Name: measurement of h2s in crude oil and crude oil headspace using multidimensional gas chromatography, deans switching and sulfur-selective detection
Uploaded: 2015-12-10T15:00:00.000+00:00
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Description: Watch this Scientific Journal Video about Measurement of H2S in Crude Oil and Crude Oil Headspace Using Multidimensional Gas Chromatography, Deans Switching and Sulfur-selective Detection at JoVE.com

The authors would like to acknowledge support from the Government of Canada's interdepartmental Program of Energy Research and Development, PERD 113, Petroleum Conversion for Cleaner Air. N.E.H would like to acknowledge her Natural Sciences and Engineering Research Council of Canada Visiting Fellowship.

<ol>
	<li>Guidotti, T. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrogen+sulphide.">Hydrogen sulphide.</a> Occ. Med. 46, 367-371 (1996).</li><li>Reiffenstein, R. J., Hulbert, W. C., Roth, S. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Toxicology+of+Hydrogen+Sulfide.">Toxicology of Hydrogen Sulfide.</a> Annu. Rev. Pharmacol. Toxicol. , 109-134 (1992).</li><li>Qi, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+Temperature+on+the+Corrosion+Behavior+of+Carbon+Steel+in+Hydrogen+Sulphide+Environments.">Effect of Temperature on the Corrosion Behavior of Carbon Steel in Hydrogen Sulphide Environments.</a> Int. J. Electrochem. Sci. 9, 2101-2112 (2014).</li><li>Ma, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+influence+of+hydrogen+sulfide+on+corrosion+of+iron+under+different+conditions.">The influence of hydrogen sulfide on corrosion of iron under different conditions.</a> Corros. Sci. 42, 1669-1683 (2000).</li><li>Kallinikos, L. E., Jess, A., Papayannakos, N. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+study+and+H2S+effect+on+refractory+DBTs+desulfurization+in+a+heavy+gasoil.">Kinetic study and H2S effect on refractory DBTs desulfurization in a heavy gasoil.</a> J. Catal. 269, 169-178 (2010).</li><li>Liu, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+investigation+of+the+effect+of+H2S+in+the+hydrodesulfurization+of+FCC+gasoline.">Kinetic investigation of the effect of H2S in the hydrodesulfurization of FCC gasoline.</a> Fuel. 123, 43-51 (2014).</li><li>Si, X., Xia, D., Xiang, Y., Zhou, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+H2S+on+the+transformation+of+1-hexene+over+NiMoS/&#947;-Al2O3+with+hydrogen.">Effect of H2S on the transformation of 1-hexene over NiMoS/&#947;-Al2O3 with hydrogen.</a> J. Nat. Gas Chem. 19, 185-188 (2010).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocarbons by Potentiometric Titration. , UOP 163-10 (2010).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Standard Test Method for Determination of Hydrogen Sulfide in Fuel Oils by Rapid Liquid Phase Extraction. , ASTM D7621-10 (2010).</li><li>Lywood, W. G., Murray, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> H2S in Crude Measurement Report. , (2012).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Standard Test Method for Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection. , ASTM D7621-10 (2009).</li><li>Liu, W., Morales, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Detection of Sulfur Compounds According to ASTM D5623 in Gasoline with Agilent's Dual Plasma Sulfur Chemiluminescence Detector (G6603A) and an Agilent 7890A Gas Chromatograph. , (2008).</li><li>Barman, B. N., Cebolla, V. L., Membrado, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chromatographic+Techniques+for+Petroleum+and+Related+Products.">Chromatographic Techniques for Petroleum and Related Products.</a> Crit. Rev. Anal. Chem. 30, 75-120 (2000).</li><li>Rodgers, R. P., McKenna, A. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Petroleum+Analysis.">Petroleum Analysis.</a> Anal. Chem. 83, 4665-4687 (2011).</li><li>Nizio, K. D., McGinitie, T. M., Harynuk, J. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Comprehensive+multidimensional+separations+for+the+analysis+of+petroleum.">Comprehensive multidimensional separations for the analysis of petroleum.</a> J. Chromatogr. A. 1255, 12-23 (2012).</li><li>Luong, J., Gras, R., Shellie, R. A., Cortes, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tandem+sulfur+chemiluminescence+and+flame+ionization+detection+with+planar+microfluidic+devices+for+the+characterization+of+sulfur+compounds+in+hydrocarbon+matrices.">Tandem sulfur chemiluminescence and flame ionization detection with planar microfluidic devices for the characterization of sulfur compounds in hydrocarbon matrices.</a> J. Chromatogr. A. 1297, 231-235 (2013).</li><li>Di Sanzo, F. P., Bray, W., Chawla, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determination+of+the+Sulfur+Components+of+Gasoline+Streams+by+Capillary+Column+Gas+Chromatography+with+Sulfur+Chemiluminescence+Detection.">Determination of the Sulfur Components of Gasoline Streams by Capillary Column Gas Chromatography with Sulfur Chemiluminescence Detection.