Steroid isotopic standards for gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS).

Science.gov (United States)

Zhang, Ying; Tobias, Herbert J; Brenna, J Thomas

2009-03-01

Carbon isotope ratio (CIR) analysis of urinary steroids using gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS) is a recognized test to detect illicit doping with synthetic testosterone. There are currently no universally used steroid isotopic standards (SIS). We adapted a protocol to prepare isotopically uniform steroids for use as a calibrant in GCC-IRMS that can be analyzed under the same conditions as used for steroids extracted from urine. Two separate SIS containing a mixture of steroids were created and coded CU/USADA 33-1 and CU/USADA 34-1, containing acetates and native steroids, respectively. CU/USADA 33-1 contains 5alpha-androstan-3beta-ol acetate (5alpha-A-AC), 5alpha-androstan-3alpha-ol-17-one acetate (androsterone acetate, A-AC), 5beta-androstan-3alpha-ol-11, 17-dione acetate (11-ketoetiocholanolone acetate, 11k-AC) and 5alpha-cholestane (Cne). CU/USADA 34-1 contains 5beta-androstan-3alpha-ol-17-one (etiocholanolone, E), 5alpha-androstan-3alpha-ol-17-one (androsterone, A), and 5beta-pregnane-3alpha, 20alpha-diol (5betaP). Each mixture was prepared and dispensed into a set of about 100 ampoules using a protocol carefully designed to minimize isotopic fractionation and contamination. A natural gas reference material, NIST RM 8559, traceable to the international standard Vienna PeeDee Belemnite (VPDB) was used to calibrate the SIS. Absolute delta(13)C(VPDB) and Deltadelta(13)C(VPDB) values from randomly selected ampoules from both SIS indicate uniformity of steroid isotopic composition within measurement reproducibility, SD(delta(13)C)<0.2 per thousand. This procedure for creation of isotopic steroid mixtures results in consistent standards with isotope ratios traceable to the relevant international reference material.

Detecting animal by-product intake using stable isotope ratio mass spectrometry (IRMS).

Science.gov (United States)

da Silva, D A F; Biscola, N P; Dos Santos, L D; Sartori, M M P; Denadai, J C; da Silva, E T; Ducatti, C; Bicudo, S D; Barraviera, B; Ferreira, R S

2016-11-01

Sheep are used in many countries as food and for manufacturing bioproducts. However, when these animals consume animal by-products (ABP), which is widely prohibited, there is a risk of transmitting scrapie - a fatal prion disease in human beings. Therefore, it is essential to develop sensitive methods to detect previous ABP intake to select safe animals for producing biopharmaceuticals. We used stable isotope ratio mass spectrometry (IRMS) for 13 C and 15 N to trace animal proteins in the serum of three groups of sheep: 1 - received only vegetable protein (VP) for 89 days; 2 - received animal and vegetable protein (AVP); and 3 - received animal and vegetable protein with animal protein subsequently removed (AVPR). Groups 2 and 3 received diets with 30% bovine meat and bone meal (MBM) added to a vegetable diet (from days 16-89 in the AVP group and until day 49 in the AVPR group, when MBM was removed). The AVPR group showed 15 N equilibrium 5 days after MBM removal (54th day). Conversely, 15 N equilibrium in the AVP group occurred 22 days later (76th day). The half-life differed between these groups by 3.55 days. In the AVPR group, 15 N elimination required 53 days, which was similar to this isotope's incorporation time. Turnover was determined based on natural 15 N signatures. IRMS followed by turnover calculations was used to evaluate the time period for the incorporation and elimination of animal protein in sheep serum. The δ 13 C and δ 15 N values were used to track animal protein in the diet. This method is biologically and economically relevant for the veterinary field because it can track protein over time or make a point assessment of animal feed with high sensitivity and resolution, providing a low-cost analysis coupled with fast detection. Isotopic profiles could be measured throughout the experimental period, demonstrating the potential to use the method for traceability and certification assessments. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Profiling of new psychoactive substances (NPS) by using stable isotope ratio mass spectrometry (IRMS): study on the synthetic cannabinoid 5F-PB-22.

Science.gov (United States)

Münster-Müller, S; Scheid, N; Holdermann, T; Schneiders, S; Pütz, M

2018-05-21

In this paper results of a pilot study on the profiling of the synthetic cannabinoid receptor agonist 5F-PB-22 (5F-QUPIC, pentylfluoro-1H-indole-3-carboxylic acid-8-quinolinyl ester) via isotope ratio mass spectrometry are presented. It is focused on δ 13 C, δ 15 N and δ 2 H isotope ratios, which are determined using elemental analyser (EA) and high temperature elemental analyser (TC/EA) coupled to an isotope ratio mass spectrometer (IRMS). By means of a sample of pure material of 5F-PB-22 it is shown that the extraction of 5F-PB-22 from herbal material, a rapid clean-up procedure, or preparative column chromatography had no influences on the isotope ratios. Furthermore, 5F-PB-22 was extracted from fourteen different herbal blend samples ("Spice products" from police seizures) and analysed via IRMS, yielding three clusters containing seven, five and two samples, distinguishable through their isotopic composition, respectively. It is assumed that herbal blends in each cluster have been manufactured from individual batches of 5F-PB-22. This article is protected by copyright. All rights reserved.

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

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

High-precision 13C and 18O measurements by continuous flow-isotope ratio mass spectrometry (CF-IRMS) in Romanian wines characterization

International Nuclear Information System (INIS)

Costinel, Diana; Ionete, Roxana; Vremera, Raluca; Stanciu, Vasile

2008-01-01

Wines characterization is an important problem to which isotopic analysis by continuous flow- IRMS has made a significant contribution. The use of mass spectrometry (MS) to determine the ratios of stable isotopes in bio-molecules now provides the means to prove the botanical and geographical origin of a wide variety of foodstuffs - and therefore, to authenticate and eliminate fraud. There is a strong need for reliable and validated methods to ensure compliance with such regulation and to protect the interests of the consumer. The right to producing wines with an appellation of origin is guaranteed by the Ministry of Agriculture, based on proposals made by the National Office of Vine and Wine (starting with the 1993 vintage year). The Ministry of Agriculture, the National Office for Vine and Wine, and the National Research Institute grants the authentication of the wines with appellation of origin. The present paper emphasize the isotopic analysis for 18 O/ 16 O and 13 C/ 12 C from wines, using a new generation Isotope Ratio MS, CF-IRMS Delta V Plus, coupled with three flexible continuous flow preparation devices (GasBench II and TC Elemental Analyser). (authors)

FTIR and NDIR spectroscopies as valuable alternatives to IRMS spectrometry for the δ(13)C analysis of food.

Science.gov (United States)

Pironti, Concetta; Proto, Antonio; Camin, Federica; Cucciniello, Raffaele; Zarrella, Ilaria; Motta, Oriana

2016-11-01

The (13)C/(12)C carbon isotope ratio is a chemical parameter with many important applications in several scientific area and the technique of choice currently used for the δ(13)C determination is the isotope ratio mass spectrometry (IRMS). This latter is highly accurate (0.1‰) and sensitive (up to 0.01‰), but at the same time expensive and complex. The objective of this work was to assess the reliability of FTIR and NDIRS techniques for the measurement of carbon stable isotope ratio of food sample, in comparison to IRMS. IRMS, NDIRS and FTIR were used to analyze samples of food, such as oil, durum, cocoa, pasta and sugar, in order to determine the natural abundance isotopic ratio of carbon in a parallel way. The results were comparable, showing a close relationship among the three techniques. The main advantage in using FTIR and NDIRS is related to their cheapness and easy-to-operate in comparison to IRMS. Copyright © 2016 Elsevier B.V. All rights reserved.

Use of Isotope Ratio Mass Spectrometry (IRMS) Determination ((18)O/(16)O) to Assess the Local Origin of Fish and Asparagus in Western Switzerland.

Science.gov (United States)

Rossier, Joël S; Maury, Valérie; de Voogd, Blaise; Pfammatter, Elmar

2014-10-01

Here we present the use of isotope ratio mass spectrometry (IRMS) for the detection of mislabelling of food produced in Switzerland. The system is based on the analysis of the oxygen isotope distribution in water (δ(18)O). Depending on the location on the earth, lake or groundwater has a specific isotopic distribution, which can serve as a fingerprint in order to verify whether a product has grown by means of the corresponding water. This report presents specifically the IRMS technique and the results obtained in the origin detection of fish grown in selected Swiss lakes as well as asparagus grown in Valais ground. Strengths and limitations of the method are presented for both cited products; on one hand, the technique is relatively universal for any product which contains significant water but on the other hand, it necessitates a rather heavy workload to build up a database of water δ(18)O values of products of different origins. This analytical tool is part of the concept of combating fraud currently in use in Switzerland.

