navier-Stokes simulations with the Flame Speed Closure (FSC) model implemented in the OpenFOAM® environment are performed to obtain the flame describing function of the combustor set-up. The standard FSC model is extended in this work to take into account the combined effect of strain and heat losses on the flame. As a second step, a linear three-time-lag-distributed model for a perfectly premixed swirl-stabilized flame is extended to the nonlinear regime. The factors causing changes in the model parameters when applying high-amplitude velocity perturbations are analysed. As a third step, time-domain simulations employing a low-order network model implemented in Simulink® are performed. In this work, the proposed method is applied to a laboratory test rig. The proposed method permits not only the unsteady frequencies of acoustic oscillations to be computed, but the amplitudes of such oscillations as well. Knowing the amplitudes of unstable pressure oscillations, it is possible to determine how these oscillations are harmful to the combustor equipment. The proposed method has a low cost because it does not require any license for computational fluid dynamics software.

Determination of fission gas yields from isotope ratios

DEFF Research Database (Denmark)

Mogensen, Mogens Bjerg

1983-01-01

This paper describes a method of calculating the actual fission yield of Kr and Xe in nuclear fuel including the effect of neutron capture reactions and decay. The bases for this calculation are the cumulative yields (ref. 1) of Kr and Xe isotopes (or pairs of isotopes) which are unaffected...... by neutron capture reactions, and measured Kr and Xe isotope ratios. Also the burnup contribution from the different fissile heavy isotopes must be known in order to get accurate fission gas yields....

New combustion, environment regulations: the answers for natural gas; Nouvelles reglementations, combustion, environnement: les reponses pour le gaz naturel

Energy Technology Data Exchange (ETDEWEB)

Le Peltier-Marc, A. [Gaz de France (GDF), 75 - Paris (France)

1997-12-31

This paper reports on the point of view from Gaz de France (GdF) company concerning the potential consequences of the use of natural gas in combustion systems with respect to the new regulations about combustion and environment. Details concerning the measures relative to the limitation of pollutants in small combustion installations (2 - 20 MW) are given (chimney height, SO{sub x}, NO{sub x} and dusts content in exhaust gases). (J.S.)

[Uncertainty evaluation of the determination of toxic equivalent quantity of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil by isotope dilution high resolution gas chromatography and high resolution mass spectrometry].

Science.gov (United States)

Du, Bing; Liu Aimin; Huang, Yeru

2014-09-01

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in soil samples were analyzed by isotope dilution method with high resolution gas chromatography and high resolution mass spectrometry (ID-HRGC/HRMS), and the toxic equivalent quantity (TEQ) were calculated. The impacts of major source of measurement uncertainty are discussed, and the combined relative standard uncertainties were calculated for each 2, 3, 7, 8 substituted con- gener. Furthermore, the concentration, combined uncertainty and expanded uncertainty for TEQ of PCDD/Fs in a soil sample in I-TEF, WHO-1998-TEF and WHO-2005-TEF schemes are provided as an example. I-TEF, WHO-1998-TEF and WHO-2005-TEF are the evaluation schemes of toxic equivalent factor (TEF), and are all currently used to describe 2,3,7,8 sub- stituted relative potencies.

Test Plan for Measuring Ventilation Rates and Combustible Gas Levels in TWRS Active Catch Tanks

Energy Technology Data Exchange (ETDEWEB)

NGUYEN, D.M.

1999-10-25

The purpose of this sampling activity is to obtain data to support an initial evaluation of potential hazards due to the presence of combustible gas in catch tanks that are currently operated by the River Protection Project (RPP). Results of the hazard analysis will be used to support closure of the flammable gas unreviewed safety question for these facilities. The data collection will be conducted in accordance with the Tank Safety Screening Data Quality Objective (Dukelow et al. 1995). Combustible gas, ammonia, and organic vapor levels in the headspace of the catch tanks will be field-measured using hand-held instruments. If a combustible gas level measurement in a tank exceeds an established threshold, gas samples will he collected in SUMMA' canisters for more extensive laboratory analysis. In addition, ventilation rates of some catch tanks will be measured to evaluate removal of flammable gas by air flowing through the tanks. This test plan identifies the sample collection, laboratory analysis, quality assurance, and reporting objectives for this data collection effort. The plan also provides the procedures for field measurement of combustible gas concentrations and ventilation rates.

Quantitative measurements of in-cylinder gas composition in a controlled auto-ignition combustion engine

Science.gov (United States)

Zhao, H.; Zhang, S.

2008-01-01

One of the most effective means to achieve controlled auto-ignition (CAI) combustion in a gasoline engine is by the residual gas trapping method. The amount of residual gas and mixture composition have significant effects on the subsequent combustion process and engine emissions. In order to obtain quantitative measurements of in-cylinder residual gas concentration and air/fuel ratio, a spontaneous Raman scattering (SRS) system has been developed recently. The optimized optical SRS setups are presented and discussed. The temperature effect on the SRS measurement is considered and a method has been developed to correct for the overestimated values due to the temperature effect. Simultaneous measurements of O2, H2O, CO2 and fuel were obtained throughout the intake, compression, combustion and expansion strokes. It shows that the SRS can provide valuable data on this process in a CAI combustion engine.

Quantitative measurements of in-cylinder gas composition in a controlled auto-ignition combustion engine

International Nuclear Information System (INIS)

Zhao, H; Zhang, S

2008-01-01

One of the most effective means to achieve controlled auto-ignition (CAI) combustion in a gasoline engine is by the residual gas trapping method. The amount of residual gas and mixture composition have significant effects on the subsequent combustion process and engine emissions. In order to obtain quantitative measurements of in-cylinder residual gas concentration and air/fuel ratio, a spontaneous Raman scattering (SRS) system has been developed recently. The optimized optical SRS setups are presented and discussed. The temperature effect on the SRS measurement is considered and a method has been developed to correct for the overestimated values due to the temperature effect. Simultaneous measurements of O 2 , H 2 O, CO 2 and fuel were obtained throughout the intake, compression, combustion and expansion strokes. It shows that the SRS can provide valuable data on this process in a CAI combustion engine

Multi-Canister Overpack (MCO) Combustible Gas Management Leak Test Acceptance Criteria (OCRWM)

International Nuclear Information System (INIS)

SHERRELL, D.L.

2000-01-01

The purpose of this document is to support the Spent Nuclear Fuel Project's combustible gas management strategy while avoiding the need to impose any requirements for oxygen free atmospheres within storage tubes that contain multi-canister overpacks (MCO). In order to avoid inerting requirements it is necessary to establish and confirm leak test acceptance criteria for mechanically sealed and weld sealed MCOs that are adequte to ensure that, in the unlikely event the leak test results for any MCO were to approach either of those criteria, it could still be handled and stored in stagnant air without compromising the SNF Project's overall strategy to prevent accumulation of combustible gas mixtures within MCOs or within their surroundings. To support that strategy, this document: (1) establishes combustible gas management functions and minimum functional requirements for the MCO's mechanical seals and closure weld(s); (2) establishes a maximum practical value for the minimum required initial MCO inert backfill gas pressure; and (3) based on items 1 and 2, establishes and confirms leak test acceptance criteria for the MCO's mechanical seal and final closure weld(s)

Severe Accident Analysis for Combustible Gas Risk Evaluation inside CFVS

International Nuclear Information System (INIS)

Lee, NaRae; Lee, JinYong; Bang, YoungSuk; Lee, DooYong; Kim, HyeongTaek

2015-01-01

The purpose of this study is to identify the composition of gases discharged into the containment filtered venting system by analyzing severe accidents. The accident scenarios which could be significant with respect to containment pressurization and hydrogen generation are derived and composition of containment atmosphere and possible discharged gas mixtures are estimated. In order to ensure the safety of the public and environment, the ventilation system should be designed properly by considering discharged gas flow rate, aerosol loads, radiation level, etc. One of considerations to be resolved is the risk due to combustible gas, especially hydrogen. Hydrogen can be generated largely by oxidation of cladding and decomposition of concrete. If the hydrogen concentration is high enough and other conditions like oxygen and steam concentration is met, the hydrogen can burn, deflagrate or detonate, which result in the damage the structural components. In particularly, after Fukushima accident, the hydrogen risk has been emphasized as an important contributor threatening the integrity of nuclear power plant during the severe accident. These results will be used to analyze the risk of hydrogen combustion inside the CFVS as boundary conditions. Severe accident simulation results are presented and discussed qualitatively with respect to hydrogen combustion. The hydrogen combustion risk inside of the CFVS has been examined qualitatively by investigating the discharge flow characteristics. Because the composition of the discharge flow to CFVS would be determined by the containment atmosphere, the severe accident progression and containment atmosphere composition have been investigated. Due to PAR operation, the hydrogen concentration in the containment would be decreased until the oxygen is depleted. After the oxygen is depleted, the hydrogen concentration would be increased. As a result, depending on the vent initiation timing (i.e. vent initiation pressure), the important

Severe Accident Analysis for Combustible Gas Risk Evaluation inside CFVS

Energy Technology Data Exchange (ETDEWEB)

Lee, NaRae; Lee, JinYong; Bang, YoungSuk; Lee, DooYong [FNC Technology Co. Ltd., Yongin (Korea, Republic of); Kim, HyeongTaek [KHNP-Central Research Institute, Daejeon (Korea, Republic of)

2015-10-15

The purpose of this study is to identify the composition of gases discharged into the containment filtered venting system by analyzing severe accidents. The accident scenarios which could be significant with respect to containment pressurization and hydrogen generation are derived and composition of containment atmosphere and possible discharged gas mixtures are estimated. In order to ensure the safety of the public and environment, the ventilation system should be designed properly by considering discharged gas flow rate, aerosol loads, radiation level, etc. One of considerations to be resolved is the risk due to combustible gas, especially hydrogen. Hydrogen can be generated largely by oxidation of cladding and decomposition of concrete. If the hydrogen concentration is high enough and other conditions like oxygen and steam concentration is met, the hydrogen can burn, deflagrate or detonate, which result in the damage the structural components. In particularly, after Fukushima accident, the hydrogen risk has been emphasized as an important contributor threatening the integrity of nuclear power plant during the severe accident. These results will be used to analyze the risk of hydrogen combustion inside the CFVS as boundary conditions. Severe accident simulation results are presented and discussed qualitatively with respect to hydrogen combustion. The hydrogen combustion risk inside of the CFVS has been examined qualitatively by investigating the discharge flow characteristics. Because the composition of the discharge flow to CFVS would be determined by the containment atmosphere, the severe accident progression and containment atmosphere composition have been investigated. Due to PAR operation, the hydrogen concentration in the containment would be decreased until the oxygen is depleted. After the oxygen is depleted, the hydrogen concentration would be increased. As a result, depending on the vent initiation timing (i.e. vent initiation pressure), the important

Application of gas chromatography to analysis of spirit-based alcoholic beverages.

Science.gov (United States)

Wiśniewska, Paulina; Śliwińska, Magdalena; Dymerski, Tomasz; Wardencki, Waldemar; Namieśnik, Jacek

2015-01-01

Spirit-based beverages are alcoholic drinks; their production processes are dependent on the type and origin of raw materials. The composition of this complex matrix is difficult to analyze, and scientists commonly choose gas chromatography techniques for this reason. With a wide selection of extraction methods and detectors it is possible to provide qualitative and quantitative analysis for many chemical compounds with various functional groups. This article describes different types of gas chromatography techniques and their most commonly used associated extraction techniques (e.g., LLE, SPME, SPE, SFE, and SBME) and detectors (MS, TOFMS, FID, ECD, NPD, AED, O or EPD). Additionally, brief characteristics of internationally popular spirit-based beverages and application of gas chromatography to the analysis of selected alcoholic drinks are presented.

Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber

KAUST Repository

Shi, Xian

2017-01-05

Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber are numerically investigated using an 1-D unsteady, shock-capturing, compressible and reacting flow solver. Different combinations of reaction front propagation and end-gas combustion modes are observed, i.e., 1) deflagration without end-gas combustion, 2) deflagration to end-gas autoignition, 3) deflagration to end-gas detonation, 4) developing or developed detonation, occurring in the sequence of increasing initial temperatures. Effects of ignition location and chamber size are evaluated: the asymmetric ignition is found to promote the reactivity of unburnt mixture compared to ignitions at center/wall, due to additional heating from asymmetric pressure waves. End-gas combustion occurs earlier in smaller chambers, where end-gas temperature rise due to compression heating from the deflagration is faster. According to the ξ−ε regime diagram based on Zeldovich theory, modes of reaction front propagation are primarily determined by reactivity gradients introduced by initial ignition, while modes of end-gas combustion are influenced by the total amount of unburnt mixture at the time when autoignition occurs. A transient reactivity gradient method is provided and able to capture the occurrence of detonation.

Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber

KAUST Repository

Shi, Xian; Ryu, Je Ir; Chen, Jyh-Yuan; Dibble, Robert W.