</a> J. High Res. Chromatog. 17, 255-258 (1994).</li><li>Deans, D. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+new+technique+for+heart+cutting+in+gas+chromatography.">A new technique for heart cutting in gas chromatography.</a> Chromatographia. 1, 18-22 (1968).</li><li>Hinshaw, J. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Valves+for+Gas+Chromatography,+Part+III:+Fluidic+Switching+Applications.">Valves for Gas Chromatography, Part III: Fluidic Switching Applications.</a> LC GC N. Am. 29, 988-994 (2011).</li><li>Seeley, J. V., Micyus, N. J., Bandurski, S. V., Seeley, S. K., McCurry, J. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Microfluidic+Deans+Switch+for+Comprehensive+Two-Dimensional+Gas+Chromatography.">Microfluidic Deans Switch for Comprehensive Two-Dimensional Gas Chromatography.</a> Anal. Chem. 79, 1840-1847 (2007).</li><li>Tranchida, P. Q., Sciarrone, D., Dugo, P., Mondello, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heart-cutting+multidimensional+gas+chromatography:+A+review+of+recent+evolution,+applications,+and+future+prospects.">Heart-cutting multidimensional gas chromatography: A review of recent evolution, applications, and future prospects.</a> Anal. Chim. Acta. 716, 66-75 (2012).</li><li>Armstrong, D. W., Reid, G. L., Luong, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gas+Separations:+A+Comparison+of+GasPro&#8482;+and+Aluminum+Oxide+PLOT+Columns+for+the+Separation+of+Highly+Volatile+Compounds.">Gas Separations: A Comparison of GasPro&#8482; and Aluminum Oxide PLOT Columns for the Separation of Highly Volatile Compounds.</a> Curr. Sep. 15, 5-11 (1996).</li><li>Ellis, J., Vickers, A. K., George, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Capillary+Column+Selectivity+and+Inertness+for+Sulfur+Gas+Analysis+in+Light+Hydrocarbon+Streams+by+Gas+Chromatography.">Capillary Column Selectivity and Inertness for Sulfur Gas Analysis in Light Hydrocarbon Streams by Gas Chromatography.</a> Fuel Chemistry Division Preprints. 47, 703-704 (2002).</li><li>Ji, Z., Majors, R. E., Guthrie, E. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Porous+layer+open-tubular+capillary+columns:+preparations,+applications+and+future+directions.">Porous layer open-tubular capillary columns: preparations, applications and future directions.</a> J. Chromatogr. A. 842, 115-142 (1999).</li><li>Luong, J., Gras, R., Shellie, R. A., Cortes, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Applications+of+planar+microfluidic+devices+and+gas+chromatography+for+complex+problem+solving.">Applications of planar microfluidic devices and gas chromatography for complex problem solving.</a> J. Sep. Sci. 36, 182-191 (2013).</li><li>Hildmann, F., Kempe, G., Speer, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Application+of+the+precolumn+back-flush+technology+in+pesticide+residue+analysis:+A+practical+view.">Application of the precolumn back-flush technology in pesticide residue analysis: A practical view.</a> J. Sep. Sci. 36, 2128-2135 (2013).</li><li>Gray, B. P., Teale, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+use+of+a+simple+backflush+technology+to+improve+sample+throughput+and+system+robustness+in+routine+gas+chromatography+tandem+mass+spectrometry+analysis+of+doping+control+samples.">The use of a simple backflush technology to improve sample throughput and system robustness in routine gas chromatography tandem mass spectrometry analysis of doping control samples.</a> J. Chromatogr. A. 1217, 4749-4752 (2010).</li><li>Hayward, T., Gras, R., Luong, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+selected+oxidation+inhibitors+in+transformer+oils+by+multidimensional+gas+chromatography+with+capillary+flow+technology.">Characterization of selected oxidation inhibitors in transformer oils by multidimensional gas chromatography with capillary flow technology.</a> Anal. Methods. 6, 8136-8140 (2014).</li><li>Hutte, R. S., Johansen, N. G., Legier, M. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Column+Selection+and+Optimization+for+Sulfur+Compound+Analyses+by+Gas+Chromatography.">Column Selection and Optimization for Sulfur Compound Analyses by Gas Chromatography.</a> J. High Res. Chromatog. 13, 421-426 (1990).</li><li>Yan, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Unique+selective+detectors+for+gas+chromatography:+Nitrogen+and+sulfur+chemiluminescence+detectors.">Unique selective detectors for gas chromatography: Nitrogen and sulfur chemiluminescence detectors.</a> J. Sep. Sci. 29, 1931-1945 (2006).</li><li>Araujo, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Key+aspects+of+analytical+method+validation+and+linearity+evaluation.">Key aspects of analytical method validation and linearity evaluation.</a> J. Chromatogr. B. 877, 2224-2234 (2009).</li></ol>