Isotope ratio mass spectrometry as a tool for source inference in forensic science: A critical review.

Science.gov (United States)

Gentile, Natacha; Siegwolf, Rolf T W; Esseiva, Pierre; Doyle, Sean; Zollinger, Kurt; Delémont, Olivier

2015-06-01

Isotope ratio mass spectrometry (IRMS) has been used in numerous fields of forensic science in a source inference perspective. This review compiles the studies published on the application of isotope ratio mass spectrometry (IRMS) to the traditional fields of forensic science so far. It completes the review of Benson et al. [1] and synthesises the extent of knowledge already gathered in the following fields: illicit drugs, flammable liquids, human provenancing, microtraces, explosives and other specific materials (packaging tapes, safety matches, plastics, etc.). For each field, a discussion assesses the state of science and highlights the relevance of the information in a forensic context. Through the different discussions which mark out the review, the potential and limitations of IRMS, as well as the needs and challenges of future studies are emphasized. The paper elicits the various dimensions of the source which can be obtained from the isotope information and demonstrates the transversal nature of IRMS as a tool for source inference. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Measurement of CO{sub 2} and N{sub 2}O at nanomolar amounts using continuous-flow isotope-ratio mass spectrometry (CF-IRMS)

Energy Technology Data Exchange (ETDEWEB)

Patel, A; Downie, S.; Webster, E.; Hopkins, D.W.; Rennie, M.J. [Univ. of Dundee (United Kingdom)

1994-12-01

We are currently developing methods using Continuous Flow Isotope Ratio Mass Spectrometry (CF-IRMS) in conjunction with a thermal desorption purification unit to measure nanomolar levels of C0{sub 2} and N{sub 2}0. Samples of the pure gases diluted in He/air and transferred to septum capped Exetainers (Labco) provided a simple means to investigate the technique. We analyzed C0{sub 2} at natural abundance in the concentration range 50 to 5 nmoles and N{sub 2}0 at two concentrations between 25 and 5 nmoles. The technique was then used to measure C0{sub 2} (natural abundance and {sup 13}C-labeled) generated from the ninhydrin reaction. The results are summarized in a table; values are expressed in delta {sup 13}C notation relative to Pee Dee Belemnite. The data show that, provided care is taken to minimize or eliminate sources of contamination (air leaks, etc.), CF-IRMS coupled with a thermal desorption unit permits measurement of {sup 13}C enrichment in much smaller amounts of isolated amino acids than has been possible until now. The new methodology, including thermal desorption, should allow stable-isotope investigations on much smaller samples than are possible with other currently available techniques-while maintaining high precision.

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

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 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.

Isotope determination of sulfur by mass spectrometry in soil samples

Directory of Open Access Journals (Sweden)

Alexssandra Luiza Rodrigues Molina Rossete

2012-12-01

Full Text Available Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-, which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2- concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms was carried out by isotope ratio mass spectrometry (IRMS. In this work, the labeled material (K2(34SO4 was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

OpenAIRE

Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

1992-01-01

The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuo...

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

Comparison of different mass spectrometry techniques in the measurement of L-[ring-13C6]phenylalanine incorporation into mixed muscle proteins

Science.gov (United States)

Zabielski, Piotr; Ford, G. Charles; Persson, X. Mai; Jaleel, Abdul; Dewey, Jerry D.; Nair, K Sreekumaran

2013-01-01

Precise measurement of low enrichment of stable isotope labeled amino-acid tracers in tissue samples is a prerequisite in measuring tissue protein synthesis rates. The challenge of this analysis is augmented when small sample size is a critical factor. Muscle samples from human participants following an 8 hour intravenous infusion of L-[ring-13C6]phenylalanine and a bolus dose of L-[ring-13C6]phenylalanine in a mouse were utilized. Liquid Chromatography tandem mass spectrometry (LC/MS/MS), Gas Chromatography tandem mass spectrometry (GC/MS/MS) and Gas Chromatography/Mass spectrometry (GC/MS) were compared to the Gas Chromatography-Combustion-Isotope Ratio mass spectrometry (GC/C/IRMS), to measure mixed muscle protein enrichment of [ring13C6]phenylalanine enrichment. The sample isotope enrichment ranged from 0.0091 to 0.1312 Molar Percent excess (MPE). As compared with GC/C/IRMS, LC/MS/MS, GC/MS/MS and GC/MS showed coefficients of determination of R2 = 0.9962 and R2 = 0.9942, and 0.9217 respectively. However, the precision of measurements (coefficients of variation) for intra-assay are 13.0%, 1.7%, 6.3% and 13.5% and for inter-assay are 9.2%, 3.2%, 10.2% and 25% for GC/C/IRMS, LC/MS/MS, GC/MS/MS and GC/MS respectively. The muscle sample sizes required to obtain these results were 8μg, 0.8μg, 3μg and 3μg for GC/C/IRMS, LC/MS/MS, GC/MS/MS, and GC/MS respectively. We conclude that LC/MS/MS is optimally suited for precise measurements of L-[ring-13C6]phenylalanine tracer enrichment in low abundance and in small quantity samples. PMID:23378099

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

Science.gov (United States)

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

2017-01-01

Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

Isotope determination of sulfur by mass spectrometry in soil samples Determinação isotópica de enxofre por espectrometria de massas (irms em amostras de solo

Directory of Open Access Journals (Sweden)

Alexssandra Luiza Rodrigues Molina Rossete

2012-12-01

Full Text Available Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-, which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2- concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms was carried out by isotope ratio mass spectrometry (IRMS. In this work, the labeled material (K2(34SO4 was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.O enxofre tem papel essencial em plantas, sendo um dos principais nutrientes em diversos processos metabólicos; ele apresenta quatro isótopos estáveis (32S, 33S, 34S e 36S, com abundância natural de 95,00, 0,76, 4,22 e 0,014 % em átomos, respectivamente. Desenvolver um método para determinação isotópica do S por espectrometria de massas de razão isotópica (IRMS em amostras de solo foi o objetivo deste trabalho. A oxidação de S orgânico a sulfato (S-SO4(2- foi avaliada utilizando a oxidação via seca com agentes oxidantes alcalinos. A concentração S-SO4(2- foi determinada pelo método turbidimétrico, e os resultados mostraram que o processo de conversão foi adequado. A obtenção do gás SO2 foi por decomposição térmica do BaSO4 em uma linha de vácuo a 900 ºC, em presença de NaPO3. A determinação isotópica do S (% em átomos de 34S foi realizada em um espectrômetro de massa (IRMS. Neste trabalho, a

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

Mass spectrometry in grape and wine chemistry. Part II: The consumer protection.

Science.gov (United States)

Flamini, Riccardo; Panighel, Annarita

2006-01-01

Controls in food industry are fundamental to protect the consumer health. For products of high quality, warranty of origin and identity is required and analytical control is very important to prevent frauds. In this article, the "state of art" of mass spectrometry in enological chemistry as a consumer safety contribute is reported. Gas chromatography-mass spectrometry (GC/MS) and liquid-chromatography-mass spectrometry (LC/MS) methods have been developed to determine pesticides, ethyl carbamate, and compounds from the yeast and bacterial metabolism in wine. The presence of pesticides in wine is mainly linked to the use of dicarboxyimide fungicides on vineyard shortly before the harvest to prevent the Botrytis cinerea attack of grape. Pesticide residues are regulated at maximum residue limits in grape of low ppm levels, but significantly lower levels in wine have to be detected, and mass spectrometry offers effective and sensitive methods. Moreover, mass spectrometry represent an advantageous alternative to the radioactive-source-containing electron capture detector commonly used in GC analysis of pesticides. Analysis of ochratoxin A (OTA) in wine by LC/MS and multiple mass spectrometry (MS/MS) permits to confirm the toxin presence without the use of expensive immunoaffinity columns, or time and solvent consuming sample derivatization procedures. Inductively coupled plasma-mass spectrometry (ICP/MS) is used to control heavy metals contamination in wine, and to verify the wine origin and authenticity. Isotopic ratio-mass spectrometry (IRMS) is applied to reveal wine watering and sugar additions, and to determine the product origin and traceability.