2017-01-01

Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber are numerically investigated using an 1-D unsteady, shock-capturing, compressible and reacting flow solver. Different combinations of reaction front propagation and end-gas combustion modes are observed, i.e., 1) deflagration without end-gas combustion, 2) deflagration to end-gas autoignition, 3) deflagration to end-gas detonation, 4) developing or developed detonation, occurring in the sequence of increasing initial temperatures. Effects of ignition location and chamber size are evaluated: the asymmetric ignition is found to promote the reactivity of unburnt mixture compared to ignitions at center/wall, due to additional heating from asymmetric pressure waves. End-gas combustion occurs earlier in smaller chambers, where end-gas temperature rise due to compression heating from the deflagration is faster. According to the ξ−ε regime diagram based on Zeldovich theory, modes of reaction front propagation are primarily determined by reactivity gradients introduced by initial ignition, while modes of end-gas combustion are influenced by the total amount of unburnt mixture at the time when autoignition occurs. A transient reactivity gradient method is provided and able to capture the occurrence of detonation.

Variations in the stable isotope ratios of specific aromatic and aliphatic hydrocarbons from coal conversion processes

Energy Technology Data Exchange (ETDEWEB)

McRae, C.; Snape, C.E.; Fallick, A.E. [University of Strathclyde, Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

1998-07-01

To establish the scope for applying gas chromatography-isotope ratio mass spectrometry ({sup {delta}-13}C GC-IRMS) to molecular recognition problems in coal utilisation, {sup 13}C/{sup 12}C isotope ratios were determined for n-alkanes and polycyclic aromatic hydrocarbons (PAHs) as a function of coal rank and process conditions. Six coals ranging from a lignite to a low volatile bituminous coal were subjected to chloroform extraction, fixed-bed pyrolysis under hydrogen pressure (hydropyrolysis) and fluidised-bed (flash) pyrolysis. No significant variations in the stable isotope ratios of n-alkanes were evident as a function of either rank or conversion regime. In contrast, the isotope ratios of PAHs show large variations with those for hydropyrolysis (-23 to -25 parts per thousand) being similar to the bulk values of the initial coals and being isotopically heavier (less negative) than their fluidised-bed pyrolysis counterparts by 2-3 parts per thousand. However, the PAHs from fluidised-bed pyrolysis, which resemble closely those obtained from high temperature coal carbonization, are still heavier (by 2-3 parts per thousand) than those from diesel particulates and coal gasification and combustion residues. This provides a firm basis for the source apportionment of airborne PAHs in the proximity of coking plants, particularly with no major variations in the PAH isotope ratios being found as a function of rank.

Conjugated heat transfer and temperature distributions in a gas turbine combustion liner under base-load operation

International Nuclear Information System (INIS)

Kim, Kyung Min; Yun, Nam Geon; Jeon, Yun Heung; Lee, Dong Hyun; Cho, Yung Hee

2010-01-01

Prediction of temperature distributions on hot components is important in development of a gas turbine combustion liner. The present study investigated conjugated heat transfer to obtain temperature distributions in a combustion liner with six combustion nozzles. 3D numerical simulations using FVM commercial codes, Fluent and CFX were performed to calculate combustion and heat transfer distributions. The temperature distributions in the combustor liner were calculated by conjugation of conduction and convection (heat transfer coefficients) obtained by combustion and cooling flow analysis. The wall temperature was the highest on the attachment points of the combustion gas from combustion nozzles, but the temperature gradient was high at the after shell section with low wall temperature

Exhaust gas recirculation system for an internal combustion engine

Science.gov (United States)

Wu, Ko-Jen

2013-05-21

An exhaust gas recirculation system for an internal combustion engine comprises an exhaust driven turbocharger having a low pressure turbine outlet in fluid communication with an exhaust gas conduit. The turbocharger also includes a low pressure compressor intake and a high pressure compressor outlet in communication with an intake air conduit. An exhaust gas recirculation conduit fluidly communicates with the exhaust gas conduit to divert a portion of exhaust gas to a low pressure exhaust gas recirculation branch extending between the exhaust gas recirculation conduit and an engine intake system for delivery of exhaust gas thereto. A high pressure exhaust gas recirculation branch extends between the exhaust gas recirculation conduit and the compressor intake and delivers exhaust gas to the compressor for mixing with a compressed intake charge for delivery to the intake system.

Comparative study of radio gas-chromatography and gas chromatography - mass spectrometry coupling in the identification of metabolites of estrogens and progesterone

International Nuclear Information System (INIS)

Adessi, G.; Nhuan, T.Q.; Jayle, M.F.

1978-01-01

Radio-gas chromatography (RGC) and gas chromatography-mass spectrometry (GC-MS) were used to identify estrogen and progesterone metabolites. The RGC enables the identification of metabolites of labelled precursors ( 3 H)-estradiol-17β and ( 14 C)-progesterone were used as precursors. The GC-MS analytical technique with mass fragmentography, offers the interest of using unlabelled precursors at physiological levels. The identification of metabolites was based on obtaining the mass spectrum or the compiled fragmentogram on the basis of the most characteristic fragment ions. More over, several metabolites can be quantified on the same fragmentogram. Results on the metabolism of estradiol-17β and progesterone by the hepatic tissue of guinea pigs are given. (Auth.)

Methane Emissions from Landfill: Isotopic Evidence for Low Percentage of Oxidation from Gas Wells, Active and Closed Cells

Science.gov (United States)

Lowry, David; Fisher, Rebecca; Zazzeri, Giulia; al-Shalaan, Aalia; France, James; Lanoisellé, Mathias; Nisbet, Euan

2017-04-01

Large landfill sites remain a significant source of methane emissions in developed and developing countries, with a global estimated flux of 29 Tg / yr in the EDGAR 2008 database. This is significantly lower than 20 years ago due to the introduction of gas extraction systems, but active cells still emit significant amounts of methane before the gas is ready for extraction. Historically the methane was either passively oxidized through topsoil layers or flared. Oxidation is still the primary method of methane removal in many countries, and covered, remediated cells across the world continue to emit small quantities of methane. The isotopic signatures of methane from landfill gas wells, and that emitted from active and closed cells have been characterized for more than 20 UK landfills since 2011, with more recent work in Kuwait and Hong Kong. Since 2013 the emission plumes have been identified by a mobile measurement system (Zazzeri et al., 2015). Emissions in all 3 countries have a characteristic δ13C signature of -58 ± 3 ‰ dominated by emissions from the active cells, despite the hot, dry conditions of Kuwait and the hot, humid conditions of Hong Kong. Gas well samples define a similar range. Surface emissions from closed cells and closed landfills are mostly in the range -56 to -52 ‰Ṫhese are much more depleted values than those observed in the 1990s (up to -35 ) when soil oxidation was the dominant mechanism of methane removal. Calculations using isotopic signatures of the amount of methane oxidised in these closed areas before emission to atmosphere range from 5 to 15%, but average less than 10%, and are too small to calculate from the high-emitting active cells. Compared to other major methane sources, landfills have the most consistent isotopic signature globally, and are distinct from the more 13C-enriched natural gas, combustion and biomass burning sources. Zazzeri, G. et al. (2015) Plume mapping and isotopic characterization of anthropogenic methane

Simultaneous analysis of urinary phthalate metabolites of residents in Korea using isotope dilution gas chromatography-mass spectrometry.

Science.gov (United States)

Kim, Miok; Song, Na Rae; Choi, Jong-Ho; Lee, Jeongae; Pyo, Heesoo

2014-02-01

Phthalates are used in industry products, household items, and medical tools as plasticizers. Human exposure to phthalates has raised concern about its toxicity. In the present study, optimization was conducted for the simultaneous analysis of eight kinds of phthalate metabolites using gas chromatography-mass spectrometry (GC-MS): MEP, MiBP, MnBP, MBzP, MiNP, MEHP, MEOHP, and MEHHP. In order to minimize the matrix effect and to do quantitative analysis, isotope dilution and LLE-GC-MS methods were performed. Urine samples were enzymatically hydrolyzed, extracted with a mixture of n-hexane and ethyl ether (8:2; v:v), and subsequently derivatized with trimethylsilylation. All eight kinds of analytes showed clear resolution and high reproducibility in GC-MS results. The method detection limit ranged from 0.05 ng/mL to 0.2 ng/mL. Calibration curves were found to be linear from 0.2 to 100 ng/mL with -(2)>0.992. The relative standard deviation of the intraday precision using water and urine ranged from 2.1% to 16.3%. The analysis was performed with urine samples that were collected from adults residing in the Republic of Korea. The analyzed concentration results were compared according to gender and region. As a result, DEHP metabolites showed the highest detected concentration (75.92 μg/g creatinine, 100%), and MiNP, a metabolite of DiNP, showed the lowest detected concentration (0.42 μg/g creatinine, 22.5%). On average, female urine (200.76 μg/g creatinine) had a higher detected concentration of ∑8 phthalate metabolites than male urine. Samples from rural regions (211.96 μg/g creatinine) had higher levels than samples from urban regions. © 2013.

Microbial metabolomics with gas chromatography/mass spectrometry

NARCIS (Netherlands)

Koek, M.M.; Muilwijk, B.; Werf, M.J. van der; Hankemeier, T.

2006-01-01

An analytical method was set up suitable for the analysis of microbial metabolomes, consisting of an oximation and silylation derivatization reaction and subsequent analysis by gas chromatography coupled to mass spectrometry. Microbial matrixes contain many compounds that potentially interfere with

Lean-rich axial stage combustion in a can-annular gas turbine engine

Science.gov (United States)

Laster, Walter R.; Szedlacsek, Peter

2016-06-14

An apparatus and method for lean/rich combustion in a gas turbine engine (10), which includes a combustor (12), a transition (14) and a combustor extender (16) that is positioned between the combustor (12) and the transition (14) to connect the combustor (12) to the transition (14). Openings (18) are formed along an outer surface (20) of the combustor extender (16). The gas turbine (10) also includes a fuel manifold (28) to extend along the outer surface (20) of the combustor extender (16), with fuel nozzles (30) to align with the respective openings (18). A method (200) for axial stage combustion in the gas turbine engine (10) is also presented.

Lipids, pots and food processing at Hočevarica, Ljubljansko barje, Slovenia

Directory of Open Access Journals (Sweden)

Nives Ogrinc

2014-12-01

Full Text Available The paper presents the results of lipid analyses of pottery samples from Ho≠evarica (Ljub- ljansko barje, Slovenia. Total lipid extracts were subjected to high temperature gas chromatography (HT-GC, gas chromatography-mass spectrometry (GC-MS and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS. The results show that some vessels were used for prepar- ing ruminant meat and vegetable, but also the remains of aquatic food were identified. The processing of non-ruminant meat was detected in a few samples. A high number of pottery samples yielded the presence of beeswax lipids. The charred residual on pottery was AMS 14C dated.

Combustion reactivity of chars from copyrolysis of coal with coke-oven gas

Energy Technology Data Exchange (ETDEWEB)

Liao Hongqiang; Sun Chenggong; Li Baoqing [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion

1997-12-31

The combustion reactivity of char from pyrolysis of Xianfeng lignite with coke-oven gas (COG) is related to the pyrolysis pressure and heating rate. Decreasing pressure and increasing heating rate enhance the char yields and combustion reactivity. The combustion reactivities of char from coal pyrolysis with COG nearly reach to that of char from hydropyrolysis, but lower than those of char from coal pyrolysis under N{sub 2}. (orig.)

Isotopic enrichment of 15N by ionic exchange chromatography

International Nuclear Information System (INIS)

Trivelin, P.C.O.

1979-01-01

The present paper presents some studies on production of 15 N-enriched ammonium sulphate with 5% atoms by ionic exchange chromatography method. Two systems are described of columns of resin, where experiments were conducted by eluition of NH 4 + bands with sodium hydroxide solution. Analyses were made of the cost of production of 15 N-enriched ammonium sulphate 5% atoms and, based on the experiments developed, a cost was obtained which was compatible with the international price of the product. The isotopic analyses of nitrogen were made by mass spectrometry. (Author) [pt

Separation of boron isotopes by ion exchange chromatography: studies with Duolite-162, a type-II resin

International Nuclear Information System (INIS)

Sharma, B.K.; Subramanian, R.; Balasubramanian, R.; Mathur, P.K.

1994-01-01

The selection of resin plays an important role in the process of separation of boron isotopes by ion exchange chromatography. The determination of (i) ion exchange capacity of Duolite-162 resin for hydroxyl - chloride exchange, (ii) hydroxyl - borate exchange, (iii) isotopic exchange separation factor by batch method and (iv) effect of concentration of boric acid on isotopic exchange separation factor to test the suitability of the above resin for this process are discussed in this report. (author)

Fast temperature programming in gas chromatography using resistive heating

NARCIS (Netherlands)

Dallüge, J.; Ou-Aissa, R.; Vreuls, J.J.; Brinkman, U.A.T.; Veraart, J.R.