The authors have nothing to disclose.

A fim de atingir uma boa medição de H2S, este método emprega um interruptor Deans, backflushing e um detector de enxofre por quimioluminescência (SCD). Uma coluna de dimetilpolissiloxano é usada como a primeira coluna dimensão GC, e serve para retardar o movimento de hidrocarbonetos mais pesados ​​presentes na amostra, de modo que eles não contaminam a coluna trama. Este efeito é reforçado por um fresco (50 ° C) separação inicial. Gases de luz passam através da primeira coluna dimensão e sã...

Análise precisa do petróleo bruto é essencial para a indústria de petróleo e gás, como regulamentos e economia da saúde e segurança são funções de qualidade do óleo. A fim de proteger os transportadores de amostras em bruto, que é necessário para determinar as propriedades de amostras em bruto a desenvolver regulamentos de segurança para ser implementado no caso de uma libertação ou derrame. Em particular, a quantificação de sulfureto de hidrogénio (H2S) é importante, devido à sua elevada toxicidade em fase gasosa; exposições tão baixas quanto 100 ppm pode ser fatal (http://www.cdc.gov/niosh/idlh/7783064.html) 1,2. Dissolveu-se H 2 S em amostras em bruto é geralmente considerado para ser corrosivo 3,4, e pode desactivar os catalisadores utilizados para tratar o óleo 5-7. A remoção do H2S a partir de fluxos de petróleo bruto é ideal, mas sem um método para medir dissolvido H2S, é difícil de avaliar o sucesso dos tratamentos de remoção. Por estas razões, este protocolo foi desenvolvido para medir Dissolved H 2 S em amostras de petróleo bruto pesado, tais como areias petrolíferas canadenses crudes. Uma série de métodos convencionais existem para a quantificação de H 2 S em amostras de petróleo ou combustível com base mais leves, mas nenhum foi validado para uso com o petróleo mais pesado geralmente extraídos das areias betuminosas do Canadá. H 2 S e os mercaptanos são determinadas utilizando uma técnica de titulação por Universal Oil Products (UOP) 163 Método 8, mas este método sofre de inclinação do utilizador-interpretação que resulta da leitura manual das curvas de titulação. Instituto do Petróleo método 570 (IP) usa uma especialidade H 2 S analisador que aquece amostras de óleo combustível 9, e os benefícios de simplicidade e portabilidade, mas carece de precisão com amostras mais pesados ​​10. A Sociedade Americana de Testes e Materiais (ASTM) Método D5623 utiliza a cromatografia gasosa (GC) com resfriamento criogênico e detecção seletiva de enxofre para medir H2S em líquidos de petróleo leves11,12. Este padrão pode ser melhorada ao utilizar uma separação ambiente e também ser aplicado a óleos brutos pesados, pelo que foi utilizada como a base para o protocolo aqui discutido. GC é uma técnica muito utilizada para a análise de amostras de petróleo. As amostras são vaporizados numa entrada quente, e separações ocorrem na fase gasosa. A separação de fase gasosa GC torna ideal para a análise de H2S, como é facilmente libertado a partir da amostra de líquido durante o aquecimento na entrada. Métodos de GC pode ser criado e adaptado para diferentes amostras de acordo com os programas de temperatura utilizadas, colunas implementado, e o uso de cromatografia multidimensional 13-15. Tem havido um grande número de recentes desenvolvimentos para a medição de H2S utilizando GC. Luong et al. Demonstraram H 2 S e outra medição composto de enxofre luz em destilados médios e leves utilizando GC multidimensional e Deans comutação, mas o método não temfoi aplicada a petróleo mais pesado 16. Di Sanzo et ai., Também quantificada H 2 S em gasolina utilizando GC, no entanto, também não tem sido usado em petróleos brutos pesados, e requer arrefecimento 17 sub-ambiente. O método aqui apresentado demonstra um tempo considerável poupança ao longo destes métodos anteriores, com um tempo de análise de completada 5 minutos, em comparação com 10 min (Luong) e 40 min (Di Sanzo). Infelizmente, a aplicação destes métodos em nosso laboratório para comparar a precisão não foi possível devido a restrições de tempo e equipamento. GC Multidimensional permite ao utilizador para explorar a selectividade de duas colunas, em vez de uma única coluna. Em GC convencional, a separação ocorre em uma coluna. No caso de GC multidimensional, a amostra é separado em duas colunas diferentes, aumentando a separação e a selectividade. O interruptor Deans é um dispositivo utilizado para empregar uma configuração de coluna bidimensional. O switch utiliza uma válvula externa de direfluxo de gás ct partir de uma entrada no interruptor para uma das duas portas de saída 18-20. O efluente da primeira coluna pode ser dirigida em qualquer direcção; neste caso, os gases de enxofre de luz são &quot;corte coração&quot; 21 a partir da primeira separação a uma camada porosa tubular aberto em coluna (LOTE) para separação secundária, que tem sido mostrado para ser excelente para a separação de H 2 S provenientes de outros gases com enxofre luz (http://www.chem.agilent.com/cag/cabu/pdf/gaspro.pdf) 22-24. Um detector de quimioluminescência enxofre é utilizado para a detecção, proporcionando selectividade para os compostos de enxofre e eliminar possíveis interferências de quaisquer outros gases leves que pode ter sido transferida para a coluna TRAMA durante o corte do coração. Hidrocarbonetos da amostra de óleo bruto são retidos na primeira coluna de dimensão e são removidas durante um procedimento de retrolavagem; isto protege a coluna PLOT de qualquer contaminação 25-27. Esta abordagem também foi implementado com sucesso para o analysis de inibidores de oxidação em óleos de transformador 28. Aqui, um método GC bidimensional é utilizado para a análise e quantificação dos dissolvido H 2 S em amostras de petróleo bruto pesado. O método é mostrado para ser aplicável sobre um amplo intervalo de concentrações de H 2 S, e também pode ser utilizado para medir H2S em amostras em fase gasosa.