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.

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

Novel method for measurement of glutathione kinetics in neonates using liquid chromatography coupled to isotope ratio mass spectrometry

NARCIS (Netherlands)

Schierbeek, Henk; te Braake, Frans; Godin, Jean-Philippe; Fay, Laurent-Bernard; van Goudoever, Johannes B.

2007-01-01

A novel analytical method using liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS) was developed for measuring the fractional synthesis rate (FSR) of glutathione (GSH) in neonates after infusion of [1-(13)C]-glycine as a tracer. After transformation of GSH into GSSG, its

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

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--part 2: forensic inter-laboratory trial: bulk carbon and nitrogen stable isotopes in a range of chemical compounds (Australia and New Zealand).

Science.gov (United States)

Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Neal, Ken; Stuart-Williams, Hilary; Hope, Janet; Walker, G Stewart; Roux, Claude

2010-01-01

Comparability of data over time and between laboratories is a key issue for consideration in the development of global databases, and more broadly for quality assurance in general. One mechanism that can be utilized for evaluating traceability is an inter-laboratory trial. This paper addresses an inter-laboratory trial conducted across a number of Australian and New Zealand isotope ratio mass spectrometry (IRMS) laboratories. The main objective of this trial was to determine whether IRMS laboratories in these countries would record comparable values for the distributed samples. Four carbon containing and four nitrogen containing compounds were distributed to seven laboratories in Australia and one in New Zealand. The laboratories were requested to analyze the samples using their standard procedures. The data from each laboratory was evaluated collectively using International Standard ISO 13528 (Statistical methods for use in proficiency testing by inter-laboratory comparisons). "Warning signals" were raised against one participant in this trial. "Action signals" requiring corrective action were raised against four participants. These participants reviewed the data and possible sources for the discrepancies. This inter-laboratory trial was successful in providing an initial snapshot of the potential for traceability between the participating laboratories. The statistical methods described in this article could be used as a model for others needing to evaluate stable isotope results derived from multiple laboratories, e.g., inter-laboratory trials/proficiency testing. Ongoing trials will be conducted to improve traceability across the Australian and New Zealand IRMS community.

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

Comparison of quantitative NMR and IRMS spectrometry for the authentication of "Polish Vodka".

Science.gov (United States)

Ciepielowski, Grzegorz; Pacholczyk-Sienicka, Barbara; Frączek, Tomasz; Klajman, Kamila; Paneth, Piotr; Albrecht, Łukasz

2018-05-31

The production of "Polish Vodka" is restricted by law to the ethyl alcohol of agricultural origins obtained from rye, wheat, barley, oat, triticale and potatoes grown on the territory of the Republic of Poland. The current labeling system should guarantee that the spirit is authentic and of good quality but not all producers are honest. Unfortunately, the authentic "Polish Vodka" is the most often counterfeited by the addition of cheaper and more accessible maize spirits. These illegal practices significantly reduce costs of the spirit production. Therefore, the determination of the botanical origin of alcohol in Poland is highly relevant. The quantitative 2 H NMR and isotope ratio mass spectrometry (IRMS) were used to investigate the authenticity of 30 samples of Polish spirits. Several isotopic parameters were used to determine the botanical origin of 10 unknown samples. Both approaches lead to the same conclusions regarding the percentage of maize-derived ethanol addition. Applied techniques are a valuable tool in the fight against counterfeiting of products. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Carbon-13 composition of bulk dry wines by irm-EA/MS and irm-13C NMR: An indicator of vine water status

Directory of Open Access Journals (Sweden)

Guyon Francois

2017-01-01

Full Text Available Measurements performed on a set of 32 authentic wines (not submitted to any oenological treatment and their ethanol, recovered by distillation, show high correlation between δ13C of bulk wine and its ethanol. These measurements were performed by isotope ratio monitoring by mass spectrometry coupled to an elemental analyzer (irm-EA/MS. Then a series of wines produced by vines of which water status was assessed during the growing season with predawn leaf water potential measurements, was studied by irm-EA/MS. As expected δ13C is correlated to vine water status conditions, as a result of stomatal closure. The ethanol of these specific wines was also analyzed by isotope ratio monitoring and by nuclear magnetic resonance (irm-13C NMR to determine carbon-13 composition on the two specific sites of the ethanol skeleton. If these measurements confirm the correlation between 13C composition and vine growth conditions, the 13C stereospecific information does not make vine water status assessment more precise.

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

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer-chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS).

Science.gov (United States)

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A; Schimmelmann, Arndt

2017-03-30

Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H 2 ) is responsible for non-quantitative H 2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. The modified EA-Cr/HTC reactor setup showed an overall H 2 -recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and

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

Fast IRMS screening of pseudoendogenous steroids in doping analyses.

Science.gov (United States)

de la Torre, Xavier; Colamonici, Cristiana; Curcio, Davide; Botrè, Francesco

2017-11-01

The detection of the abuse of pseudoendogenous steroids (testosterone and/or its precursors) is currently based, when possible, on the application of the steroid module of the World Anti-Doping Agency (WADA), athlete biological passport (ABP), implemented through the global database, ADAMS. When a suspicious sample is detected, the confirmation by isotope ratio mass spectrometry (IRMS) is required. It is well known that this confirmation procedure is time consuming and expensive and can be only applied on a reduced number of samples. In previous studies we have demonstrated that the longitudinal evaluation of the IRMS data is able to detect positive samples that otherwise will be evaluated as negative, improving the efficacy of the fight against doping in sport. This would require the analysis of a much larger volume of samples by IRMS. The aim of the present work is to describe an IRMS screening method allowing to increase the throughput of samples that can be analyzed by IRMS. The detection efficacy of the method is compared with the confirmation method in use, and to assess its robustness and applicability, all the samples of a major cycling stage competition were analyzed, with the agreement of the testing authority, under routine conditions and response times. The results obtained permit to conclude that the IRMS screening method here proposed has adequate selectivity and produces results that overlap with the already validated method currently in use permitting to analyze a much higher volume of samples even during a major event without compromising the detection capacity. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Development of a sensitive GC-C-IRMS method for the analysis of androgens.

Science.gov (United States)

Polet, Michael; Van Gansbeke, Wim; Deventer, Koen; Van Eenoo, Peter

2013-02-01

The administration of anabolic steroids is one of the most important issues in doping control and is detectable through a change in the carbon isotopic composition of testosterone and/or its metabolites. Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), however, remains a very laborious and expensive technique and substantial amounts of urine are needed to meet the sensitivity requirements of the IRMS. This can be problematic because only a limited amount of urine is available for anti-doping analysis on a broad spectrum of substances. In this work we introduce a new type of injection that increases the sensitivity of GC-C-IRMS by a factor of 13 and reduces the limit of detection, simply by using solvent vent injections instead of splitless injection. This drastically reduces the amount of urine required. On top of that, by only changing the injection technique, the detection parameters of the IRMS are not affected and there is no loss in linearity. Copyright © 2012 John Wiley & Sons, Ltd.