1999-01-01

The features of a resistive-heated capillary column for fast temperature-programmed gas chromatography (GC) have been evaluated. Experiments were carried out using a commercial available EZ Flash GC, an assembly which can be used to upgrade existing gas chromatographs. The capillary column is placed

Quantification of 13 priority polycyclic aromatic hydrocarbons in human urine by headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Campo, Laura [Department of Occupational and Environmental Health, University of Milan and Fondazione IRCCS Ospedale Maggiore Policlinico, Mangiagalli e Regina Elena, Milan (Italy)], E-mail: laura.campo@unimi.it; Mercadante, Rosa; Rossella, Federica; Fustinoni, Silvia [Department of Occupational and Environmental Health, University of Milan and Fondazione IRCCS Ospedale Maggiore Policlinico, Mangiagalli e Regina Elena, Milan (Italy)

2009-01-12

Polycyclic aromatic hydrocarbons (PAHs) are common environmental pollutants in both living and working environments. The aim of this study was the development of a headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry (HS-SPME/GC-IDMS) method for the simultaneous quantification of 13 PAHs in urine samples. Different parameters affecting PAHs extraction by HS-SPME were considered and optimized: type/thickness of fiber coatings, extraction temperature/time, desorption temperature/time, ionic strength and sample agitation. The stability of spiked PAHs solutions and of real urine samples stored up to 90 days in containers of different materials was evaluated. In the optimized method, analytes were absorbed for 60 min at 80 deg. C in the sample headspace with a 100 {mu}m polydimethylsiloxane fiber. The method is very specific, with linear range from the limit of quantification to 8.67 x 10{sup 3} ng L{sup -1}, a within-run precision of <20% and a between-run precision of <20% for 2-, 3- and 4-ring compounds and of <30% for 5-ring compounds, trueness within 20% of the spiked concentration, and limit of quantification in the 2.28-2.28 x 10{sup 1} ng L{sup -1} range. An application of the proposed method using 15 urine samples from subjects exposed to PAHs at different environmental levels is shown.

Combustion of coal gas fuels in a staged combustor

Science.gov (United States)

Rosfjord, T. J.; Mcvey, J. B.; Sederquist, R. A.; Schultz, D. F.

1982-01-01

Gaseous fuels produced from coal resources generally have heating values much lower than natural gas; the low heating value could result in unstable or inefficient combustion. Coal gas fuels may contain ammonia which if oxidized in an uncontrolled manner could result in unacceptable nitrogen oxide exhaust emission levels. Previous investigations indicate that staged, rich-lean combustion represents a desirable approach to achieve stable, efficient, low nitrogen oxide emission operation for coal-derived liquid fuels contaning up to 0.8-wt pct nitrogen. An experimental program was conducted to determine whether this fuel tolerance can be extended to include coal-derived gaseous fuels. The results of tests with three nitrogen-free fuels having heating values of 100, 250, and 350 Btu/scf and a 250 Btu/scf heating value doped to contain 0.7 pct ammonia are presented.

DIRECT-DEPOSITION INFRARED SPECTROMETRY WITH GAS AND SUPERCRITICAL FLUID CHROMATOGRAPHY

Science.gov (United States)

A direct-deposition Fourier transform infrared (FT-IR) system has been evaluated for applicability to gas chromatography (GC) and supercritical fluid chromatography (SFC) of environmental analytes. A 100-um i.d. fused-silica transfer line was used for GC, and a 50-um transfer lin...

Radiogas chromatography mass spectrometry in the selected ion monitoring mode

International Nuclear Information System (INIS)

Doerfler, D.L.; Rosenblum, E.R.; Malloy, J.M.; Naworal, J.D.; McManus, I.R.; Campbell, I.M.

1980-01-01

The value of selected ion monitoring in analyzing biological radio isotope incorporation experiments by radiogas chromatography mass spectrometry is illustrated with reference to the biosynthesis of the mycotoxin mycophenolic acid in Penicillium brevicompactum and the mode of action of the anticholesterolemic drug 20,25-diazacholesterol. Both examples used 1-[ 14 C]acetate precursors. It is shown that the increased sensitivity and specificity of the selected ion monitoring mode detector permits straightforward detection and identification of the relatively small cellular pools associated with metabolic intermediates. The computer program RADSIM is described. Problems that still exist in using radiogas gas chromatography mass spectrometry technology to analyse isotope incorporation experiments are discussed. (author)

Combined Cycle Power Generation Employing Pressure Gain Combustion

Energy Technology Data Exchange (ETDEWEB)

Holley, Adam [United Technologies Corporation, East Hartford, CT (United States). Research Center

2017-05-15

The Phase I program assessed the potential benefit of applying pressure gain combustion (PGC) technology to a natural gas combined cycle power plant. A conceptual design of the PGC integrated gas turbine was generated which was simulated in a detailed system modeling tool. The PGC integrated system was 1.93% more efficient, produced 3.09% more power, and reduced COE by 0.58%. Since the PGC system used had the same fuel flow rate as the baseline system, it also reduced CO₂ emissions by 3.09%. The PGC system did produce more NOx than standard systems, but even with the performanceand cost penalties associated with the cleanup system it is better in every measure. This technology benefits all of DOE’s stated program goals to improve plant efficiency, reduce CO₂ production, and reduce COE.

Advanced modeling of oxy-fuel combustion of natural gas

Energy Technology Data Exchange (ETDEWEB)

Chungen Yin

2011-01-15

The main goal of this small-scale project is to investigate oxy-combustion of natural gas (NG) through advanced modeling, in which radiation, chemistry and mixing will be reasonably resolved. 1) A state-of-the-art review was given regarding the latest R and D achievements and status of oxy-fuel technology. The modeling and simulation status and achievements in the field of oxy-fuel combustion were also summarized; 2) A computer code in standard c++, using the exponential wide band model (EWBM) to evaluate the emissivity and absorptivity of any gas mixture at any condition, was developed and validated in detail against data in literature. A new, complete, and accurate WSGGM, applicable to both air-fuel and oxy-fuel combustion modeling and applicable to both gray and non-gray calculation, was successfully derived, by using the validated EWBM code as the reference mode. The new WSGGM was implemented in CFD modeling of two different oxy-fuel furnaces, through which its great, unique advantages over the currently most widely used WSGGM were demonstrated. 3) Chemical equilibrium calculations were performed for oxy-NG flame and air-NG flame, in which dissociation effects were considered to different degrees. Remarkable differences in oxy-fuel and air-fuel combustion were revealed, and main intermediate species that play key roles in oxy-fuel flames were identified. Different combustion mechanisms are compared, e.g., the most widely used 2-step global mechanism, refined 4-step global mechanism, a global mechanism developed for oxy-fuel using detailed chemical kinetic modeling (CHEMKIN) as reference. 4) Over 15 CFD simulations were done for oxy-NG combustion, in which radiation, chemistry, mixing, turbulence-chemistry interactions, and so on were thoroughly investigated. Among all the simulations, RANS combined with 2-step and refined 4-step mechanism, RANS combined with CHEMKIN-based new global mechanism for oxy-fuel modeling, and LES combined with different combustion

Single-run determination of polybrominated diphenyl ethers (PBDEs) di- to deca-brominated in fish meal, fish oil and fish feed by isotope dilution: application of automated sample purification and gas chromatography/ion trap tandem mass spectrometry (GC/ITMS).

Science.gov (United States)

Blanco, Sonia Lucía; Vieites, Juan M

2010-07-05

The present paper describes the application of automated cleanup and fractionation procedures of the Power Prep system (Fluid Management Systems) for the determination of polybrominated diphenyl ethers (PBDEs) in feeding stuffs and fish meal and oil. Gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITMS) allowed the analysis of di- to deca-BDEs in the samples matrices used in fish aquaculture. The method developed enabled the determination of 26 native PBDE congeners and 11 (13)C(12)-labelled congeners, including deca-BDE 209, in a single-run analysis, using isotope dilution. The automated cleanup, consisting of a succession of multilayer silica and basic alumina columns previously applied by Wyrzykowska et al. (2009) [28] in combustion flue gas, was successfully applied in our complex matrices. The method allowed an increase in productivity, i.e. lower time was required to process samples, and simultaneous purification of several samples was achieved at a time, reducing analyst dedication and human error input. Average recoveries of 43-96% were obtained. GC/ITMS can overcome the complexity originating from the sample matrix, eliminating matrix effects by tandem MS, to enable the detection of congeners penta- to nona-BDEs where interferent masses were present. The provisional detection limits, estimated in the samples, were 5-30 pg for di-, tri-, tetra-, and penta-BDEs, 20-65 pg for hexa-, hepta-, octa- and nona-BDEs, and 105 pg for deca-BDE. Reduction of deca-BDE 209 blank values is of concern to ongoing research. Good accuracy was obtained by application of the whole procedure, representing an efficient, low-cost and fast alternative for routine analyses. Copyright 2010 Elsevier B.V. All rights reserved.

Intelligent Integration between Human Simulated Intelligence and Expert Control Technology for the Combustion Process of Gas Heating Furnace

Directory of Open Access Journals (Sweden)

Yucheng Liu

2014-01-01

Full Text Available Due to being poor in control quality of the combustion process of gas heating furnace, this paper explored a sort of strong robust control algorithm in order to improve the control quality of the combustion process of gas heating furnace. The paper analyzed the control puzzle in the complex combustion process of gas heating furnace, summarized the cybernetics characteristic of the complex combustion process, researched into control strategy of the uncertainty complex control process, discussed the control model of the complex process, presented a sort of intelligent integration between human-simulated intelligence and expert control technology, and constructed the control algorithm for the combustion process controlling of gas heating furnace. The simulation results showed that the control algorithm proposed in the paper is not only better in dynamic and steady quality of the combustion process, but also obvious in energy saving effect, feasible, and effective in control strategy.

Modelling non-steady-state isotope enrichment of leaf water in a gas-exchange cuvette environment.

Science.gov (United States)

Song, Xin; Simonin, Kevin A; Loucos, Karen E; Barbour, Margaret M

2015-12-01

with a cuvette setting. Using an experiment conducted on cotton leaves, we show that the modified NSS model performed well in predicting the time constant for the exponential approach of leaf water toward steady state under cuvette conditions. Such a result demonstrates the applicability of this new model to gas-exchange cuvette conditions where the transpiration flux directly influences δv , and therefore suggests the need to incorporate this model into future isotope studies that employ a laser-cuvette coupled system. © 2015 John Wiley & Sons Ltd.

Multiple-isotope separation in gas centrifuge

International Nuclear Information System (INIS)

Wood, Houston G.; Mason, T.C.; Soubbaramayer

1996-01-01

In previous works, the Onsager's pancake equation was used to provide solution to the internal counter-current flow field, which is necessary to calculate solutions to the isotope transport equation. The diffusion coefficient was assumed to be constant which is a good approximation for gases with large molecular weights, and small differences in the molecular weights of the various isotopes. A new optimization strategy was presented for determining the operating parameters of a gas centrifuge to be used for multiple-component isotope separation. Scoop drag, linear wall temperature gradient, the feed rate ant the cut have been chosen as operating parameters for the optimization. The investigation was restricted to a single centrifuge, and the problem of cascading for multiple-isotope separation was not addressed. The model describing the flow and separation phenomena in centrifuge includes a set of equations describing the fluid dynamics of the counter-current flow and the diffusion equations written for each isotope of the mixture. In this paper, an optimization algorithm is described and applied to an example for the re enrichment of spent reactor uranium

Method to make accurate concentration and isotopic measurements for small gas samples

Science.gov (United States)

Palmer, M. R.; Wahl, E.; Cunningham, K. L.

2013-12-01

Carbon isotopic ratio measurements of CO2 and CH4 provide valuable insight into carbon cycle processes. However, many of these studies, like soil gas, soil flux, and water head space experiments, provide very small gas sample volumes, too small for direct measurement by current constant-flow Cavity Ring-Down (CRDS) isotopic analyzers. Previously, we addressed this issue by developing a sample introduction module which enabled the isotopic ratio measurement of 40ml samples or smaller. However, the system, called the Small Sample Isotope Module (SSIM), does dilute the sample during the delivery with inert carrier gas which causes a ~5% reduction in concentration. The isotopic ratio measurements are not affected by this small dilution, but researchers are naturally interested accurate concentration measurements. We present the accuracy and precision of a new method of using this delivery module which we call 'double injection.' Two portions of the 40ml of the sample (20ml each) are introduced to the analyzer, the first injection of which flushes out the diluting gas and the second injection is measured. The accuracy of this new method is demonstrated by comparing the concentration and isotopic ratio measurements for a gas sampled directly and that same gas measured through the SSIM. The data show that the CO2 concentration measurements were the same within instrument precision. The isotopic ratio precision (1σ) of repeated measurements was 0.16 permil for CO2 and 1.15 permil for CH4 at ambient concentrations. This new method provides a significant enhancement in the information provided by small samples.

Isotope-dilution gas chromatography-mass spectrometry method for the analysis of hydroxyurea.

Science.gov (United States)

Garg, Uttam; Scott, David; Frazee, Clint; Kearns, Gregory; Neville, Kathleen

2015-06-01

Hydroxyurea is used in the treatment of various malignancies and sickle cell disease. There are limited studies on the pharmacokinetics of hydroxyurea, particularly in pediatric patients. An accurate, precise, and sensitive method is needed to support such studies and to monitor therapeutic adherence. We describe a novel gas chromatography-mass spectrometry (GC-MS) method for the determination of hydroxyurea concentration in plasma using stable labeled hydroxyurea C N2 as an internal standard. The method involved an organic extraction followed by the preparation of trimethylsilyl (TMS) derivatives of hydroxyurea for GC-MS selected ion-monitoring analysis. The following mass-to-charge (m/z) ratio ions for silated hydroxyurea and hydroxyurea C N2 were monitored: hydroxyurea-quantitative ion 277, qualifier ions 292 and 249; hydroxyurea C N2-quantitative ion 280, qualifier ion 295. This method was evaluated for reportable range, accuracy, within-run and between-run imprecisions, and limits of quantification. The reportable range for the method was 0.1-100 mcg/mL. All results were accurate within an allowable error of 15%. Within-run and between-run imprecisions were hydroxyurea described here is accurate, sensitive, precise, and robust. Its characteristics make the method suitable for supporting pharmacokinetic studies and/or clinical therapeutic monitoring.