<table><tbody><tr><td>Deans switch</td><td>Agilent</td><td>G2855A</td><td>Or equivalent flow switching device</td></tr><tr><td>Restrictor tubing&amp;nbsp;</td><td>Agilent</td><td>160-2615-10</td><td>Fused silica, deactivated, 180 &amp;micro;m</td></tr><tr><td>HP-PONA column</td><td>Agilent</td><td>19091S-001</td><td></td></tr><tr><td>GasPro column</td><td>Agilent</td><td>113-4332</td><td></td></tr><tr><td>Sulfur chemiluminescence detector, 355</td><td>Agilent/Sievers</td><td>G6603A</td><td></td></tr><tr><td>H&lt;sub&gt;2&lt;/sub&gt;S calibration standard, in He</td><td>Air Liquide</td><td>Custom order</td><td>211 ppm H&lt;sub&gt;2&lt;/sub&gt;S</td></tr><tr><td>CS&lt;sub&gt;2&lt;/sub&gt;</td><td>Fisher Scientific</td><td>C184-500</td><td></td></tr><tr><td>Toluene, HPLC grade</td><td>Fisher Scientific</td><td>T290-4</td><td></td></tr><tr><td>Gas bag, 2 L</td><td>Calibrated Instruments, Inc.</td><td>GSB-P/2</td><td>Twist on/off nozzle</td></tr><tr><td>250 &amp;micro;l gas tight syringe</td><td>Hamilton</td><td>81130</td><td></td></tr><tr><td>500 ml amber glass bottle</td><td>Scientific Specialties</td><td>N73616</td><td></td></tr><tr><td>Open top screw caps</td><td>Scientific Specialties</td><td>169628</td><td></td></tr><tr><td>Tegrabond disc for screw caps</td><td>Chromatographic Specialties</td><td>C889125C</td><td>25 mm, 10/90 MIL</td></tr><tr><td>1 ml gas tight syringe</td><td>Hamilton</td><td>81330</td><td></td></tr><tr><td>2.5% H&lt;sub&gt;2&lt;/sub&gt;S in He gas standard</td><td>Air Liquide</td><td>Custom order</td><td></td></tr></tbody></table>

measurement of h2s in crude oil and crude oil headspace using multidimensional gas chromatography, deans switching and sulfur-selective detection