A 244Pu spike reference material CBNM IRM-042A

International Nuclear Information System (INIS)

Verbruggen, A.; Gallet, M.; Hendrickx, F.; Bievre, P. de

1991-01-01

An highly enriched 244 Pu isotopic reference material (CBNM IRM-042a) has been prepared and certified for 244 Pu isotope concentration. The certified value of (2.257 7 ± 0.004 4).10 18 atoms 242 Pu.kg -1 of solution has been established by isotope dilution mass spectrometry. The plutonium isotopic composition has been determined by thermal ionization mass spectrometry and calibration of these measurements by means of synthetic 242 Pu/ 239 Pu mixtures. The isotopic reference material is supplied in a sealed glass ampoule containing approximately 10 g of a 5M nitric acid solution at an approximate concentration of 1 μg Pu per g solution. This isotopic reference material is part of a systematic CBNM programme to supply spike isotopic reference materials of various isotopes at different concentrations

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

Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

Science.gov (United States)

Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

2014-01-01

The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuous-flow technique using capillary GC/combustion IRMS. Quadriceps muscles were removed from four Sprague–Dawley rats after each was infused at a different rate with (1-13C)leucine for 6–8 h. Muscle leucine enrichment (at.% excess) measured by both methods differed by less than 4%, except at low (13C)leucine enrichments (IRMS was used to assess muscle (13C)leucine enrichment and fractional muscle protein synthesis rate in ten normal young men and women infused with (1,2-13C2)leucine for 12–14 h. This approach reduced the variability of the isotope abundance measure and gave estimates of muscle protein synthesis rate (0.050 ± 0.011% h−1 (mean ± SEM); range = 0.023–0.147% h−1) that agree with published values determined using the standard analytical approach. The measurement of (13C)leucine enrichment from skeletal muscle protein by capillary GC/combustion IRMS provides a simple, acceptable and practical alternative to preparative GC/ninhydrin IRMS. PMID:1420371

Calibration and Data Processing in Gas Chromatography Combustion Isotope Ratio Mass Spectrometry

Science.gov (United States)

Zhang, Ying; Tobias, Herbert J.; Sacks, Gavin L.; Brenna, J. Thomas

2013-01-01

Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis (13C/12C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the Δ13C = δ13CM – δ13CE difference measurements required for establishing adverse analytical findings for metabolites relative to endogenous reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

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

NARCIS (Netherlands)

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

2008-01-01

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

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.

Differentiation of partial acylglycerols derived from different animal fats by EA-IRMS and GCMS techniques

Energy Technology Data Exchange (ETDEWEB)

Nina Naquiah, A.N.; Marikkar, J.M.N.; Shuhaimi, M.

2016-07-01

A study was carried out to compare partial acylglycerols of lard with those of chicken fat, beef fat and mutton fat using Gas Chromatography Mass Spectrometry (GC-MS) and Elemental Analysis–Isotope Ratio Mass Spectrometry (EA-IRMS). Mono- (MAG) and di-(DAG) acylglycerols of animal fats were prepared according to a chemical glycerolysis method and isolated using column chromatography. The fatty acid composition and δ13C carbon isotope ratio of MAG and DAG derived from individual animal fat were determined separately to establish their identity characteristics. The results showed that the δ13C values of MAG and DAG of lard were significantly different from those of MAG and DAG derived from chicken fat, beef fat and mutton fat. According to the loading plots based on a principle component analysis (PCA), fatty acids namely stearic, oleic and linoleic were the most discriminating parameters to distinctly identify MAG and DAG derived from different animal fats. This demonstrated that the EA-IRMS and the PCA of fatty acid data have considerable potential for discriminating MAG and DAG derived from lard from other animal fats for Halal authentication purposes. (Author)

A simplified procedure for GC/C/IRMS analysis of underivatized 19-norandrosterone in urine following HPLC purification.

Science.gov (United States)

de la Torre, Xavier; Colamonici, Cristiana; Curcio, Davide; Molaioni, Francesco; Pizzardi, Marta; Botrè, Francesco

2011-04-01

Nandrolone and/or its precursors are included in the World Anti-doping Agency (WADA) list of forbidden substances and methods and as such their use is banned in sport. 19-Norandrosterone (19-NA) the main metabolite of these compounds can also be produced endogenously. The need to establish the origin of 19-NA in human urine samples obliges the antidoping laboratories to use isotope ratio mass spectrometry (IRMS) coupled to gas chromatography (GC/C/IRMS). In this work a simple liquid chromatographic method without any additional derivatization step is proposed, allowing to drastically simplify the urine pretreatment procedure, leading to extracts free of interferences permitting precise and accurate IRMS analysis. The purity of the extracts was verified by parallel analysis by gas chromatography coupled to mass spectrometry with GC conditions identical to those of the GC/C/IRMS assay. The method has been validated according to ISO17025 requirements (within assay precision of ±0.3‰ and between assay precision of ±0.4‰). The method has been tested with samples obtained after the administration of synthetic 19-norandrostenediol and samples collected during pregnancy where 19-NA is known to be produced endogenously. Twelve drugs and synthetic standards able to produce through metabolism 19-NA have shown to present δ(13)C values around -29‰ being quite homogeneous (-28.8±1.5; mean±standard deviation) while endogenously produced 19-NA has shown values comparable to other endogenous produced steroids in the range -21 to -24‰ as already reported. The efficacy of the method was tested on real samples from routine antidoping analyses. Copyright © 2011 Elsevier Inc. All rights reserved.

Improved detection of sugar addition to maple syrup using malic acid as internal standard and in 13C isotope ratio mass spectrometry (IRMS).

Science.gov (United States)

Tremblay, Patrice; Paquin, Réal

2007-01-24

Stable carbon isotope ratio mass spectrometry (delta13C IRMS) was used to detect maple syrup adulteration by exogenous sugar addition (beet and cane sugar). Malic acid present in maple syrup is proposed as an isotopic internal standard to improve actual adulteration detection levels. A lead precipitation method has been modified to isolate quantitatively malic acid from maple syrup using preparative reversed-phase liquid chromatography. The stable carbon isotopic ratio of malic acid isolated from this procedure shows an excellent accuracy and repeatability of 0.01 and 0.1 per thousand respectively, confirming that the modified lead precipitation method is an isotopic fractionation-free process. A new approach is proposed to detect adulteration based on the correlation existing between the delta13Cmalic acid and the delta13Csugars-delta13Cmalic acid (r = 0.704). This technique has been tested on a set of 56 authentic maple syrup samples. Additionally, authentic samples were spiked with exogeneous sugars. The mean theoretical detection level was statistically lowered using this technique in comparison with the usual two-standard deviation approach, especially when maple syrup is adulterated with beet sugar : 24 +/- 12% of adulteration detection versus 48 +/- 20% (t-test, p = 7.3 x 10-15). The method was also applied to published data for pineapple juices and honey with the same improvement.

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

On the use of IRMS in forensic science: proposals for a methodological approach.

Science.gov (United States)

Gentile, Natacha; Besson, Luc; Pazos, Diego; Delémont, Olivier; Esseiva, Pierre

2011-10-10

The flourishing number of publications on the use of isotope ratio mass spectrometry (IRMS) in forensic science denotes the enthusiasm and the attraction generated by this technology. IRMS has demonstrated its potential to distinguish chemically identical compounds coming from different sources. Despite the numerous applications of IRMS to a wide range of forensic materials, its implementation in a forensic framework is less straightforward than it appears. In addition, each laboratory has developed its own strategy of analysis on calibration, sequence design, standards utilisation and data treatment without a clear consensus. Through the experience acquired from research undertaken in different forensic fields, we propose a methodological framework of the whole process using IRMS methods. We emphasize the importance of considering isotopic results as part of a whole approach, when applying this technology to a particular forensic issue. The process is divided into six different steps, which should be considered for a thoughtful and relevant application. The dissection of this process into fundamental steps, further detailed, enables a better understanding of the essential, though not exhaustive, factors that have to be considered in order to obtain results of quality and sufficiently robust to proceed to retrospective analyses or interlaboratory comparisons. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Differentiation of lard, chicken fat, beef fat and mutton fat by GCMS and EA-IRMS techniques.

Science.gov (United States)

Ahmad Nizar, Nina Naquiah; Nazrim Marikkar, Jalaldeen Mohamed; Hashim, Dzulkifly Mat

2013-01-01

A study was conducted to differentiate lard, chicken fat, beef fat and mutton fat using Gas Chromatography Mass Spectrometry (GC-MS) and Elemental Analyzer-Isotope Ratio Mass Spectrometry (EA-IRMS). The comparison of overall fatty acid data showed that lard and chicken fat share common characteristics by having palmitic, oleic and linoleic acid as major fatty acids while beef and mutton fats shared common characteristics by possessing palmitic, stearic and oleic acid as major fatty acids. The direct comparisons among the fatty acid data, therefore, may not be suitable for discrimination of different animal fats. When the fatty acid distributional data was subjected to Principle Component Analysis (PCA), it was demonstrated that stearic, oleic and linoleic acids as the most discriminating parameters in the clustering of animal fats into four subclasses. The bulk carbon analysis of animal fats using EA-IRMS showed that determination of the carbon isotope ratios (δ¹³C) would be a good indicator for discriminating lard, chicken fat, beef fat and mutton fat. This would lead to a faster and more efficient method to ascertain the source of origin of fats used in food products.

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.

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

Mass Spectrometric Investigation of Silicon Extremely Enriched in (28)Si: From (28)SiF4 (Gas Phase IRMS) to (28)Si Crystals (MC-ICP-MS).