Method for increasing the calorific value of gas produced by the in situ combustion of coal

Science.gov (United States)

Shuck, Lowell Z.

1978-01-01

The present invention relates to the production of relatively high Btu gas by the in situ combustion of subterranean coal. The coal bed is penetrated with a horizontally-extending borehole and combustion is initiated in the coal bed contiguous to the borehole. The absolute pressure within the resulting combustion zone is then regulated at a desired value near the pore pressure within the coal bed so that selected quantities of water naturally present in the coal will flow into the combustion zone to effect a hydrogen and carbon monoxide-producing steam-carbon reaction with the hot carbon in the combustion zone for increasing the calorific value of the product gas.

Thermodynamic characteristics of a low concentration methane catalytic combustion gas turbine

International Nuclear Information System (INIS)

Yin, Juan; Su, Shi; Yu, Xin Xiang; Weng, Yiwu

2010-01-01

Low concentration methane, emitted from coal mines, landfill, animal waste, etc. into the atmosphere, is not only a greenhouse gas, but also a waste energy source if not utilised. Methane is 23 times more potent than CO 2 in terms of trapping heat in the atmosphere over a timeframe of 100 years. This paper studies a novel lean burn catalytic combustion gas turbine, which can be powered with about 1% methane (volume) in air. When this technology is successfully developed, it can be used not only to mitigate the methane for greenhouse gas reduction, but also to utilise such methane as a clean energy source. This paper presents our study results on the thermodynamic characteristics of this new lean burn catalytic combustion gas turbine system by conducting thermal performance analysis of the turbine cycle. The thermodynamic data including thermal efficiencies and exergy loss of main components of the turbine system are presented under different pressure ratios, turbine inlet temperatures and methane concentrations.

The combustion behavior of diesel/CNG mixtures in a constant volume combustion chamber

Science.gov (United States)

Firmansyah; Aziz, A. R. A.; Heikal, M. R.

2015-12-01

The stringent emissions and needs to increase fuel efficiency makes controlled auto-ignition (CAI) based combustion an attractive alternative for the new combustion system. However, the combustion control is the main obstacles in its development. Reactivity controlled compression ignition (RCCI) that employs two fuels with significantly different in reactivity proven to be able to control the combustion. The RCCI concept applied in a constant volume chamber fuelled with direct injected diesel and compressed natural gas (CNG) was tested. The mixture composition is varied from 0 - 100% diesel/CNG at lambda 1 with main data collection are pressure profile and combustion images. The results show that diesel-CNG mixture significantly shows better combustion compared to diesel only. It is found that CNG is delaying the diesel combustion and at the same time assisting in diesel distribution inside the chamber. This combination creates a multipoint ignition of diesel throughout the chamber that generate very fast heat release rate and higher maximum pressure. Furthermore, lighter yellow color of the flame indicates lower soot production in compared with diesel combustion.

Isotope applications in the environmental field

International Nuclear Information System (INIS)

DeWitt, R.

1978-01-01

Established uses of enriched isotopes in the environmental field were surveyed to determine future trends in isotope needs. Based on established isotope uses, on the projected increase in the pollution problem, and on the apparent social and economic pressure for pollution abatement, a significant demand for enriched isotopes appears to be developing for the assessment and control of air, water, and soil pollutants. Isotopic techniques will be used in combination with conventional methods of detection and measurement, such as gas chromatography, x-ray fluorescence, and atomic absorption. Recent advances in economical isotope separation methods, instrumentation, and methodology promise to place isotopic technology within the reach of most research and industrial institutions. Increased application of isotope techniques appears most likely to occur in areas where data are needed to characterize the movement, behavior, and fate of pollutants in the environment

Stochastic modelling of turbulent combustion for design optimization of gas turbine combustors

Science.gov (United States)

Mehanna Ismail, Mohammed Ali

The present work covers the development and the implementation of an efficient algorithm for the design optimization of gas turbine combustors. The purpose is to explore the possibilities and indicate constructive suggestions for optimization techniques as alternative methods for designing gas turbine combustors. The algorithm is general to the extent that no constraints are imposed on the combustion phenomena or on the combustor configuration. The optimization problem is broken down into two elementary problems: the first is the optimum search algorithm, and the second is the turbulent combustion model used to determine the combustor performance parameters. These performance parameters constitute the objective and physical constraints in the optimization problem formulation. The examination of both turbulent combustion phenomena and the gas turbine design process suggests that the turbulent combustion model represents a crucial part of the optimization algorithm. The basic requirements needed for a turbulent combustion model to be successfully used in a practical optimization algorithm are discussed. In principle, the combustion model should comply with the conflicting requirements of high fidelity, robustness and computational efficiency. To that end, the problem of turbulent combustion is discussed and the current state of the art of turbulent combustion modelling is reviewed. According to this review, turbulent combustion models based on the composition PDF transport equation are found to be good candidates for application in the present context. However, these models are computationally expensive. To overcome this difficulty, two different models based on the composition PDF transport equation were developed: an improved Lagrangian Monte Carlo composition PDF algorithm and the generalized stochastic reactor model. Improvements in the Lagrangian Monte Carlo composition PDF model performance and its computational efficiency were achieved through the

Determination of chlorine in graphite by combustion-ion chromatography

International Nuclear Information System (INIS)

Chen Lianzhong; Watanabe, Kazuo; Itoh, Mitsuo.

1995-09-01

A combustion/ion chromatographic method has been studied for the sensitive determination of chlorine in graphite. A graphite sample was burnt at 900degC in a silica reaction tube at an oxygen flow rate of 200 ml/min. Chlorine evolved was absorbed in 20 ml of a 0.1 mM sodium carbonate solution. The solution was evaporated to dryness. The residue was dissolved with a small volume of water. Chlorine in the solution was determined using ion chromatography. The method was applied to JAERI graphite certified reference materials and practical graphite materials. The detection limit was about 0.8 μgCl/g for a 2.0 g sample. The precision was about 2.5% (relative standard deviation) for samples with chlorine content of 70 μg/g level. The method is also usable for coal samples. (author)

Chemical stability of levoglucosan: An isotopic perspective

Science.gov (United States)

Sang, X. F.; Gensch, I.; Kammer, B.; Khan, A.; Kleist, E.; Laumer, W.; Schlag, P.; Schmitt, S. H.; Wildt, J.; Zhao, R.; Mungall, E. L.; Abbatt, J. P. D.; Kiendler-Scharr, A.

2016-05-01

The chemical stability of levoglucosan was studied by exploring its isotopic fractionation during the oxidation by hydroxyl radicals. Aqueous solutions as well as mixed (NH4)2SO4-levoglucosan particles were exposed to OH. In both cases, samples experiencing different extents of processing were isotopically analyzed by Thermal Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS). From the dependence of levoglucosan δ13C and concentration on the reaction extent, the kinetic isotope effect (KIE) of the OH oxidation reactions was determined to be 1.00187±0.00027 and 1.00229±0.00018, respectively. Both show good agreement within the uncertainty range. For the heterogeneous oxidation of particulate levoglucosan by gas-phase OH, a reaction rate constant of (2.67±0.03)·10-12 cm3 molecule-1S-1 was derived. The laboratory kinetic data, together with isotopic source and ambient observations, give information on the extent of aerosol chemical processing in the atmosphere.

Flashback mechanisms in lean premixed gas turbine combustion

CERN Document Server

Benim, Ali Cemal

2014-01-01

Blending fuels with hydrogen offers the potential to reduce NOx and CO2 emissions in gas turbines, but doing so introduces potential new problems such as flashback.  Flashback can lead to thermal overload and destruction of hardware in the turbine engine, with potentially expensive consequences. The little research on flashback that is available is fragmented. Flashback Mechanisms in Lean Premixed Gas Turbine Combustion by Ali Cemal Benim will address not only the overall issue of the flashback phenomenon, but also the issue of fragmented and incomplete research.Presents a coherent review of f

Gas chromatography of β-diketonates

International Nuclear Information System (INIS)

Burgett, C.A.

1976-01-01

The history of separation of metal complexes by gas chromatography is reviewed. The greatest success has been achieved with metal halides or metal β-diketonates, particularly with chelates of the small elements, Be and Al, and the extremely inert chromium diketonates. Many problems still remain concerning the development of suitable chromatographic techniques for many chelates; however, the technique of synergic solvent extraction, mixed-ligand complex chromatography, the synthesis of new heteroatomic ligands, and the advent of new liquid phases are discussed as means to increase the number of unique techniques for separation and analysis of metals. Methods are suggested and references are cited for chromatographic analysis of elements in the following groups: alkali metals, alkaline earths, Group IIIA, IVB, VB, VIB, VIIB, VIII, IB, and IIB. Special attention is given to separation of the volatile complexes of Sc, Y, the lanthanides, the actinides, and Pb. 156 references

Boron isotope separation by ion exchange chromatography using weakly basic anion exchange resin

International Nuclear Information System (INIS)

Sakuma, Yoichi; Aida, Masao; Okamoto, Makoto; Kakihana, Hidetake

1980-01-01

Isotopic plateau displacement chromatography, a useful method for isotope separation is presented. The boric acid band formed in a column of weakly basic anion exchange resin Diaion WA21 can be eluted with pure water. In order to obtain good accumulation of the isotope effect, a series of experiments with different migration length were carried out. The boron-10 enriched part of the boric acid absorbed band was always preceded by the isotopic plateau part, in which the atomic fraction of boron-10 was maintained at its original value. The atomic fraction of boron-10 at the end of the chromatogram increased with migration length, and in the case of 256-m migration, boron-10 was enriched from its original atomic fraction of 19.84 to 91.00%, the separation factor S being constant irrespective of migration length: S = 1.0100 +- 0.0005. (author)

Combustion heating value gas in a gas turbine

Energy Technology Data Exchange (ETDEWEB)

Kelsall, G [CTDD, British Coal Corporation, Cheltenham (United Kingdom); Cannon, M [European Gas Turbines Ltd., Lincoln (United Kingdom)

1997-12-31

Advanced coal and/or biomass based power generation systems offer the potential for high efficiency electricity generation with minimum environmental impact. An important component for many of these advanced power generation cycles is the gas turbine, for which development of a combustion system to burn low calorific value coal derived fuel gas, at turbine inlet temperatures of typically 1 100 - 1 260 deg C and with minimum pollutant emissions, is a key issue. A phased combustor development programme is under-way burning low calorific value fuel gas (3.6 - 4.1 MJ/m{sup 3}) with low emissions, particularly NO{sub x} derived from fuel-bound nitrogen. The first and second phases of the combustor development programme have been completed. The first phase used a generic tubo-annular, prototype combustor based on conventional design principles. Combustor performance for this first prototype combustor was encouraging. The second phase assessed five design variants of the prototype combustor, each variant achieving a progressive improvement in combustor performance. The operating conditions for this assessment were selected to represent a particular medium sized industrial gas turbine operating as part of an Air Blown Gasification Cycle (ABGC). The test conditions assessed therefore included the capability to operate the combustor using natural gas as a supplementary fuel, to suit one possible start-up procedure for the cycle. The paper presents a brief overview of the ABGC development initiative and discusses the general requirements for a gas turbine operating within such a cycle. In addition, it presents full combustor performance results for the second phase of turbine combustor development and discusses the rationale for the progressive design modifications made within that programme. The strategy for the further development of the combustor to burn low calorific value fuel gas with very low conversion of fuel-bound nitrogen to NO{sub x} is presented. (orig.) 6 refs.

Combustion heating value gas in a gas turbine

Energy Technology Data Exchange (ETDEWEB)

Kelsall, G. [CTDD, British Coal Corporation, Cheltenham (United Kingdom); Cannon, M. [European Gas Turbines Ltd., Lincoln (United Kingdom)

1996-12-31

Advanced coal and/or biomass based power generation systems offer the potential for high efficiency electricity generation with minimum environmental impact. An important component for many of these advanced power generation cycles is the gas turbine, for which development of a combustion system to burn low calorific value coal derived fuel gas, at turbine inlet temperatures of typically 1 100 - 1 260 deg C and with minimum pollutant emissions, is a key issue. A phased combustor development programme is under-way burning low calorific value fuel gas (3.6 - 4.1 MJ/m{sup 3}) with low emissions, particularly NO{sub x} derived from fuel-bound nitrogen. The first and second phases of the combustor development programme have been completed. The first phase used a generic tubo-annular, prototype combustor based on conventional design principles. Combustor performance for this first prototype combustor was encouraging. The second phase assessed five design variants of the prototype combustor, each variant achieving a progressive improvement in combustor performance. The operating conditions for this assessment were selected to represent a particular medium sized industrial gas turbine operating as part of an Air Blown Gasification Cycle (ABGC). The test conditions assessed therefore included the capability to operate the combustor using natural gas as a supplementary fuel, to suit one possible start-up procedure for the cycle. The paper presents a brief overview of the ABGC development initiative and discusses the general requirements for a gas turbine operating within such a cycle. In addition, it presents full combustor performance results for the second phase of turbine combustor development and discusses the rationale for the progressive design modifications made within that programme. The strategy for the further development of the combustor to burn low calorific value fuel gas with very low conversion of fuel-bound nitrogen to NO{sub x} is presented. (orig.) 6 refs.