Um método para a análise do sulfureto de hidrogénio dissolvido em amostras de óleo bruto é demonstrada usando cromatografia em fase gasosa. A fim de eliminar efectivamente a interferências, uma configuração bidimensional coluna é usado, com um interruptor Deans empregue para transferir o sulfureto de hidrogénio a partir da primeira para a segunda coluna (corte de coração). Amostras brutas líquidos são primeiro separados sobre uma coluna de dimetilpolissiloxano, e gases leves e são ainda separados sobre uma coluna de camada porosa ligada tubular aberto (LOTE) que é capaz de separar o sulfureto de hidrogénio a partir de outras espécies de enxofre de luz coração corte. O sulfureto de hidrogénio é então detectada com um detector de quimioluminescência de enxofre, a adição de uma camada adicional de selectividade. A seguir à separação e de detecção de sulfureto de hidrogénio, o sistema é backflushed para remover os hidrocarbonetos de elevado ponto de ebulição presentes nas amostras em bruto e para preservar a integridade cromatográfica. Sulfureto de hidrogénio dissolvido foi quantificado em amostras líquidas a partir de 1.1 para 500 ppm, demonstrando a aplicabilidade larga para uma gama de amostras. O método também tem sido aplicado com sucesso para a análise de amostras de gás a partir do espaço interno de petróleo e gás processo de sacos, com a medição a partir de 0,7 a 9700 ppm de sulfureto de hidrogénio.

De modo a obter a quantificação fiável de H 2 S para as amostras tanto de líquidos e gases, é necessária uma calibração adequada. Para injecções de calibração e as injecções de amostra, o H 2 S de pico não deve ser sobreposto com picos vizinhos e deve ter uma área de pico reprodutíveis. Figura 3 mostra uma injecção de uma amostra do gás, quando o gás é demasiado concentrada para este método. Verificou-se que as concentrações de gás de superior a 500 ppm ut...

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Measurement of H2S in Crude Oil and Crude Oil Headspace Using Multidimensional Gas Chromatography, Deans Switching and Sulfur-selective Detection

A multidimensional gas chromatography method for the analysis of dissolved hydrogen sulfide in liquid crude oil samples is presented. A Deans switch is used to heart-cut light sulfur gases for separation on a secondary column and detection on a sulfur chemiluminescence detector.

Medição de H<sub&gt; 2</sub&gt; S em Crude Oil and Crude Oil Headspace Usando Cromatografia Gasosa Multidimensional, Deans Comutação e Detecção de Enxofre-seletivo

A method for the analysis of dissolved hydrogen sulfide in crude oil samples is demonstrated using gas chromatography. In order to effectively eliminate ...

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Measurement of H2S in Crude Oil and Crude Oil Headspace Using Multidimensional Gas Chromatography, Deans Switching and Sulfur-selective Detection

19.1K visualizações.  Natural Resources Canada. A multidimensional gas chromatography method for the analysis of dissolved hydrogen sulfide in liquid crude oil samples is presented. A Deans switch is used to heart-cut light sulfur gases for separation on a secondary column and detection on a sulfur chemiluminescence detector. 

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Characterizing Bacterial Volatiles using Secondary Electrospray Ionization Mass Spectrometry (SESI-MS)

Secondary electrospray ionization mass spectrometry (SESI-MS) is a method developed for the rapid detection of volatile compounds, without the need for sample pretreatment. The method was first described by Fenn and colleagues1 and has been applied to the detection of illicit drugs2 and explosives3-4, the characterization of skin volatiles5, and the analysis of breath6-7.
SESI ionization occurs by proton transfer reactions between the electrospray solution and the volatile analyte, and is therefore suitable for the analysis of hetero-organic molecules, just as in traditional electrospray ionization (ESI). However, unlike standard ESI, the proton transfer process of SESI occurs in the vapor phase rather than in solution (Fig. 1), and therefore SESI is best suited for detecting organic volatiles and aerosols.
We are expanding the use of SESI-MS to the detection of bacterial volatiles as a method for bacterial identification and characterization8. We have demonstrated that SESI-MS volatile fingerprinting, combined with a statistical analysis method, can be used to differentiate bacterial genera, species, and mixed cultures in a variety of growth media.8 Here we provide the steps for obtaining bacterial volatile fingerprints using SESI-MS, including the instrumental parameters that should be optimized to ensure robust bacterial identification and characterization.