Science.gov (United States)

Pramann, Axel; Rienitz, Olaf

2016-06-07

A new generation of silicon crystals even further enriched in (28)Si (x((28)Si) > 0.999 98 mol/mol), recently produced by companies and institutes in Russia within the framework of a project initiated by PTB, were investigated with respect to their isotopic composition and molar mass M(Si). A modified isotope dilution mass spectrometric (IDMS) method treating the silicon as the matrix containing a so-called virtual element (VE) existing of the isotopes (29)Si and (30)Si solely and high resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) were applied in combination. This method succeeds also when examining the new materials holding merely trace amounts of (29)Si (x((29)Si) ≈ 5 × 10(-6) mol/mol) and (30)Si (x((30)Si) ≈ 7 × 10(-7) mol/mol) extremely difficult to detect with lowest uncertainty. However, there is a need for validating the enrichment in (28)Si already in the precursor material of the final crystals, silicon tetrafluoride (SiF4) gas prior to crystal production. For that purpose, the isotopic composition of selected SiF4 samples was determined using a multicollector magnetic sector field gas-phase isotope ratio mass spectrometer. Contaminations of SiF4 by natural silicon due to storing and during the isotope ratio mass spectrometry (IRMS) measurements were observed and quantified. The respective MC-ICP-MS measurements of the corresponding crystal samples show-in contrast-several advantages compared to gas phase IRMS. M(Si) of the new crystals were determined to some extent with uncertainties urel(M) < 1 × 10(-9). This study presents a clear dependence of the uncertainty urel(M(Si)) on the degree of enrichment in (28)Si. This leads to a reduction of urel(M(Si)) during the past decade by almost 3 orders of magnitude and thus further reduces the uncertainty of the Avogadro constant NA which is one of the preconditions for the redefinition of the SI unit kilogram.

Detection of petroleum contamination in river sediments from Quebec City region using GC-IRMS

International Nuclear Information System (INIS)

Rogers, K.M.; Savard, M.M.

1999-01-01

Isotopic analysis by compound specific gas chromatography-isotope ratio mass spectrometry (GC-IRMS) is used to detect and characterize petroleum pollution in surficial sediments along the St Lawrence River, near Quebec City. Unusually mature n-alkane distributions have been found in some recent intertidal sediments in the region. GC-IRMS results suggest that the n-alkanes are not derived from indigenous organic sources because they carry delta 13 C values between -30.0 and -27.0 per mille, as well as very small isotopic differences between odd and even numbered n-alkanes, which are both typically associated with petroleum products. Comparison of these sediments with bunker fuel, an oil used in the shipping industry, has shown a close isotopic correlation in some sites, which is further supported by biomarkers. Overall, the contamination has been dispersed along the river but is generally localized around the industrial region where hydrocarbon transfer from shore storage to ships takes place. This study illustrates how GC-IRMS can be used effectively in the detection and characterization of petroleum pollutants in sediments. (author)

Validation of the doubly labeled water method using off-axis integrated cavity output spectroscopy and isotope ratio mass spectrometry.

Science.gov (United States)

Melanson, Edward L; Swibas, Tracy; Kohrt, Wendy M; Catenacci, Vicki A; Creasy, Seth A; Plasqui, Guy; Wouters, Loek; Speakman, John R; Berman, Elena S F

2018-02-01

When the doubly labeled water (DLW) method is used to measure total daily energy expenditure (TDEE), isotope measurements are typically performed using isotope ratio mass spectrometry (IRMS). New technologies, such as off-axis integrated cavity output spectroscopy (OA-ICOS) provide comparable isotopic measurements of standard waters and human urine samples, but the accuracy of carbon dioxide production (V̇co 2 ) determined with OA-ICOS has not been demonstrated. We compared simultaneous measurement V̇co 2 obtained using whole-room indirect calorimetry (IC) with DLW-based measurements from IRMS and OA-ICOS. Seventeen subjects (10 female; 22 to 63 yr) were studied for 7 consecutive days in the IC. Subjects consumed a dose of 0.25 g H 2 18 O (98% APE) and 0.14 g 2 H 2 O (99.8% APE) per kilogram of total body water, and urine samples were obtained on days 1 and 8 to measure average daily V̇co 2 using OA-ICOS and IRMS. V̇co 2 was calculated using both the plateau and intercept methods. There were no differences in V̇co 2 measured by OA-ICOS or IRMS compared with IC when the plateau method was used. When the intercept method was used, V̇co 2 using OA-ICOS did not differ from IC, but V̇co 2 measured using IRMS was significantly lower than IC. Accuracy (~1-5%), precision (~8%), intraclass correlation coefficients ( R = 0.87-90), and root mean squared error (30-40 liters/day) of V̇co 2 measured by OA-ICOS and IRMS were similar. Both OA-ICOS and IRMS produced measurements of V̇co 2 with comparable accuracy and precision compared with IC.

LC/IRMS analysis: A powerful technique to trace carbon flow in microphytobenthic communities in intertidal sediments

Science.gov (United States)

Moerdijk-Poortvliet, Tanja C. W.; Stal, Lucas J.; Boschker, Henricus T. S.

2014-09-01

Microphytobenthic communities are important for primary production in intertidal marine sediments. Extracellular polymeric substances (EPS), comprising polysaccharides and proteins, play a key role in the structure and functioning of microphytobenthic biofilms and allow interactions between the benthic microalgae and the associated heterotrophic bacteria. The use of stable isotopes has provided major insights into the functioning of these microbial ecosystems. Until recently, gas chromatography-isotope ratio mass spectrometry (GC/IRMS) was the principal method for compound specific stable isotope analysis in these studies. Liquid chromatography linked to IRMS (LC/IRMS) is a more recently developed technique that broadens the range of compounds that can be targeted, in particular enabling the analysis of 13C in non-volatile, aqueous soluble organic compounds, such as carbohydrates and amino acids. In this paper we present an overview of the possibilities and limitations of the LC/IRMS technique to study metabolic processes in microphytobenthic biofilms consisting of mainly diatoms. With a preliminary in-situ labeling experiment, we show that the biosynthesis of carbohydrates and amino acids in EPS and total carbohydrate and amino acid pools can be determined by LC/IRMS. Water extractable EPS were composed predominantly of carbohydrates, whereas amino acids played a minor role, both in terms of content and production. By using LC/IRMS, we will be able to quantify the biosynthesis of metabolites and, hence, to unravel in detail the metabolic pathways of the transfer of carbon from the diatoms via EPS to the bacteria.

Compound-specific nitrogen and carbon isotope analysis of nitroaromatic compounds in aqueous samples using solid-phase microextraction coupled to GC/IRMS.

Science.gov (United States)

Berg, Michael; Bolotin, Jakov; Hofstetter, Thomas B

2007-03-15

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry was used to determine the delta15N and delta13C signatures of selected nitroaromatic contaminants such as the explosive 2,4,6-trinitrotoluene (TNT) for derivation of isotopic enrichment factors of contaminant transformation. Parameters for efficient extraction of nitroaromatic compounds (NACs) and substituted anilines from water samples were evaluated by SPME-GC/MS. delta13C signatures determined by SPME-GC/IRMS and elemental analyzer IRMS (EA-IRMS) were in good agreement, generally within +/-0.7 per thousand, except for 2,4-dinitrotoluene (2,4-DNT) and TNT, which showed slight deviations (IRMS were between 73 and 780 microg L-1 and correlated with the extraction efficiencies of the compounds determined by SPME-GC/MS. Nitrogen isotope measurements by SPME-GC/IRMS were of similar precision (standard deviations IRMS within +/-1.3 per thousand (+2.5 per thousand for TNT), but no systematic trend was found for the deviations. LODs of delta15N measurements ranged from 1.6 to 9.6 mg L-1 for nitrotoluenes, chlorinated NACs and DNTs (22 mg L-1 for TNT). The SPME-GC/IRMS method is well suited for the determination of isotopic enrichment factors of various NAC transformation processes and provides so far unexplored possibilities to elucidate behavior and degradation mechanisms of nitroaromatic contaminants in soils and groundwaters.

Headspace solid phase microextraction--GC/C-IRMS for delta13CVPDB measurements of mono-aromatic hydrocarbons using EA-IRMS calibration.