Gas Chromatography-Mass Spectrometric Analysis of Nematicidal ...

African Journals Online (AJOL)

Purpose: To investigate the chemical composition and nematicidal activity of the essential oil of. Valeriana amurensis ... Methods: The essential oil of V. amurensis roots was obtained by hydrodistillation and analyzed by gas chromatography (GC) ..... Aβ1-40 and Caspase-3 in Alzheimer's disease model rat's brain. J Chin ...

Gas Chromatography Mass Spectrometry of Quassia undulata Seed ...

African Journals Online (AJOL)

Prof. Ogunji

The use of gas chromatography mass spectrometry (GC MS) as a sensitive and specific technique ... cold flow properties and stability of the fuel to oxidation, peroxidation and polymerization .... determinants of both the physical and chemical ...

Historical and future emission of hazardous air pollutants (HAPs) from gas-fired combustion in Beijing, China.

Science.gov (United States)

Xue, Yifeng; Nie, Lei; Zhou, Zhen; Tian, Hezhong; Yan, Jing; Wu, Xiaoqing; Cheng, Linglong

2017-07-01

The consumption of natural gas in Beijing has increased in the past decade due to energy structure adjustments and air pollution abatement. In this study, an integrated emission inventory of hazardous air pollutants (HAPs) emitted from gas-fired combustion in Beijing was developed for the period from 2000 to 2014 using a technology-based approach. Future emission trends were projected through 2030 based on current energy-related and emission control policies. We found that emissions of primary HAPs exhibited an increasing trend with the rapid increase in natural gas consumption. Our estimates indicated that the total emissions of NO X , particulate matter (PM) 10 , PM 2.5 , CO, VOCs, SO 2 , black carbon, Pb, Cd, Hg, As, Cr, Cu, Ni, Zn, polychlorinated dibenzo-p-dioxins and dibenzofurans, and benzo[a]pyrene from gas-fired combustion in Beijing were approximately 22,422 t, 1042 t, 781 t, 19,097 t, 653 t, 82 t, 19 t, 0.6 kg, 0.1 kg, 43 kg, 52 kg, 0.3 kg, 0.03 kg, 4.3 kg, 0.6 kg, 216 μg, and 242 g, respectively, in 2014. To mitigate the associated air pollution and health risks caused by gas-fired combustion, stricter emission standards must be established. Additionally, combustion optimization and flue gas purification system could be used for lowering NO X emissions from gas-fired combustion, and gas-fired facilities should be continuously monitored based on emission limits. Graphical abstract Spatial distribution and typical live photos of gas-fired boiler in Beijing.

Direct Growth of Bacteria in Headspace Vials Allows for Screening of Volatiles by Gas Chromatography Mass Spectrometry

OpenAIRE

Collin M. Timm; Evan P. Lloyd; Amanda Egan; Ray Mariner; David Karig

2018-01-01

Bacterially produced volatile organic compounds (VOCs) can modify growth patterns of eukaryotic hosts and competing/cohabiting microbes. These compounds have been implicated in skin disorders and attraction of biting pests. Current methods to detect and characterize VOCs from microbial cultures can be laborious and low-throughput, making it difficult to understand the behavior of microbial populations. In this work we present an efficient method employing gas chromatography/mass spectrometry ...

High Relative Abundance of Biofuel Sourced Ethanol in Precipitation in the US and Brazil Determined Using Compound Specific Stable Carbon Isotopes

Science.gov (United States)

Shimizu, M. S.; Felix, J. D. D.; Casas, M.; Avery, G. B., Jr.; Kieber, R. J.; Mead, R. N.; Willey, J. D.; Lane, C.

2017-12-01

Ethanol biofuel production and consumption have increased exponentially over the last two decades to help reduce greenhouse gas emissions. Currently, 85% of global ethanol production and consumption occurs in the US and Brazil. Increasing biofuel ethanol usage in these two countries enhances emissions of uncombusted ethanol to the atmosphere contributing to poor air quality. Although measurements of ethanol in the air and the precipitation reveal elevated ethanol concentrations in densely populated cities, other sources such as natural vegetation can contribute to emission to the atmosphere. Previous modeling studies indicated up to 12% of atmospheric ethanol is from anthropogenic emissions. Only one gas phase study in southern Florida attempted to constrain the two sources through direct isotopic measurements. The current study used a stable carbon isotope method to constrain sources of ethanol in rainwater from the US and Brazil. A method was developed using solid phase microextraction (SPME) with subsequent analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Stable carbon isotope signatures (δ13C) of vehicle ethanol emission sources for both the US (-9.8‰) and Brazil (-12.7‰) represented C4 plants as feedstock (corn and sugarcane) for biofuel production. An isotope mixing model using biofuel from vehicles (C4 plants) and biogenic (C3 plants) end-members was implemented to estimate ethanol source apportionment in the rain. We found that stable carbon isotope ratio of ethanol in the rain ranged between -22.6‰ and -12.7‰. Our results suggest that the contribution of biofuel to atmospheric ethanol can be higher than previously estimated. As biofuel usage increasing globally, it is essential to determine the relative abundance of anthropogenic ethanol in other areas of the world.

High-temperature CO / HC gas sensors to optimize firewood combustion in low-power fireplaces

Directory of Open Access Journals (Sweden)

B. Ojha

2017-06-01

Full Text Available In order to optimize firewood combustion in low-power firewood-fuelled fireplaces, a novel combustion airstream control concept based on the signals of in situ sensors for combustion temperature, residual oxygen concentration and residual un-combusted or partly combusted pyrolysis gas components (CO and HC has been introduced. A comparison of firing experiments with hand-driven and automated airstream-controlled furnaces of the same type showed that the average CO emissions in the high-temperature phase of the batch combustion can be reduced by about 80 % with the new control concept. Further, the performance of different types of high-temperature CO / HC sensors (mixed-potential and metal oxide types, with reference to simultaneous exhaust gas analysis by a high-temperature FTIR analysis system, was investigated over 20 batch firing experiments (∼ 80 h. The distinctive sensing behaviour with respect to the characteristically varying flue gas composition over a batch firing process is discussed. The calculation of the Pearson correlation coefficients reveals that mixed-potential sensor signals correlate more with CO and CH4; however, different metal oxide sensitive layers correlate with different gas species: 1 % Pt / SnO2 designates the presence of CO and 2 % ZnO / SnO2 designates the presence of hydrocarbons. In the case of a TGS823 sensor element, there was no specific correlation with one of the flue gas components observed. The stability of the sensor signals was evaluated through repeated exposure to mixtures of CO, N2 and synthetic air after certain numbers of firing experiments and exhibited diverse long-term signal instabilities.

Characterization of the fermentation process by gas chromatography Lasiodiplodia theobromae and gas chromatography coupled with mass spectrometry

International Nuclear Information System (INIS)

Castillo Portela, Grolamys; Eng Sanchez, Felipe; Nogueiras Lima, Clara

2014-01-01

Lasiodiplodia theobromae is a fungus, which has been reported by some authors as a high yield producer of the phytohormone jasmonic acid (JA). An indigenous strain of this fungus has been used for producing a fermentation broth with a high JA concentration by the Cuban Research Institute for Sugar Cane Derivatives (ICIDCA), registered as BIOJAS. The broth has been applied to some agricultural crops and demonstrated its economic feasibility as plant growth regulator and biological control of various phytopathogenic microorganisms and pests. Both fermentation broth and biomass from this fungus contain some other metabolites having bioactive properties, for instance, fatty acids. This paper shows the composition and quantification of fatty acids in the biomass using Gas Chromatography (GC) and the identification of substances profile in fermentation broth by Gas Chromatography coupled to Mass Spectrometry (GC-MS). The most fatty acids in the biomass are palmitic, stearic, oleic, linoleic and linolenic acids, being oleic acid the major component. On the other hand, 2,32 % of fatty acid esters; 2,47 % of alkenes; 14,40 % of alcohols; 30,15 % of aldehydes and 21,73 % of paraffins were detected in the composition of fermentation broth

Hyphenated techniques in multidimensional gas chromatography for analysis of wine aroma and related odorants

OpenAIRE

Chin, Sung Tong

2017-01-01

The advent of analytical multidimensional gas chromatography (MDGC) techniques, with recent development in comprehensive two-dimensional gas chromatography (GC×GC) as well as microfluidic technology in conventional heart-cut MDGC, has achieved excellent separation efficiency for advanced characterization of complex volatile and semi-volatile samples, which is unlikely to be accomplished by single dimensional chromatography. This dissertation work has highlighted the potential opportunities fo...

Multiresidue analysis of pesticides in olive oil by gel permeation chromatography followed by gas chromatography-tandem mass-spectrometric determination

International Nuclear Information System (INIS)

Sanchez, Andres Garcia; Martos, Natividad Ramos; Ballesteros, Evaristo

2006-01-01

A method for the multiresidue analysis of olive oil samples for 26 pesticides is proposed. Residual pesticides are extracted from oil using an n-hexane/acetonitrile mixture, extracts being cleaned-up by gel permeation chromatography (GPC) for analysis by gas chromatography-tandem mass spectrometry (GC-MS/MS). Electron ionization and chemical ionization are employed in a single analysis for the determination of pesticides. Pesticide recoveries from virgin and refined olive oil spiked with 10, 100 and 250 μg/kg concentrations of the pesticides ranged from 83.8 to 110.3%. The proposed method features good sensitivity: its limits of quantification are low enough to allow pesticide residues to be determined at concentrations below the maximum residue levels legally accepted. The precision, expressed as relative standard deviation, ranges from 4.93 to 8.11%. Applicability was tested on 40 olive oil samples. Several pesticides were detected in most of the virgin olive oil samples. By contrast, refined olive samples contained few pesticides, and only endosulfan sulphate was detected in all

Influence of moist combustion gas on performance of a sub-critical turbine

International Nuclear Information System (INIS)

Yang Wenbin; Su Ming

2005-01-01

In the HAT cycle, as the absolute humidity of the moist combustion gas increases, the performance of the turbine will also change. In this paper, one model to calculate the thermodynamic properties of the moist combustion gas is introduced, and another model to calculate the performance of the turbine is formulated based on the equations of one dimensional flow. Using these models with the geometric parameters of the turbine fixed, at the design working condition, the performance of the turbine is calculated and analyzed for different absolute humidities. Finally, some conclusions about the turbine performance are presented

Influence of carbonation under oxy-fuel combustion flue gas on the leachability of heavy metals in MSWI fly ash.

Science.gov (United States)

Ni, Peng; Xiong, Zhuo; Tian, Chong; Li, Hailong; Zhao, Yongchun; Zhang, Junying; Zheng, Chuguang

2017-09-01

Due to the high cost of pure CO 2 , carbonation of MSWI fly ash has not been fully developed. It is essential to select a kind of reaction gas with rich CO 2 instead of pure CO 2 . The CO 2 uptake and leaching toxicity of heavy metals in three typical types of municipal solid waste incinerator (MSWI) fly ash were investigated with simulated oxy-fuel combustion flue gas under different reaction temperatures, which was compared with both pure CO 2 and simulated air combustion flue gas. The CO 2 uptake under simulated oxy-fuel combustion flue gas were similar to that of pure CO 2 . The leaching concentration of heavy metals in all MSWI fly ash samples, especially in ash from Changzhou, China (CZ), decreased after carbonation. Specifically, the leached Pb concentration of the CZ MSWI fly ash decreased 92% under oxy-fuel combustion flue gas, 95% under pure CO 2 atmosphere and 84% under the air combustion flue gas. After carbonation, the leaching concentration of Pb was below the Chinese legal limit. The leaching concentration of Zn from CZ sample decreased 69% under oxy-fuel combustion flue gas, which of Cu, As, Cr and Hg decreased 25%, 33%, 11% and 21%, respectively. In the other two samples of Xuzhou, China (XZ) and Wuhan, China (WH), the leaching characteristics of heavy metals were similar to the CZ sample. The speciation of heavy metals was largely changed from the exchangeable to carbonated fraction because of the carbonation reaction under simulated oxy-fuel combustion flue gas. After carbonation reaction, most of heavy metals bound in carbonates became more stable and leached less. Therefore, oxy-fuel combustion flue gas could be a low-cost source for carbonation of MSWI fly ash. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gas-chromatographic separation of hydrogen isotopes mixtures on capillary molecular sieve 5 A column at 173 K

International Nuclear Information System (INIS)

Bidica, N.; Preda, A.; Stanciu, V.

2002-01-01

Analysis of a gas mixture of hydrogen species, is not too easy because the differences in their physical-chemical properties are very small; the most different are their masses, and consequently most common analytical method appear to be the mass-spectrometry. However, the impossibility to distinguish between two ions (atomic or molecular) with the same mass renders this method as unapplicable. Another problem is the decay of tritium with production of 3 He. These disadvantages of mass-spectrometry have made that other analytical methods, like gas chromatography, to be considered and developed. Thus, there are many papers about various chromatographic columns especially prepared for hydrogen species separation but the preparation and treatment of these columns are very difficult to reproduce. Besides these, there are two other main disadvantages: column operating temperature is very low and long retention times for hydrogen species (more than half an hour) are required. However, the gas-chromatography method still remains an appropriate one. The method described in this paper was based on using a capillary molecular sieve 5A column which has been operated for this kind of separation. The retention times were relatively short, about 8-9 minutes. The carrier gas was Ne and the detector - TCD. In the paper chromatograms for various carrier flow rates and various hydrogen isotope mixtures are presented. The results demonstrated a quite good efficiency for H 2 , HD, D 2 and a not very good one for orthoH 2 -paraH 2 . (authors)

Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis.