Characterizing Bacterial Volatiles using Secondary Electrospray Ionization Mass Spectrometry SESI-MS

Secondary electrospray ionization mass spectrometry (SESI-MS) enables the detection of volatile organic compounds (VOCs) without the need for any sample pretreatment. This protocol provides instructions for the rapid (within minutes) characterization of bacterial VOCs using SESI-MS.

Caracterizando Voláteis bacteriana secundária usando ionização Espectrometria de Massa (SESI-MS)

Secondary electrospray ionization mass spectrometry (SESI-MS) is a method developed for the rapid detection of volatile compounds, without the need for ...

Bioengenharia

Quantitative Detection of Trace Explosive Vapors by Programmed Temperature Desorption Gas Chromatography-Electron Capture Detector

The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive vapor samples. The direct liquid deposition method yields a higher fidelity between the analysis of vapor samples and the analysis of solution standards than using separate injection methods for vapors and solutions, i.e., samples collected on vapor collection tubes and standards prepared in solution vials. Additionally, the method can account for instrumentation losses, which makes it ideal for minimizing variability and quantitative trace chemical detection. Gas chromatography with an electron capture detector is an instrumentation configuration sensitive to nitro-energetics, such as TNT and RDX, due to their relatively high electron affinity. However, vapor quantitation of these compounds is difficult without viable vapor standards. Thus, we eliminate the requirement for vapor standards by combining the sensitivity of the instrumentation with a direct liquid deposition protocol to analyze trace explosive vapor samples.

Trace explosive vapors of TNT and RDX collected on sorbent-filled thermal desorption tubes were analyzed using a programmed temperature desorption system coupled to GC with an electron capture detector. The instrumental analysis is combined with direct liquid deposition method to reduce sample variability and account for instrumentation drift and losses.

Detecção quantitativa de rastreamento vapores explosivos por temperatura programada Desorption Gas Chromatography-Electron Captura Detector

The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive ...

Química

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ &#948;34S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in &#948;34S values, spanning from -41.6 to +114.8&#8240;, which is much wider than the range of &#948;34S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS &#948;34S values than the framboids. Such 34S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS

Analyses of the sulfur isotopic composition (&#948;34S) of pyrite from methane-bearing sediments have typically focused on bulk samples. Here, we applied secondary ion mass spectroscopy to analyze the &#948;34S values of various pyrite generations to understand the diagenetic history of pyritization.

Preparação de pirita Authigenic de sedimentos de metano-rolamento para In Situ enxofre isótopo análise usando o SIMS

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and ...

Ambiente

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The composition of heavy crude oils and shale oils varies substantially depending on the origin of the mixture. In particular they contain an increased amount of nitrogen containing compounds compared to the conventionally used sweet crude oils. As nitrogen compounds have an influence on the operation of thermal processes occurring in coker units and steam crackers, and as some species are considered as environmentally hazardous, a detailed analysis of the reactions involving nitrogen containing compounds under pyrolysis conditions provides valuable information. Therefore a novel method has been developed and validated with a feedstock containing a high nitrogen content, i.e., a shale oil. First, the feed was characterized offline by comprehensive two-dimensional gas chromatography (GC &#215; GC) coupled with a nitrogen chemiluminescence detector (NCD). In a second step the on-line analysis method was developed and tested on a steam cracking pilot plant by feeding pyridine dissolved in heptane. The former being a representative compound for one of the most abundant classes of compounds present in shale oil. The composition of the reactor effluent was determined via an in-house developed automated sampling system followed by immediate injection of the sample on a GC &#215; GC coupled with a time-of-flight mass spectrometer (TOF-MS), flame ionization detector (FID) and NCD. A novel method for quantitative analysis of nitrogen containing compounds using NCD and 2-chloropyridine as an internal standard has been developed and demonstrated.

A method combining comprehensive two-dimensional gas chromatography with nitrogen chemiluminescence detection has been developed and applied to on-line analysis of nitrogen containing compounds in a complex hydrocarbon matrix.

Análise on-line de compostos contendo azoto em matrizes de hidrocarbonetos complexos

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The ...

Rapid Collection of Floral Fragrance Volatiles using a Headspace Volatile Collection Technique for GC-MS Thermal Desorption Sampling

Fragrances of many flower families have been sampled and the volatiles analyzed. Knowing the compounds that make up the fragrances can be an important step to conservation of flowers that are threatened or endangered. Because floral fragrance is critical for attracting pollinators, this method could be used to better understand or even enhance pollination. We present a protocol using a portable charcoal air filter and vacuum to collect floral fragrance volatiles, which are then analyzed by a GC-MS. By using this method, fragrance volatiles can be sampled using a non-destructive method with a machine that is easily transported. This methodology uses a rapid sampling procedure, cutting sampling time down from 2-3 hours to approximately 10 minutes. Using GC-MS, the fragrance compounds can be identified individually, based on authentic standards. The steps used for collecting fragrance and control data are presented, from material setup to collecting the data output.