Science.gov (United States)

Ebongué, Véronique Woule; Geypens, Benny; Berglund, Michael; Taylor, Philip

2009-03-01

This work aims at comparing the delta(13)C(VPDB) of mono-aromatic hydrocarbons benzene, toluene, ethylbenzene and xylene isomers (BTEX) measured by elemental analyser (EA)-isotope ratio mass spectrometer (IRMS) with the delta(13)C(VPDB) measured on the same compounds by headspace solid phase microextraction - GC/C-IRMS (hSPME - GC/C-IRMS) with the final goal of using these compounds as internal standards on the latter system. The EA-IRMS measurements were done using calcium and lithium carbonate isotopic reference materials: NBS19 and L-SVEC for establishing the delta(13)C(VPDB) scale. The EA-IRMS measurements with helium dilution of a set of five reference materials (USGS40, USGS41, IAEA-CH-6, IAEA-CH-3 and IAEA-601) show systematic bias of 1 per thousand relative to their assigned values. This bias due to the dilution mechanism in the used ConfloII interface device could not be avoided. As the selected hydrocarbons: BTEX could not be analysed by EA-IRMS without helium dilution, their delta(13)C(VPDB) must be corrected from this observed bias using an external calibration. The CO(2) gas calibrated using EA-IRMS without helium dilution, was used as an in-house reference for the delta(13)C(VPDB) measurements of the BTEX by the hSPME - GC/C-IRMS system. The comparison made between the delta(13)C(VPDB) measured on the same BTEX compounds by EA-IRMS (with external calibration) and by hSPME - GC/C-IRMS techniques showed good agreement.

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.

Accelerator-based ultrasensitive mass spectrometry

International Nuclear Information System (INIS)

Gove, H.E.

1985-01-01

This chapter describes a new mass spectrometry technique involving charged particle accelerators normally used for basic research in nuclear science. Topics considered include the limitations of conventional mass spectrometry, the limitations of the direct measurement of radioactive decay, mass spectrometry using a tandem electrostatic accelerator, mass spectrometry using a cyclotron, how accelerator mass spectrometry circumvents the limitations of conventional mass spectrometry, measurements of stable isotopes, nuclear physics and astrophysics applications, modifications to existing accelerators, descriptions of dedicated systems, and future applications

Potential of ion chromatography coupled to isotope ratio mass spectrometry via a liquid interface for beverages authentication.

Science.gov (United States)

Guyon, Francois; Gaillard, Laetitia; Brault, Audrey; Gaultier, Nicolas; Salagoïty, Marie-Hélène; Médina, Bernard

2013-12-27

New tools for the determination of characteristic parameters for food authentication are requested to prevent food adulteration from which health concerns, unfair competition could follow. A new coupling in the area of compound-specific carbon 13 isotope ratio (δ(13)C) analysis was developed to simultaneously quantify δ(13)C values of sugars and organic acids. The coupling of ion chromatography (IC) together with isotope ratio mass spectrometry (IRMS) can be achieved using a liquid interface allowing a chemical oxidation (co) of organic matter. Synthetic solutions containing 1 polyol (glycerol), 3 carbohydrates (sucrose, glucose and fructose) and 12 organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric) were used to optimize chromatographic conditions (concentration gradient and 3 types of column) and the studied isotopic range (-32.28 to -10.65‰) corresponds to the values found in food products. Optimum chromatographic conditions are found using an IonPac AS15, an elution flow rate of 0.3mLmin(-1) and a linear concentration gradient from 2 to 76mM (rate 21mMmin(-1)). Comparison between δ(13)C value individually obtained for each compound with the coupling IRMS and elemental analyzer, EA-IRMS, and the ones measured on the mixture of compounds by IC-co-IRMS does not reveal any isotope fractionation. Thus, under these experimental conditions, IC-co-IRMS results are accurate and reproducible. This new coupling was tested on two food matrices, an orange juice and a sweet wine. Some optimization is necessary as the concentration range between sugars and organic acids is too large: an increase in the filament intensity of the IRMS is necessary to simultaneously detect the two compound families. These first attempts confirm the good results obtained on synthetic solutions and the strong potential of the coupling IC-co-IRMS in food authentication area. Copyright © 2013 Elsevier B.V. All rights reserved.

Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging.

Science.gov (United States)

Kiss, András; Smith, Donald F; Jungmann, Julia H; Heeren, Ron M A

2013-12-30

Microscope mode imaging for secondary ion mass spectrometry is a technique with the promise of simultaneous high spatial resolution and high-speed imaging of biomolecules from complex surfaces. Technological developments such as new position-sensitive detectors, in combination with polyatomic primary ion sources, are required to exploit the full potential of microscope mode mass spectrometry imaging, i.e. to efficiently push the limits of ultra-high spatial resolution, sample throughput and sensitivity. In this work, a C60 primary source was combined with a commercial mass microscope for microscope mode secondary ion mass spectrometry imaging. The detector setup is a pixelated detector from the Medipix/Timepix family with high-voltage post-acceleration capabilities. The system's mass spectral and imaging performance is tested with various benchmark samples and thin tissue sections. The high secondary ion yield (with respect to 'traditional' monatomic primary ion sources) of the C60 primary ion source and the increased sensitivity of the high voltage detector setup improve microscope mode secondary ion mass spectrometry imaging. The analysis time and the signal-to-noise ratio are improved compared with other microscope mode imaging systems, all at high spatial resolution. We have demonstrated the unique capabilities of a C60 ion microscope with a Timepix detector for high spatial resolution microscope mode secondary ion mass spectrometry imaging. Copyright © 2013 John Wiley & Sons, Ltd.

Development of a GC/C/IRMS method--confirmation of a novel steroid profiling approach in doping control.

Science.gov (United States)

Van Renterghem, Pieter; Polet, Michael; Brooker, Lance; Van Gansbeke, Wim; Van Eenoo, Peter

2012-09-01

In doping control, an athlete can only be convicted with the misuse with endogenous steroids like testosterone (T), if abnormal values of steroid metabolites and steroid ratios are observed and if the subsequent analysis with isotope ratios mass spectrometry (IRMS) confirms the presence of exogenously administered androgens. In this work, we compare the results of a novel steroid profiling approach with the performance an in-house developed IRMS method. The developed IRMS has the advantage over other methods to be relatively short in time and with target compounds androsterone, etiocholanolone, 5β-androstane 3α,17β-diol and 5α-androstane 3α,17β-diol. Pregnanediol was used as an endogenous reference compound (ERC). Reference limits for the IRMS values were established and applied as decision limits for the evaluation of excretion urine from administration with oral T, T-gel, dihydrotestosterone (DHT) - gel and dehydroepiandrosterone (DHEA). Results indicated the importance of both androstanediols as important IRMS markers where relative values compared to an ERC (Δδ(13)C) yielded better detection accuracy than absolute δ(13)C-values. The detection times of all administered endogenous steroids were evaluated using the proposed thresholds. The results of traditional steroid profiling and a new approach based upon minor steroid metabolites monitoring introduced in a longitudinal framework were evaluated with IRMS. With traditional steroid profiling methods, 95% of the atypical samples could be confirmed whereas an additional 74% of IRMS confirmed was provided by a new biomarkers strategy. These results prove that the other steroid profiling strategies can improve the efficiency in detection of misuse with endogenous steroids. Copyright © 2012 Elsevier Inc. All rights reserved.

Forensic Mass Spectrometry

Science.gov (United States)

Hoffmann, William D.; Jackson, Glen P.

2015-07-01

Developments in forensic mass spectrometry tend to follow, rather than lead, the developments in other disciplines. Examples of techniques having forensic potential born independently of forensic applications include ambient ionization, imaging mass spectrometry, isotope ratio mass spectrometry, portable mass spectrometers, and hyphenated chromatography-mass spectrometry instruments, to name a few. Forensic science has the potential to benefit enormously from developments that are funded by other means, if only the infrastructure and personnel existed to adopt, validate, and implement the new technologies into casework. Perhaps one unique area in which forensic science is at the cutting edge is in the area of chemometrics and the determination of likelihood ratios for the evaluation of the weight of evidence. Such statistical techniques have been developed most extensively for ignitable-liquid residue analyses and isotope ratio analysis. This review attempts to capture the trends, motivating forces, and likely impact of developing areas of forensic mass spectrometry, with the caveat that none of this research is likely to have any real impact in the forensic community unless: (a) The instruments developed are turned into robust black boxes with red and green lights for positives and negatives, respectively, or (b) there are PhD graduates in the workforce who can help adopt these sophisticated techniques.