Science.gov (United States)

Kehimkar, Benjamin; Hoggard, Jamin C; Marney, Luke C; Billingsley, Matthew C; Fraga, Carlos G; Bruno, Thomas J; Synovec, Robert E

2014-01-31

There is an increased need to more fully assess and control the composition of kerosene-based rocket propulsion fuels such as RP-1. In particular, it is critical to make better quantitative connections among the following three attributes: fuel performance (thermal stability, sooting propensity, engine specific impulse, etc.), fuel properties (such as flash point, density, kinematic viscosity, net heat of combustion, and hydrogen content), and the chemical composition of a given fuel, i.e., amounts of specific chemical compounds and compound classes present in a fuel as a result of feedstock blending and/or processing. Recent efforts in predicting fuel chemical and physical behavior through modeling put greater emphasis on attaining detailed and accurate fuel properties and fuel composition information. Often, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is employed to provide chemical composition information. Building on approaches that used GC-MS, but to glean substantially more chemical information from these complex fuels, we recently studied the use of comprehensive two dimensional (2D) gas chromatography combined with time-of-flight mass spectrometry (GC×GC-TOFMS) using a "reversed column" format: RTX-wax column for the first dimension, and a RTX-1 column for the second dimension. In this report, by applying chemometric data analysis, specifically partial least-squares (PLS) regression analysis, we are able to readily model (and correlate) the chemical compositional information provided by use of GC×GC-TOFMS to RP-1 fuel property information such as density, kinematic viscosity, net heat of combustion, and so on. Furthermore, we readily identified compounds that contribute significantly to measured differences in fuel properties based on results from the PLS models. We anticipate this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an

Quantification of 2-acetyl-1-pyrroline in rice by stable isotope dilution assay through headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Maraval, Isabelle [UMR Qualisud, CIRAD, 73 Rue J. F. Breton, 34398 Montpellier Cedex 5 (France); UMR Qualisud, Universite Montpellier 2, place E. Bataillon, 34095 Montpellier Cedex 5 (France); Sen, Kemal [Department of Food Engineering, Faculty of Agriculture, University of Cukurova, 01330 Adana (Turkey); Agrebi, Abdelhamid; Menut, Chantal; Morere, Alain [UMR 5247, Institut des Biomolecules Max Mousseron (IBMM), CNRS, Universites Montpellier 2 et 1, Ecole Nationale Superieure de Chimie de Montpellier, 8 Rue de l' Ecole Normale, 34296 Montpellier Cedex 5 (France); Boulanger, Renaud [UMR Qualisud, CIRAD, 73 Rue J. F. Breton, 34398 Montpellier Cedex 5 (France); Gay, Frederic [CIRAD, DORAS Centre, Research and Development Building, Kasetsart University, Bangkok 10900 (Thailand); Mestres, Christian [UMR Qualisud, CIRAD, 73 Rue J. F. Breton, 34398 Montpellier Cedex 5 (France); Gunata, Ziya, E-mail: zgunata@univ-montp2.fr [UMR Qualisud, Universite Montpellier 2, place E. Bataillon, 34095 Montpellier Cedex 5 (France)

2010-08-24

A new and convenient synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor compound in rice, and its ring-deuterated analog, 2-acetyl-1-d{sub 2}-pyrroline (2AP-d{sub 2}), was reported. A stable isotope dilution assay (SIDA), involving headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-positive chemical ionization-ion trap-tandem mass spectrometry (GC-PCI-IT-MS-MS), was developed for 2AP quantification. A divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used for HS-SPME procedure and parameters affecting analytes recovery, such as extraction time and temperature, pH and salt, were studied. The repeatability of the method (n = 10) expressed as relative standard deviation (RSD) was 11.6%. A good linearity was observed from 5.9 to 779 ng of 2AP (r{sup 2} = 0.9989). Limits of detection (LOD) and quantification (LOQ) for 2AP were 0.1 and 0.4 ng g{sup -1} of rice, respectively. The recovery of spiked 2AP from rice matrix was almost complete. The developed method was applied to the quantification of 2AP in aerial parts and grains of scented and non-scented rice cultivars.

Measuring gluconeogenesis using a low dose of 2H2O: advantage of isotope fractionation during gas chromatography.

Science.gov (United States)

Katanik, Jill; McCabe, Brendan J; Brunengraber, Daniel Z; Chandramouli, Visvanathan; Nishiyama, Fumie J; Anderson, Vernon E; Previs, Stephen F

2003-05-01

The contribution of gluconeogenesis to glucose production can be measured by enriching body water with (2)H(2)O to approximately 0.5% (2)H and determining the ratio of (2)H that is bound to carbon-5 vs. carbon-2 of blood glucose. This labeling ratio can be measured using gas chromatography-mass spectrometry after the corresponding glucose carbons are converted to formaldehyde and then to hexamethylenetetramine (HMT). We present a technique for integrating ion chromatograms that allows one to use only 0.05% (2)H in body water (i.e., 10 times less than the current dose). This technique takes advantage of the difference in gas chromatographic retention times of naturally labeled HMT and [(2)H]HMT. We discuss the advantage(s) of using a low dose of (2)H(2)O to quantify the contribution of gluconeogenesis.

Droplet evaporation and combustion in a liquid-gas multiphase system

Science.gov (United States)

Muradoglu, Metin; Irfan, Muhammad

2017-11-01

Droplet evaporation and combustion in a liquid-gas multiphase system are studied computationally using a front-tracking method. One field formulation is used to solve the flow, energy and species equations with suitable jump conditions. Both phases are assumed to be incompressible; however, the divergence-free velocity field condition is modified to account for the phase change at the interface. Both temperature and species gradient driven phase change processes are simulated. Extensive validation studies are performed using the benchmark cases: The Stefan and the sucking interface problems, d2 law and wet bulb temperature comparison with the psychrometric chart values. The phase change solver is then extended to incorporate the burning process following the evaporation as a first step towards the development of a computational framework for spray combustion. We used detailed chemistry, variable transport properties and ideal gas behaviour for a n-heptane droplet combustion; the chemical kinetics being handled by the CHEMKIN. An operator-splitting approach is used to advance temperature and species mass fraction in time. The numerical results of the droplet burning rate, flame temperature and flame standoff ratio show good agreement with the experimental and previous numeric.

Impact of CO_2-enriched combustion air on micro-gas turbine performance for carbon capture

International Nuclear Information System (INIS)

Best, Thom; Finney, Karen N.; Ingham, Derek B.; Pourkashanian, Mohamed

2016-01-01

Power generation is one of the largest anthropogenic greenhouse gas emission sources; although it is now reducing in carbon intensity due to switching from coal to gas, this is only part of a bridging solution that will require the utilization of carbon capture technologies. Gas turbines, such as those at the UK Carbon Capture Storage Research Centre's Pilot-scale Advanced CO_2 Capture Technology (UKCCSRC PACT) National Core Facility, have high exhaust gas mass flow rates with relatively low CO_2 concentrations; therefore solvent-based post-combustion capture is energy intensive. Exhaust gas recirculation (EGR) can increase CO_2 levels, reducing the capture energy penalty. The aim of this paper is to simulate EGR through enrichment of the combustion air with CO_2 to assess changes to turbine performance and potential impacts on complete generation and capture systems. The oxidising air was enhanced with CO_2, up to 6.29%vol dry, impacting mechanical performance, reducing both engine speed by over 400 revolutions per minute and compression temperatures. Furthermore, it affected complete combustion, seen in changes to CO and unburned hydrocarbon emissions. This impacted on turbine efficiency, which increased specific fuel consumption (by 2.9%). CO_2 enhancement could therefore result in significant efficiency gains for the capture plant. - Highlights: • Experimental investigation of the impact of exhaust gas recirculation (EGR) on GT performance. • Combustion air was enhanced with CO_2 to simulate EGR. • EGR impact was ascertained by CO and unburned hydrocarbon changes. • Primary factor influencing performance was found to be oxidiser temperature. • Impact of CO_2 enhancement on post-combustion capture efficiency.

Gas chromatographic isolation of individual compounds from complex matrices for radiocarbon dating.

Science.gov (United States)

Eglinton, T I; Aluwihare, L I; Bauer, J E; Druffel, E R; McNichol, A P

1996-03-01

This paper describes the application of a novel, practical approach for isolation of individual compounds from complex organic matrices for natural abundance radiocarbon measurement. This is achieved through the use of automated preparative capillary gas chromatography (PCGC) to separate and recover sufficient quantities of individual target compounds for (14)C analysis by accelerator mass spectrometry (AMS). We developed and tested this approach using a suite of samples (plant lipids, petroleums) whose ages spanned the (14)C time scale and which contained a variety of compound types (fatty acids, sterols, hydrocarbons). Comparison of individual compound and bulk radiocarbon signatures for the isotopically homogeneous samples studied revealed that Δ(14)C values generally agreed well (±10%). Background contamination was assessed at each stage of the isolation procedure, and incomplete solvent removal prior to combustion was the only significant source of additional carbon. Isotope fractionation was addressed through compound-specific stable carbon isotopic analyses. Fractionation of isotopes during isolation of individual compounds was minimal (radiocarbon measurements. The addition of carbon accompanying derivatization of functionalized compounds (e.g., fatty acids and sterols) prior to chromatographic separation represents a further source of potential error. This contribution can be removed using a simple isotopic mass balance approach. Based on these preliminary results, the PCGC-based approach holds promise for accurately determining (14)C ages on compounds specific to a given source within complex, heterogeneous samples.

Identification of organic acids as potential biomarkers in the urine of autistic children using gas chromatography/mass spectrometry.

Science.gov (United States)

Kałużna-Czaplińska, Joanna; Żurawicz, Ewa; Struck, Wiktoria; Markuszewski, Michał

2014-09-01

There is a need to identify metabolic phenotypes in autism as they might each require unique approaches to prevention. Biological markers can help define autism subtypes and reveal potential therapeutic targets. The aim of the study was to identify alterations of small molecular weight compounds and to find potential biomarkers. Gas chromatography/mass spectrometry was employed to evaluate major metabolic changes in low molecular weight urine metabolites of 14 children with autism spectrum disorders vs. 10 non-autistic subjects. The results prove the usefulness of an identified set of 21 endogenous compounds (including 14 organic acids), whose levels are changed in diseased children. Gas chromatography/mass spectrometry method combined with multivariate statistical analysis techniques provide an efficient way of depicting metabolic perturbations of diseases, and may potentially be applicable as a novel strategy for the noninvasive diagnosis and treatment of autism. Copyright © 2014 Elsevier B.V. All rights reserved.

ICP-MS as the method of the determination of gallium, indium and thallium isotope ratios in the studies of isotope effects in the chromatography systems

International Nuclear Information System (INIS)

Herdzik, I.

2006-01-01

The procedure of the determination of gallium, indium and thallium isotope ratios and its application to the studies of the isotope effects in chromatography systems by the ICP-MS method (inductively coupled plasma-mass spectrometry) are presented. It was shown that it is possible to determine the isotope ratios of gallium ( 69/71 Ga), indium ( 113/115 In) and thallium ( 203/205 Tl) with the relative standard deviation 0.03-0.07%. Such precision appeared to be sufficient to calculate the unit separation factors in the column chromatographic processes. (author) [pl

Gas chromatography mass spectrometry : key technology in metabolomics

NARCIS (Netherlands)

Koek, Maud Marijtje

2009-01-01

Metabolomics involves the unbiased quantitative and qualitative analysis of the complete set of metabolites present in cells, body fluids and tissues. Gas chromatography coupled to mass spectrometry (GC-MS) is very suitable for metabolomics analysis, as it combines high separation power with

Extending the molecular application range of gas chromatography

NARCIS (Netherlands)

Kaal, E.; Janssen, H.-G.

2008-01-01

Gas chromatography is an important analytical technique for qualitative and quantitative analysis in a wide range of application areas. It is fast, provides a high peak capacity, is sensitive and allows combination with a wide range of selective detection methods including mass spectrometry.

Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

International Nuclear Information System (INIS)

Manard, Manuel J.; Weeks, Stephan; Kyle, Kevin

2010-01-01

The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and

Technology for emission control in internal combustion engines; Kakushu nainen kikan ni okeru hai gas joka gijutsu

Energy Technology Data Exchange (ETDEWEB)

Shioji, M. [Kyoto University, Kyoto (Japan)

1998-09-01

Described herein are emission control technology and exhaust gas cleaning measures for internal combustion engines. Gas turbines burn relatively high-quality fuels, such as natural gas, kerosene, diesel oil and gas oil, where the major concerns are to reduce NOx and dust emissions. The NOx abatement techniques fall into two general categories; wet processes which inject water or steam, and dry processes which depend on improved combustion. Power generation and cogeneration which burn natural gas adopt lean, premixed combustion and two-stage combustion as the major approaches. Low-speed, large-size diesel engines, which realize very high thermal efficiency, discharge high concentrations of NOx. Delayed fuel injection timing is the most easy NOx abatement technique to meet the related regulations, but is accompanied by decreased fuel economy. Use of water-emulsified fuel, water layer injection and multi-port injection can reduce NOx emissions without decreasing fuel economy, depending on optimization methods adopted. Automobile gasoline engines are required to further clean exhaust gases by catalystic systems. 9 refs., 10 figs., 6 tabs.