Here, we present a protocol for collecting the floral fragrance volatiles from blooming flowers, using a non-destructive sampling procedure.

Coleção rápida de voláteis florais da fragrância usando uma técnica da coleção do volatile do Headspace para a amostragem térmica da desorção de GC-MS

Fragrances of many flower families have been sampled and the volatiles analyzed. Knowing the compounds that make up the fragrances can be an important ...

Bioquímica

A Practical and Low-Cost Setup to Measure Methane in Aqueous Samples

Measuring Dissolved Methane in Aquatic Ecosystems Using An Optical Spectroscopy Gas Analyzer

Measuring greenhouse gas (GHG) fluxes and pools in ecosystems are becoming increasingly common in ecological studies due to their relevance to climate change. With it, the need for analytical platforms adaptable to measuring different pools and fluxes within research groups also grows. This study aims to develop a procedure to use portable optical spectroscopy-based gas analyzers, originally designed and marketed for gas flux measurements, to measure GHG concentrations in aqueous samples. The protocol involves the traditional headspace equilibration technique followed by the injection of a headspace gas subsample into a chamber connected through a closed loop to the inlet and outlet ports of the gas analyzer. The chamber is fabricated from a generic mason jar and simple laboratory supplies, and it is an ideal solution for samples that may require pre-injection dilution. Methane concentrations measured with the chamber are tightly correlated (r2 &#62; 0.98) with concentrations determined separately through gas chromatography-flame ionization detection (GC-FID) on subsamples from the same vials. The procedure is particularly relevant for field studies in remote areas where chromatography equipment and supplies are not readily available, offering a practical, cheaper, and more efficient solution for measuring methane and other dissolved greenhouse gas concentrations in aquatic systems.

This study demonstrates an approach to measure methane gas concentrations in aqueous samples using portable optical analyzers coupled to an injection chamber in a closed loop. The results are similar to conventional gas chromatography, presenting a practical and low-cost alternative particularly suitable for remote field studies.

Measuring greenhouse gas (GHG) fluxes and pools in ecosystems are becoming increasingly common in ecological studies due to their relevance to climate ...

Sampling and Analysis of Animal Scent Signals

We have developed an effective methodology for sampling and analysis of odor signals, by using headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry, to understand how they may be used in animal communication. This technique allows the semi-quantitative analysis of the volatile components of odor secretions by enabling the separation and tentative identification of the components in the sample, followed by the analysis of peak area ratios to look for trends that could signify compounds that may be involved in signaling. The key strengths of this current approach are the range of sample types that can be analyzed; the lack of need for any complex sample preparation or extractions; the ability to separate and analyze the components of a mixture; the identification of the components detected; and the capability to provide semi-quantitative and potentially quantitative information on the components detected. The main limitation to the methodology relates to the samples themselves. Since the components of specific interest are volatile, and these could easily be lost, or their concentrations altered, it is important that the samples are stored and transported appropriately after their collection. This also means that sample storage and transport conditions are relatively costly. This method can be applied to a variety of samples (including urine, feces, hair and scent-gland odor secretions). These odors consist of complex mixtures, occurring in a range of matrices, and thus necessitate the use of techniques to separate the individual components and extract the compounds of biological interest.

We have developed an effective methodology for sampling and analysis of odor signals in order to understand how they may be used in animal communication. Particularly, we use headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry to analyze the volatile components of animal odors and scent-markings.

Amostragem e Análise de Sinais de Aroma Animal

We have developed an effective methodology for sampling and analysis of odor signals, by using headspace solid-phase microextraction coupled with gas ...

Comportamento

Qualitative Characterization of the Aqueous Fraction from Hydrothermal Liquefaction of Algae Using 2D Gas Chromatography with Time-of-flight Mass Spectrometry

Two-dimensional gas chromatography coupled with time-of-flight mass spectrometry is a powerful tool for identifying and quantifying chemical components in complex mixtures. It is often used to analyze gasoline, jet fuel, diesel, bio-diesel and the organic fraction of bio-crude/bio-oil. In most of those analyses, the first dimension of separation is non-polar, followed by a polar separation. The aqueous fractions of bio-crude and other aqueous samples from biofuels production have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fractions obtained from the hydrothermal liquefaction of algae were characterized by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation in the second. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column configuration. Results from qualitative characterization of the aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry are highlighted.