Amino acid δ13C analysis of hair proteins and bone collagen using liquid chromatography/isotope ratio mass spectrometry

DEFF Research Database (Denmark)

Raghavan, Maanasa; McCullagh, James S. O.; Lynnerup, Niels

2010-01-01

We report a novel method for the chromatographic separation and measurement of stable carbon isotope ratios (delta(13)C) of individual amino acids in hair proteins and bone collagen using the LC-IsoLink system, which interfaces liquid chromatography (LC) with isotope ratio mass spectrometry (IRMS......). This paper provides baseline separation of 15 and 13 of the 18 amino acids in bone collagen and hair proteins, respectively. We also describe an approach to analysing small hair samples for compound-specific analysis of segmental hair sections. The LC/IRMS method is applied in a historical context...... by the delta(13)C analysis of hair proteins and bone collagen recovered from six individuals from Uummannaq in Greenland. The analysis of hair and bone amino acids from the same individual, compared for the first time in this study, is of importance in palaeodietary reconstruction. If hair proteins can be used...

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

The measurement of muscle protein synthesis in broilers with a flooding dose technique: use of 15N-labelled phenylalanine, GC-MS and GC-C-IRMS.

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Dänicke, S; Böttcher, W; Simon, O; Jeroch, H

2001-01-01

An experiment was carried out to measure fractional muscle protein synthesis rates (k(s)) in broilers with injection of a flooding dose of phenylalanine (1 ml/100 g body weight of 150 mM phenylalanine; 38 atom percent excess (APE) [15N]phenylalanine). K(s) was calculated from the [15N] enrichment in phenylalanine of tissue-free and protein-bound phenylalanine using both gas chromatography mass spectrometry (GC-MS) and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) for measurements after a 10 min isotope incorporation period. The tertiary-butyldimethylsilyl (t-BDMS) derivatives of phenylalanine were used for gas chromatographic separation in both systems. GC-MS and GC-C-IRMS were calibrated for a range of 7 to 37 [15N]APE and 0 to 0.62 [15N]APE, respectively, and for sample sizes of 0.45 to 4.5 nmol phenylalanine and 7 to 40 nmol phenylalanine, respectively. Reproducibility of standards as a measure of precision varied from 0.06 to 0.29 [15N]APE and from 0.0004 to 0.0018 [15N]APE in GC-MS and GC-C-IRMS, respectively. K(s) was measured in the m. pectoralis major of broilers fed rye based diets (56%) which were provided either unsupplemented (-) or supplemented (+) with an enzyme preparation containing xylanase. K(s) in breast muscles was significantly increased from 21.8%/d to 23.9%/d due to enzyme supplementation. It can be concluded from the study that the measurement of protein synthesis in broilers with the flooding dose technique can be carried out by using [15N]phenylalanine, GC-MS and GC-C-IRMS.

Imaging mass spectrometry statistical analysis.

Science.gov (United States)

Jones, Emrys A; Deininger, Sören-Oliver; Hogendoorn, Pancras C W; Deelder, André M; McDonnell, Liam A

2012-08-30

Imaging mass spectrometry is increasingly used to identify new candidate biomarkers. This clinical application of imaging mass spectrometry is highly multidisciplinary: expertise in mass spectrometry is necessary to acquire high quality data, histology is required to accurately label the origin of each pixel's mass spectrum, disease biology is necessary to understand the potential meaning of the imaging mass spectrometry results, and statistics to assess the confidence of any findings. Imaging mass spectrometry data analysis is further complicated because of the unique nature of the data (within the mass spectrometry field); several of the assumptions implicit in the analysis of LC-MS/profiling datasets are not applicable to imaging. The very large size of imaging datasets and the reporting of many data analysis routines, combined with inadequate training and accessible reviews, have exacerbated this problem. In this paper we provide an accessible review of the nature of imaging data and the different strategies by which the data may be analyzed. Particular attention is paid to the assumptions of the data analysis routines to ensure that the reader is apprised of their correct usage in imaging mass spectrometry research. Copyright © 2012 Elsevier B.V. All rights reserved.

Mass spectrometry in clinical chemistry

International Nuclear Information System (INIS)

Pettersen, J.E.

1977-01-01

A brief description is given of the functional elements of a mass spectrometer and of some currently employed mass spectrometric techniques, such as combined gas chromatography-mass spectrometry, mass chromatography, and selected ion monitoring. Various areas of application of mass spectrometry in clinical chemistry are discussed, such as inborn errors of metabolism and other metabolic disorders, intoxications, quantitative determinations of drugs, hormones, gases, and trace elements, and the use of isotope dilution mass spectrometry as a definitive method for the establishment of true values for concentrations of various compounds in reference sera. It is concluded that mass spectrometry is of great value in clinical chemistry. (Auth.)

Potential of IRMS technology for tracing gamma-butyrolactone (GBL).

Science.gov (United States)

Marclay, François; Pazos, Diego; Delémont, Olivier; Esseiva, Pierre; Saudan, Christophe

2010-05-20

Popularity of gamma-hydroxybutyric acid (GHB) is fairly stable among drug users, while the consumption of its chemical precursor, gamma-butyrolactone (GBL), is a growing phenomenon. Although conventional analytical methods allow to detect this substance in various matrices, linking a trace and a source is still a difficult challenge. However, as several synthesis pathways and chemical precursors exist for the production of GBL, its carbon isotopic signature may vary extensively. For that purpose, a method has been developed to determine the carbon isotopes content of GBL by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The delta(13)C-values of 19 bulk samples purchased worldwide were in the range from -23.1 to -45.8 per thousand (SDIRMS for discriminating between seizures of GBL and for source determination.

Atomic mass spectrometry

International Nuclear Information System (INIS)

Sanz-Medel, A.

1997-01-01

The elemental inorganic analysis seems to be dominated today by techniques based on atomic spectrometry. After an evaluation of advantages and limitations of using mass analysers (ion detectors) versus conventional photomultipliers (photon detector) a brief review of the more popular techniques of the emerging Atomic Mass spectrometry is carried out. Their huge potential for inorganic trace analysis is such that in the future we could well witness how this end of the century and millennium marked the fall of the photons empire in Analytical Atomic Spectrometry. (Author)

Mass spectrometry and tandem mass spectrometry of citrus limonoids.

Science.gov (United States)

Tian, Qingguo; Schwartz, Steven J

2003-10-15

Methods for atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) of citrus limonoid aglycones and electrospray ionization tandem mass spectrometry (ESI-MS/MS) of limonoid glucosides are reported. The fragmentation patterns of four citrus limonoid aglycones (limonin, nomilin, obacunone, and deacetylnomilin) and six limonoid glucosides, that is, limonin 17-beta-D-glucopyranoside (LG), nomilin 17-beta-D-glucopyranoside (NG), nomilinic acid 17-beta-D-glucopyranoside (NAG), deacetyl nomilinic acid 17-beta-D-glucopyranoside (DNAG), obacunone 17-beta-D-glucopyranoside (OG), and obacunoic acid 17-beta-D-glucopyranoside (OAG) were investigated using a quadruple mass spectrometer in low-energy collisionally activated dissociation (CAD). The four limonoid aglycones and four limonoid glucosides (LG, OG, NAG, and DNAG) were purified from citrus seeds; the other two limonoid glucosides (NG and OAG) were tentatively identified in the crude extract of grapefruit seeds by ESI mass spectrometry in both positive and negative ion analysis. Ammonium hydroxide or acetic acid was added to the mobile phase to facilitate ionization. During positive ion APCI analysis of limonoid aglycones, protonated molecular ion, [M + H]+, or adduct ion, [M + NH3 + H]-, was formed as base peaks when ammonium hydroxide was added to the mobile phase. Molecular anions or adduct ions with acetic acid ([M + HOAc - H] and [M + HOAc]-) or a deprotonated molecular ion were produced during negative ion APCI analysis of limonoid aglycones, depending on the mobile-phase modifier used. Positive ion ESI-MS of limonoid glucosides produced adduct ions of [M + H + NH3]+, [M + Na]+, and [M + K]+ when ammonium hydroxide was added to the mobile phase. After collisionally activated dissociation (CAD) of the limonoid aglycone molecular ions in negative ion APCI analysis, fragment ions indicated structural information of the precursor ions, showing the presence of methyl, carboxyl, and oxygenated ring

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.