Combustion characteristics of natural gas-hydrogen hybrid fuel turbulent diffusion flame

Energy Technology Data Exchange (ETDEWEB)

El-Ghafour, S.A.A.; El-dein, A.H.E.; Aref, A.A.R. [Mechanical Power Engineering Department, Faculty of Engineering, Suez Canal University, Port-Said (Egypt)

2010-03-15

Combustion characteristics of natural gas - hydrogen hybrid fuel were investigated experimentally in a free jet turbulent diffusion flame flowing into a slow co-flowing air stream. Experiments were carried out at a constant jet exit Reynolds number of 4000 and with a wide range of NG-H{sub 2} mixture concentrations, varied from 100%NG to 50%NG-50% H{sub 2} by volume. The effect of hydrogen addition on flame stability, flame length, flame structure, exhaust species concentration and pollutant emissions was conducted. Results showed that, hydrogen addition sustains a progressive improvement in flame stability and reduction in flame length, especially for relatively high hydrogen concentrations. Hydrogen-enriched flames found to have a higher combustion temperatures and reactivity than natural gas flame. Also, it was found that hydrogen addition to natural gas is an ineffective strategy for NO and CO reduction in the studied range, while a significant reduction in the %CO{sub 2} molar concentration by about 30% was achieved. (author)

DEVELOPMENT OF SAMPLING AND ANALYTICAL METHODS FOR THE MEASUREMENT OF NITROUS OXIDE FROM FOSSIL FUEL COMBUSTION SOURCES

Science.gov (United States)

The report documents the technical approach and results achieved while developing a grab sampling method and an automated, on-line gas chromatography method suitable to characterize nitrous oxide (N2O) emissions from fossil fuel combustion sources. The two methods developed have...

Fractionation of oxygen and hydrogen isotopes at the hydrate gas forming in the sea sediments

International Nuclear Information System (INIS)

Pashkina, V.I.; Esikov, A.D.

1990-01-01

The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies show that heavy isotopes of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ 18 O=+1.99per mille, δD=+23per mille relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading. (orig.) [de

Method and apparatus for manufacturing gas tags

International Nuclear Information System (INIS)

Gross, K.C.; Laug, M.T.

1996-01-01

For use in the manufacture of gas tags employed in a gas tagging failure detection system for a nuclear reactor, a plurality of commercial feed gases each having a respective noble gas isotopic composition are blended under computer control to provide various tag gas mixtures having selected isotopic ratios which are optimized for specified defined conditions such as cost. Using a new approach employing a discrete variable structure rather than the known continuous-variable optimization problem, the computer controlled gas tag manufacturing process employs an analytical formalism from condensed matter physics known as stochastic relaxation, which is a special case of simulated annealing, for input feed gas selection. For a tag blending process involving M tag isotopes with N distinct feed gas mixtures commercially available from an enriched gas supplier, the manufacturing process calculates the cost difference between multiple combinations and specifies gas mixtures which approach the optimum defined conditions. The manufacturing process is then used to control tag blending apparatus incorporating tag gas canisters connected by stainless-steel tubing with computer controlled valves, with the canisters automatically filled with metered quantities of the required feed gases. 4 figs

A combustion setup to precisely reference δ13C and δ2H isotope ratios of pure CH4 to produce isotope reference gases of δ13C-CH4 in synthetic air

Directory of Open Access Journals (Sweden)

H. Schaefer

2012-09-01

Full Text Available Isotope records of atmospheric CH4 can be used to infer changes in the biogeochemistry of CH4. One factor currently limiting the quantitative interpretation of such changes are uncertainties in the isotope measurements stemming from the lack of a unique isotope reference gas, certified for δ13C-CH4 or δ2H-CH4. We present a method to produce isotope reference gases for CH4 in synthetic air that are precisely anchored to the VPDB and VSMOW scales and have δ13C-CH4 values typical for the modern and glacial atmosphere. We quantitatively combusted two pure CH4 gases from fossil and biogenic sources and determined the δ13C and δ2H values of the produced CO2 and H2O relative to the VPDB and VSMOW scales within a very small analytical uncertainty of 0.04‰ and 0.7‰, respectively. We found isotope ratios of −39.56‰ and −56.37‰ for δ13C and −170.1‰ and −317.4‰ for δ2H in the fossil and biogenic CH4, respectively. We used both CH4 types as parental gases from which we mixed two filial CH4 gases. Their δ13C was determined to be −42.21‰ and −47.25‰ representing glacial and present atmospheric δ13C-CH4. The δ2H isotope ratios of the filial CH4 gases were found to be −193.1‰ and −237.1‰, respectively. Next, we mixed aliquots of the filial CH4 gases with ultrapure N2/O2 (CH4 ≤ 2 ppb producing two isotope reference gases of synthetic air with CH4 mixing ratios near atmospheric values. We show that our method is reproducible and does not introduce isotopic fractionation for δ13C within the uncertainties of our detection limit (we cannot conclude this for δ2H because our system is currently not prepared for δ2H-CH4 measurements in air samples. The general principle of our method can be applied to produce synthetic isotope reference gases targeting δ2H-CH4 or other gas species.

The use of the isotopic composition of individual compounds for correlating spilled oils and refined products in the environment with suspected sources

International Nuclear Information System (INIS)

Philp, R.P.; Allen, J.; Kuder, T.

2002-01-01

Gas chromatography (GC) and gas chromatography/mass spectrometry (CGMS) are two methods generally used to correlate crude oils and refined products found in the environment with their suspected pollution sources. In certain cases, this can be done with bulk carbon isotope compositions, but with crude condensates, or refined products, the lack of biomarkers prohibits the successful use for making unique correlations. Such products can be correlated using an alternative method which makes use of combined gas chromatography-isotope ratio and mass spectrometry (GCIRMS). This method makes it possible to determine the carbon and hydrogen isotopic composition of individual compounds in crude oil, thus producing isotopic fingerprints that could be used in correlation studies. The feasibility of using of GCIRMS to correlate various spilled products in different environments was the main focus of this study. The authors are not proposing that this method will replace GC or GCMS, but are suggesting that it is a powerful tool that could be used in conjunction with the early methods. Carbon and hydrogen isotopic fractionation has been reported for light components such as benzene and toluene. Higher carbon numbered compounds do not seem to undergo major carbon isotopic fractionation as a result of weathering. Hydrogen variations are currently undergoing investigation for compounds with a carbon number greater than C10. Also, isotopic fractionation for refined products has the potential to attenuate naturally. 33 refs., 6 figs

Plasma wave detection in laser spectroscopy and gas chromatography

International Nuclear Information System (INIS)

Franzke, J.; Irmer, A. von; Veza, D.; Niemax, K.

1995-01-01

Frequency changes of plasma oscillations in low-pressure discharges are used for sensitive detection of atomic or molecular trace gases. Analyte selectivity can be either obtained by resonant laser excitation or by gas chromatography

Hazardous air pollutant emissions from gas-fired combustion sources: emissions and the effects of design and fuel type

Energy Technology Data Exchange (ETDEWEB)

England, G.C.; McGrath, T.P. [GE-Energy and Environmental Research Corp., Irvine, CA (United States); Gilmer, L. [Equilon Enterprises, Bellaire, TX (United States); Seebold, J.G. [Chevron Research and Technology Co., Richmond, CA (United States); Lev-On, M. [ARCO, Los Angeles, CA (United States); Hunt, T. [American Petroleum Institute, Washington, DC (United States)

2001-07-01

Air emissions from gas-fired combustion devices such as boilers, process heaters, gas turbines and stationary reciprocating engines contain hazardous air pollutants (HAPs) subjected to consideration under the federal clean air act (CAA). This work presents a recently completed major research project to develop an understanding of HAP emissions from gas-fired boilers and process heaters and new HAP emission factors based on field emission tests of gas-fired external combustion devices used in the petroleum industry. The effect of combustion system design and operating parameters on HAP emissions determined by both field and research tests are discussed. Data from field tests of gas-fired petroleum industry boilers and heaters generally show very low emission levels of organic HAPs. A comparison of the emission data for boilers and process heaters, including units with and without various forms of NO{sub x} emission controls, showed no significant difference in organic HAP emission characteristics due to process or burner design. This conclusion is also supported by the results of research tests with different burner designs. Based on field tests of units fired with natural gas and various petroleum industry process gases and research tests in which gas composition was intentionally varied, organic HAP emissions were not determined to be significantly affected by the gas composition. Research data indicate that elevated organic HAP emission levels are found only under extreme operating conditions (starved air or high excess air combustion) associated with poor combustion. (author)

Hazardous air pollutant emissions from gas-fired combustion sources: emissions and the effects of design and fuel type

International Nuclear Information System (INIS)

England, G.C.; McGrath, T.P.; Gilmer, L.; Seebold, J.G.; Lev-On, M.; Hunt, T.

2001-01-01

Air emissions from gas-fired combustion devices such as boilers, process heaters, gas turbines and stationary reciprocating engines contain hazardous air pollutants (HAPs) subjected to consideration under the federal clean air act (CAA). This work presents a recently completed major research project to develop an understanding of HAP emissions from gas-fired boilers and process heaters and new HAP emission factors based on field emission tests of gas-fired external combustion devices used in the petroleum industry. The effect of combustion system design and operating parameters on HAP emissions determined by both field and research tests are discussed. Data from field tests of gas-fired petroleum industry boilers and heaters generally show very low emission levels of organic HAPs. A comparison of the emission data for boilers and process heaters, including units with and without various forms of NO x emission controls, showed no significant difference in organic HAP emission characteristics due to process or burner design. This conclusion is also supported by the results of research tests with different burner designs. Based on field tests of units fired with natural gas and various petroleum industry process gases and research tests in which gas composition was intentionally varied, organic HAP emissions were not determined to be significantly affected by the gas composition. Research data indicate that elevated organic HAP emission levels are found only under extreme operating conditions (starved air or high excess air combustion) associated with poor combustion. (author)

Inductively coupled plasma-mass spectrometry for elemental analysis and isotope ratio determinations in individual organic compounds separated by gas chromatography

International Nuclear Information System (INIS)

Chong, N.S.; Houk, R.S.

1987-01-01

A gas chromatograph (GC) with a packed column was interfaced to an inductively coupled plasma-mass spectrometer (ICP-MS) to yield atomic mass spectra from volatile organic compounds. Atomization of injected compounds was nearly complete and independent of molecular structure, so that elemental ratios could be determined. Detection limits were in the range 0.001 to 400 ng s -1 , depending on the ionization energy of the element and its abundance in the background spectrum. The relative standard deviation of measured isotope ratios varied from 0.4% for Br (i.e., a ratio close to unity) to 18% for N (a very large ratio). Thus, GC-ICP-MS provides elemental and isotope ratio information that is complementary to the molecular information derived from GC-MS with conventional ionization methods

Use of nitrogen stable isotope analysis to understand char nitrogen evolution during the fluidized-bed co-combustion of coal and sewage sludge

Energy Technology Data Exchange (ETDEWEB)

Ana Arenillas; Roberto Garcia; Chenggong Sun; Colin E. Snape; Angel H. Moreno; Fernando Rubiera; Jose J. Pis [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering

2005-04-01

NOx emissions from sewage sludge combustion are a concern, because of the usually high nitrogen content of this fuel. The interactions during co-combustion in a fluidized-bed reactor of sewage sludge and a bituminous coal were evaluated, in relation to the nitrogen evolution during the combustion process. The nitrogen stable isotope measurements provide novel results regarding the tracing of nitrogen during combustion. Our preliminary results show that the co-combustion chars retain more nitrogen than expected, with the additional nitrogen being mainly derived from the sludge. Additional measurements are planned on the resultant co-combustion gases, to aid source apportionment of the NOx arising from coal/sewage interactions. 14 refs., 3 figs., 2 tabs.

Sample preparation techniques for the determination of natural 15N/14N variations in amino acids by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS).

Science.gov (United States)

Hofmann, D; Gehre, M; Jung, K

2003-09-01

In order to identify natural nitrogen isotope variations of biologically important amino acids four derivatization reactions (t-butylmethylsilylation, esterification with subsequent trifluoroacetylation, acetylation and pivaloylation) were tested with standard mixtures of 17 proteinogenic amino acids and plant (moss) samples using GC-C-IRMS. The possible fractionation of the nitrogen isotopes, caused for instance by the formation of multiple reaction products, was investigated. For biological samples, the esterification of the amino acids with subsequent trifluoroacetylation is recommended for nitrogen isotope ratio analysis. A sample preparation technique is described for the isotope ratio mass spectrometric analysis of amino acids from the non-protein (NPN) fraction of terrestrial moss. 14N/15N ratios from moss (Scleropodium spec.) samples from different anthropogenically polluted areas were studied with respect to ecotoxicologal bioindication.

MEMS-Based Micro Gas Chromatography: Design, Fabrication and Characterization

OpenAIRE

Zareian-Jahromi, Mohammad Amin

2009-01-01

This work is focused on the design, fabrication and characterization of high performance MEMS-based micro gas chromatography columns having wide range of applications in the pharmaceutical industry, environmental monitoring, petroleum distillation, clinical chemistry, and food processing. The first part of this work describes different approaches to achieve high-performance microfabricated silicon-glass separation columns for micro gas chromatographic (µGC) systems. The capillary width effec...