A two-dimensional gas chromatography-time-of-flight mass spectrometry method is described for characterization of the aqueous fraction of bio-crude produced from hydrothermal liquefaction of algae. This protocol can also be employed to analyze the aqueous fraction of liquid products from fast pyrolysis, catalytic fast pyrolysis, catalytic deoxygenation and hydro-treating.

Caracterização qualitativa da fração aquosa de Hydrothermal Liquefação de algas por cromatografia gasosa 2D com Time-of-flight Espectrometria de Massa

Two-dimensional gas chromatography coupled with time-of-flight mass spectrometry is a powerful tool for identifying and quantifying chemical components in ...

Nitrogen Compound Characterization in Fuels by Multidimensional Gas Chromatography

Certain nitrogen-containing compounds can contribute to fuel instability during storage. Hence, detection and characterization of these compounds is crucial. There are significant challenges to overcome when measuring trace compounds in a complex matrix such as fuels. Background interferences and matrix effects can create limitations to routine analytical instrumentation, such as GC-MS. In order to facilitate specific and quantitative measurements of trace nitrogen compounds in fuels, a nitrogen-specific detector is ideal. In this method, a nitrogen chemiluminescence detector (NCD) is used to detect nitrogen compounds in fuels. NCD utilizes a nitrogen-specific reaction that does not involve the hydrocarbon background. Two-dimensional (GCxGC) gas chromatography is a powerful characterization technique as it provides superior separation capabilities to one-dimensional gas chromatography methods. When GCxGC is paired with a NCD, the problematic nitrogen compounds found in fuels can be extensively characterized without background interference. The method presented in this manuscript details the process for measuring different nitrogen-containing compound classes in fuels with little sample preparation. Overall, this GCxGC-NCD method has been shown to be a valuable tool to enhance the understanding of the chemical composition of nitrogen-containing compounds in fuels and their impact on fuel stability. The % RSD for this method is &#60;5% for intraday and &#60;10% for interday analyses; the LOD is 1.7 ppm and the LOQ is 5.5 ppm.

Here, we present a method utilizing two-dimensional gas chromatography and nitrogen chemiluminescence detection (GCxGC-NCD) to extensively characterize the different classes of nitrogen-containing compounds in diesel and jet fuels.

Caracterização do composto de nitrogênio em combustíveis por cromatografia multidimensional de gás

Certain nitrogen-containing compounds can contribute to fuel instability during storage. Hence, detection and characterization of these compounds is ...

Detecção de trimetilamina em medicina derivada de animais por Headspace GC-MS

An Improved Technique for Trimethylamine Detection in Animal-Derived Medicine by Headspace Gas Chromatography-Tandem Quadrupole Mass Spectrometry

Animal-derived medicines have distinctive characteristics and significant curative effects, but most of them have an obvious fishy odor, resulting in the poor compliance of clinical patients. Trimethylamine (TMA) is one of the key fishy odor components in animal-derived medicine. It is difficult to identify TMA accurately using the existing detection method due to the increased pressure in the headspace vial caused by the rapid acid-base reaction after the addition of lye, which causes TMA to escape from the headspace vial, stalling the research progress of the fishy odor of animal-derived medicine. In this study, we proposed a controlled detection method that introduced a paraffin layer as an isolation layer between acid and lye. The rate of TMA production could be effectively controlled by slowly liquefying the paraffin layer through thermostatic furnace heating. This method showed satisfactory linearity, precision experiments, and recoveries with good reproducibility and high sensitivity. It provided technical support for the deodorization of animal-derived medicine.

Autor em destaque: Uma técnica aprimorada para detecção de trimetilamina em medicina derivada de animais por cromatografia gasosa headspace-espectrometria de massa quadrupolo em tandem  

Here, a headspace gas chromatography-tandem quadrupole mass spectrometry (HS-GC-MS/MS) method suitable for the determination of trimethylamine (TMA) in animal-derived medicines is described. The protocol includes sample pretreatment, headspace treatment, analysis conditions, methodological validation, and the determination of TMA in animal-derived medicines.

Uma Técnica Aprimorada para Detecção de Trimetilamina em Medicina Derivada de Animais por Cromatografia Gasosa Headspace-Espectrometria de Massas em Tandem Quadrupolo

Animal-derived medicines have distinctive characteristics and significant curative effects, but most of them have an obvious fishy odor, resulting in the ...

Medição de H

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