On the noble gas isotopic fractionation in naturally occurring gases

International Nuclear Information System (INIS)

Marty, B.

1984-01-01

The isotopic composition of neon in the mantle is an important geochemical constraint on the formation of the earth and subsequent degassing. Some deviation of neon isotopic composition in natural gas and rock samples from the atmospheric value which can not be accounted for by the known nuclear process has been reported, and Nagao et al. interpreted the deviation as the result of mass fractionation in natural gas in Japan. The possible cause of such fractionation was investigated. Gaseous diffusion, such as (a) free-molecule diffusion, (b) mutual diffusion and (c) thermal diffusion, is able to cause isotopic fractionation. After the detailed consideration on these three diffusion processes, conclusion that free-molecule diffusion occurs only in very particular condition, and it is questionable that thermal diffusion occurs in nature, were obtained. (b) which means the interaction of two or more gases, is supposed to occur in nature, and is able to confirm experimentally. In mutual diffusion only, gas transfer is concerned, but other form of fractionation should not be neglected. In solid diffusion, gas is trapped by fine grained sedimentary rocks, and may be fractionated by adsorption and communication to exterior through minute channels. Underground water also works as noble gas reservoir. For example, when gas stream is in contact with water, continuous exchange is possible to take place at the interface of gas and liquid, which contributes to the fractionation. (Ishimitsu, A.)

Gas separation process using membranes with permeate sweep to remove CO.sub.2 from gaseous fuel combustion exhaust

Science.gov (United States)

Wijmans, Johannes G [Menlo Park, CA; Merkel, Timothy C [Menlo Park, CA; Baker, Richard W [Palo Alto, CA

2012-05-15

A gas separation process for treating exhaust gases from the combustion of gaseous fuels, and gaseous fuel combustion processes including such gas separation. The invention involves routing a first portion of the exhaust stream to a carbon dioxide capture step, while simultaneously flowing a second portion of the exhaust gas stream across the feed side of a membrane, flowing a sweep gas stream, usually air, across the permeate side, then passing the permeate/sweep gas back to the combustor.

Non-polar lipids characterization of Quinoa (Chenopodium quinoa) seed by comprehensive two-dimensional gas chromatography with flame ionization/mass spectrometry detection and non-aqueous reversed-phase liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection.

Science.gov (United States)

Fanali, Chiara; Beccaria, Marco; Salivo, Simona; Tranchida, Peter; Tripodo, Giusy; Farnetti, Sara; Dugo, Laura; Dugo, Paola; Mondello, Luigi

2015-07-08

A chemical characterization of major lipid components, namely, triacylglycerols, fatty acids and the unsaponifiable fraction, in a Quinoa seed lipids sample is reported. To tackle such a task, non-aqueous reversed-phase high-performance liquid chromatography with mass spectrometry detection was employed. The latter was interfaced with atmospheric pressure chemical ionization for the analysis of triacylglycerols. The main triacylglycerols (>10%) were represented by OLP, OOL and OLL (P = palmitoyl, O = oleoyl, L = linoleoyl); the latter was present in the oil sample at the highest percentage (18.1%). Furthermore, fatty acid methyl esters were evaluated by gas chromatography with flame ionization detection. 89% of the total fatty acids was represented by unsaturated fatty acid methyl esters with the greatest percentage represented by linoleic and oleic acids accounting for approximately 48 and 28%, respectively. An extensive characterization of the unsaponifiable fraction of Quinoa seed lipids was performed for the first time, by using comprehensive two-dimensional gas chromatography with dual mass spectrometry/flame ionization detection. Overall, 66 compounds of the unsaponifiable fraction were tentatively identified, many constituents of which (particularly sterols) were confirmed by using gas chromatography with high-resolution time-of-flight mass spectrometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas pollutants from detonation and combustion of industrial explosives

Energy Technology Data Exchange (ETDEWEB)

Campos, J.; Pines, A.; Gois, J.C.; Portugal, A. (University of Coimbra, Coimbra (Portugal). Mechanical Engineering Dept.)

1993-01-01

The potential hazards of fumes, from blasting operations in underground mines, have long been recognised. Beyond this normal use of explosives, there are also large amounts of energy substances which cannot be used because their life time is outdated or they are not within the minimal quality requirements. There is a lack of information concerning tests, procedures and theoretical predictions of pollutant concentrations in fumes from detonation and combustion operations with industrial explosives. The most common industrial explosives in Portugal are ammonium nitrate-fuel oil compositions (anfo), and dynamite. Recently, ammonium nitrate based emulsion explosives are more and more used in industrial applications. This paper presents the structure and fundamental thermodynamic equations of THOR computer code to calculate the combustion and detonation products (CO[sub 2], CO, H[sub 2]O, N[sub 2], O[sub 2], H[sub 2], OH, NO, H, N, O, HCN, NH[sub 3], NO[sub 2], N[sub 2]O, CH[sub 4] gases and two kinds of solid carbon - graphite and diamond) for the minimum value of Gibbs free energy, using three well known equations of state - BKW, H9 and H12. Detonation experiments are described and gas analysis discussed. Measured pollutants concentrations (CO, CO[sub 2], NO and NO[sub 2]), as a function of volume of explosion chamber, prove the dependence of expansion mechanisms on CO and NO formation and recombination and validate theoretical predictions. Incineration of explosives in a fluidised bed is described. Products composition from isobare adiabatic combustion of selected explosives has been calculated and correlated with previous calculations for a detonation regime. The obtained results demonstrate the possibility of predicting gas composition of detonation and combustion products of industrial explosives. 22 refs., 14 figs., 1 tab.

Experimental study of xenon isotopes production by gas centrifuge

International Nuclear Information System (INIS)

Zhou Mingsheng; Liang Xiongwen; Zhang Yonggang; Dong Jinping

2006-01-01

The gas centrifuge technology is studied for the separation of Xe isotopes. The nature Xe is chosen as processing gas. A four-state cascade is designed to separate 124 Xe to a concentration of being greater than 65% in three separation runs. 124 Xe can be enriched to a concentration 99% in more separation runs using a cascade of more gas centrifuges. (authors)

Assessment of methods for analyzing gaseous mixtures of hydrogen isotopes and helium

International Nuclear Information System (INIS)

Attalla, A.; Bishop, C.T.; Bohl, D.R.; Buxton, T.L.; Sprague, R.E.; Warner, D.K.

1976-01-01

Mass spectrographic methods have served well in the past to analyze gaseous mixtures of the hydrogen isotopes. Alternate methods of analyses are reviewed which offer wider ranges and variety of isotopic determinations. This report describes possible improvements of the mass spectrographic determinations, gas chromatography, anti-Stokes Raman spectroscopy, microwave-induced optical emission spectroscopy, and methods of measuring tritium using radiation detection devices. Precision, accuracy, limitations, and costs are included for some of the methods mentioned. Costs range from $70,000 for the anti-Stokes Raman spectroscopy equipment, which can determine hydrogen isotopes but not helium, to less than $10,000 for the gas chromatographic equipment, which can determine hydrogen isotopes and helium with precision and accuracy comparable to those of the mass spectrometer

Gas chromatography in blood carbon monoxide monitoring

Energy Technology Data Exchange (ETDEWEB)

Drasche, H.; Funk, L.; Herbolsheimer, R.

1975-05-01

A description of a gas chromatography method for monitoring blood carboxyhaemoglobin (HbCO) levels in a very small quantity (100 mcl) of capillary blood: reagents and apparatus, procedures, calculation of results. To calculate HbCO content, an aliquot portion of water-diluted blood is saturated with CO; this saturation obviates the need to determine the haemoglobin or iron blood levels.

Simultaneous Assay of Isotopic Enrichment and Concentration of Guanidinoacetate and Creatine by Gas Chromatography-Mass Spectrometry

Science.gov (United States)

Kasumov, Takhar; Gruca, Lourdes L.; Dasarathy, Srinivasan; Kalhan, Satish C.

2012-01-01

A gas chromatographic-mass spectrometric (GC-MS) method for the simultaneous measurement of isotopic enrichment and concentration of guanidinoacetic acid and creatine in plasma sample for kinetic studies is reported. The method, based on preparation of the bis(trifluoromethyl)-pyrimidine methyl ester derivatives of guanidinoacetic acid and creatine, is robust and sensitive. The lowest measurable m1 and m3 enrichment for guanidinoacetic acid and creatine, respectively, was 0.3%. The calibration curves for measurements of concentration were linear over a range of 0.5-250 μM guanidinoacetic acid and 2-500 μM for creatine. The method was reliable for inter-assay and intra-assay precision, accuracy and linearity. The technique was applied in a healthy adult to determine in vivo fractional synthesis rate of creatine using primed- constant rate infusion of [1-13C]glycine. It was found that isotopic enrichment of guanidinoacetic acid reached plateau by 30 min of infusion of [1-13C]glycine, indicating either a small pool size or a rapid turnover rate or both, of guanidinoacetic acid. In contrast, tracer appearance in creatin was slow (slope: 0.00097), suggesting a large pool size and a slow rate of synthesis of creatine. This method can be used to estimate rate of synthesis of creatine in-vivo in human and animal studies. PMID:19646413

Investigation of mercury-containing proteins by enriched stable isotopic tracer and size-exclusion chromatography hyphenated to inductively coupled plasma-isotope dilution mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Shi Junwen [Laboratory for Bio-Environmental Health Sciences of Nanoscale Materials and Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)]|[Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Feng Weiyue [Laboratory for Bio-Environmental Health Sciences of Nanoscale Materials and Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)]. E-mail: fengwy@mail.ihep.ac.cn; Wang Meng [Laboratory for Bio-Environmental Health Sciences of Nanoscale Materials and Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)]|[Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Zhang Fang [Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Li Bai [Laboratory for Bio-Environmental Health Sciences of Nanoscale Materials and Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wang Bing; Zhu Motao [Laboratory for Bio-Environmental Health Sciences of Nanoscale Materials and Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)]|[Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Chai Zhifang [Laboratory for Bio-Environmental Health Sciences of Nanoscale Materials and Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)]|[Institute of Nuclear Technology, Shenzhen University, Shenzhen 518060 (China)]|[Institute of Nanochemistry and Nanosafety, Shanghai University, Shanghai (China)

2007-01-30

In order to investigate trace mercury-containing proteins in maternal rat and their offspring, a method of enriched stable isotopic tracer ({sup 196}Hg and {sup 198}Hg) combined with size-exclusion chromatography (SEC) coupled to inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS) was developed. Prior to the analysis, {sup 196}Hg- and {sup 198}Hg-enriched methylmercury was administrated to the pregnant rats. Then the mercury-containing proteins in serum and brain cytosol of the dam and pup rats were separated by size-exclusion columns and the mercury was detected by ICP-MS. The ICP-MS spectrogram of the tracing samples showed significantly elevated {sup 196}Hg and {sup 198}Hg isotopic signals compared with the natural ones, indicating that the detection sensitivity could be increased by the tracer method. The contents of mercury in chromatographic fractions of the dam and pup rat brain cytosol were quantitatively estimated by post-column reverse ID-ICP-MS. The quantitative speciation differences of mercury in brain cytosol between the dam and pup rats were observed, indicating that such studies could be useful for toxicological estimation. Additionally, the isotopic ratio measurement of {sup 198}Hg/{sup 202}Hg in the tracing samples could be used to identify the artifact mercury species caused in the analytical procedure. The study demonstrates that the tracer method combined with high-performance liquid chromatography (HPLC)-ICP-IDMS could provide reliably qualitative and quantitative information on mercury-containing proteins in organisms.

Investigation of mercury-containing proteins by enriched stable isotopic tracer and size-exclusion chromatography hyphenated to inductively coupled plasma-isotope dilution mass spectrometry

International Nuclear Information System (INIS)

Shi Junwen; Feng Weiyue; Wang Meng; Zhang Fang; Li Bai; Wang Bing; Zhu Motao; Chai Zhifang

2007-01-01

In order to investigate trace mercury-containing proteins in maternal rat and their offspring, a method of enriched stable isotopic tracer ( 196 Hg and 198 Hg) combined with size-exclusion chromatography (SEC) coupled to inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS) was developed. Prior to the analysis, 196 Hg- and 198 Hg-enriched methylmercury was administrated to the pregnant rats. Then the mercury-containing proteins in serum and brain cytosol of the dam and pup rats were separated by size-exclusion columns and the mercury was detected by ICP-MS. The ICP-MS spectrogram of the tracing samples showed significantly elevated 196 Hg and 198 Hg isotopic signals compared with the natural ones, indicating that the detection sensitivity could be increased by the tracer method. The contents of mercury in chromatographic fractions of the dam and pup rat brain cytosol were quantitatively estimated by post-column reverse ID-ICP-MS. The quantitative speciation differences of mercury in brain cytosol between the dam and pup rats were observed, indicating that such studies could be useful for toxicological estimation. Additionally, the isotopic ratio measurement of 198 Hg/ 202 Hg in the tracing samples could be used to identify the artifact mercury species caused in the analytical procedure. The study demonstrates that the tracer method combined with high-performance liquid chromatography (HPLC)-ICP-IDMS could provide reliably qualitative and quantitative information on mercury-containing proteins in organisms