A comprehensive procedure based on gas chromatography–isotope ratio mass spectrometry following high performance liquid chromatography purification for the analysis of underivatized testosterone and its analogues in human urine

International Nuclear Information System (INIS)

Torre, Xavier de la; Colamonici, Cristiana; Curcio, Davide; Molaioni, Francesco; Botrè, Francesco

2012-01-01

Highlights: ► Overall approach for urine samples purification by HPLC for subsequent GC/C/IRMS analysis in doping control. ► Detection of pseudo-endogenous androgenic steroids (i.e. testosterone, androstenedione) misuse in sports. ► Routine analysis of steroids by GC/C/IRMS in sports drug testing. - Abstract: The confirmation by GC/C/IRMS of the exogenous origin of pseudo-endogenous steroids from human urine samples requires extracts of adequate purity. A strategy based on HPLC sample purification prior to the GC/C/IRMS analysis of human urinary endogenous androgens (i.e. testosterone, androsterone and/or androstenediols), is presented. A method without any additional derivatization step is proposed, allowing to simplify the urine pretreatment procedure, leading to extracts free of interferences permitting precise and accurate IRMS analysis, without the need of correcting the measured delta values for the contribution of the derivatizing agent. The HPLC extracts were adequately combined to both reduce the number of GC/C/IRMS runs and to have appropriate endogenous reference compounds (ERC; i.e. pregnanediol, 11-keto-etiocholanolone) on each GC–IRMS run. The purity of the extracts was assessed by their parallel analysis by gas chromatography coupled to mass spectrometry, with GC conditions identical to those of the GC/C/IRMS assay. The method has been validated according to ISO17025 requirements (within assay precision below 0.3 ‰ 13 C delta units and between assay precision below 0.6 ‰ 13 C delta units for most of the compounds investigated) fulfilling the World Anti-Doping Agency requirements.

Evaluation of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) for the quality assessment of citrus liqueurs.

Science.gov (United States)

Schipilliti, Luisa; Bonaccorsi, Ivana; Cotroneo, Antonella; Dugo, Paola; Mondello, Luigi

2013-02-27

Citrus liqueurs are alcoholic beverages obtained by maceration. The European Parliament protects these alcoholic beverages, forbidding the addition of nature-identical flavoring substances. However, for economical and technological reasons, producers often add natural and/or synthetic flavors to the alcoholic syrup, obtaining artificial spirit drinks. The aim of this study is to investigate the authenticity of Italian liqueurs, of lemon, bergamot, and mandarin (locally known as "limoncello", "bargamino", and "mandarinetto"), comparing the carbon isotope ratios with values determined in genuine cold-pressed peel oils. Authenticity assessment was performed using headspace-solid phase microextraction coupled to gas chromatography-combustion-isotope ratio mass spectrometry. Additional analyses were performed by direct enantioselective gas chromatography to determine the enantiomeric distribution of selected chiral volatiles and by gas chromatography-mass spectrometry for the qualitative analyses of the samples. The method allowed confirmation of genuineness. Enantioselective gas chromatography analyses confirmed the results, demonstrating the reliability of the method.

Eleventh ISMAS workshop on mass spectrometry

International Nuclear Information System (INIS)

Aggarwal, S.K.; Jaison, P.G.

2004-10-01

This volume deals with the latest developments in this field, exposing the innumerable applications of mass spectrometry. The topics covered include basic fundamentals of mass spectrometry, qualitative and quantitative aspects and data interpretation, maintenance of mass spectrometers, selection of a mass spectrometer, its applications in various branches of science as well as recent advances in mass spectrometry. Emphasis is also laid on the practical aspects of mass spectrometry. Papers relevant to INIS are indexed separately

Online stable carbon isotope ratio measurement in formic acid, acetic acid, methanol and ethanol in water by high performance liquid chromatography-isotope ratio mass spectrometry

International Nuclear Information System (INIS)

Tagami, Keiko; Uchida, Shigeo

2008-01-01

A suitable analysis condition was determined for high performance liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS) while making sequential measurements of stable carbon isotope ratios of δ 13 C in formic acid, acetic acid, methanol and ethanol dissolved in water. For this online column separation method, organic reagents are not applicable due to carbon contamination; thus, water and KH 2 PO 4 at low concentrations were tested as mobile phase in combination with a HyPURITY AQUASTAR TM column. Formic acid, acetic acid, methanol and ethanol were separated when 2 mM KH 2 PO 4 aqueous solution was used. Under the determined analysis condition for HPLC-IRMS, carbon concentrations could be measured quantitatively as well as carbon isotope ratio when carbon concentration was higher than 0.4 mM L for each chemical

Ninth ISMAS workshop on mass spectrometry

International Nuclear Information System (INIS)

Aggarwal, S.K.

2000-12-01

Mass spectrometry has wide-ranging applications in such diverse areas as nuclear industry, agriculture, drugs, environment, petroleum and lentils. There is an urgent need to absorb and assimilate state-of-the-art technological developments in the field. Emerging trends in atomic mass spectrometry, advances in organic mass spectrometry, qualitative and quantitative analyses by mass spectrometry and mass spectrometry in oceanography are some of the areas that need to be expeditiously examined and are covered in this volume. Papers relevant to INIS are indexed separately

Performance evaluation of elemental analysis/isotope ratio mass spectrometry methods for the determination of the D/H ratio in tetramethylurea and other compounds--results of a laboratory inter-comparison.

Science.gov (United States)

Bréas, Olivier; Thomas, Freddy; Zeleny, Reinhard; Calderone, Giovanni; Jamin, Eric; Guillou, Claude

2007-01-01

Tetramethylurea (TMU) with a certified D/H ratio is the internal standard for Site-specific Natural Isotope Fractionation measured by Nuclear Magnetic Resonance (SNIF-NMR) analysis of wine ethanol for detection of possible adulterations (Commission Regulation 2676/90). A new batch of a TMU certified reference material (CRM) is currently being prepared. Whereas SNIF-NMR has been employed up to now, Elemental Analysis/Isotope Ratio Mass Spectrometry ((2)H-EA-IRMS) was envisaged as the method of choice for value assignment of the new CRM, as more precise (better repeatable) data might be obtained, resulting in lower uncertainty of the certified value. In order to evaluate the accuracy and intra- and inter-laboratory reproducibility of (2)H-EA-IRMS methods, a laboratory inter-comparison was carried out by analysing TMU and other organic compounds, as well as some waters. The results revealed that experienced laboratories are capable of generating robust and well comparable data, which highlights the emerging potential of IRMS in food authenticity testing. However, a systematic bias between IRMS and SNIF-NMR reference data was observed for TMU; this lack of data consistency rules out the (2)H-IRMS technique for the characterisation measurement of the new TMU CRM.

Use of isotope ratio mass spectrometry to differentiate between endogenous steroids and synthetic homologues in cattle: a review.

Science.gov (United States)

Janssens, Geert; Courtheyn, Dirk; Mangelinckx, Sven; Prévost, Stéphanie; Bichon, Emmanuelle; Monteau, Fabrice; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

2013-04-15

Although substantial technical advances have been achieved during the past decades to extend and facilitate the analysis of growth promoters in cattle, the detection of abuse of synthetic analogs of naturally occurring hormones has remained a challenging issue. When it became clear that the exogenous origin of steroid hormones could be traced based on the (13)C/(12)C isotope ratio of the substances, GC/C/IRMS has been successfully implemented to this aim since the end of the past century. However, due to the costly character of the instrumental setup, the susceptibility of the equipment to errors and the complex and time consuming sample preparation, this method is up until now only applied by a limited number of laboratories. In this review, the general principles as well as the practical application of GC/C/IRMS to differentiate between endogenous steroids and exogenously synthesized homologous compounds in cattle will be discussed in detail, and will be placed next to other existing and to be developed methods based on isotope ratio mass spectrometry. Finally, the link will be made with the field of sports doping, where GC/C/IRMS has been established within the World Anti-Doping Agency (WADA) approved methods as the official technique to differentiate between exogenous and endogenous steroids over the past few years. Copyright © 2013 Elsevier B.V. All rights reserved.

Single-step transesterification with simultaneous concentration and stable isotope analysis of fatty acid methyl esters by gas chromatography-combustion-isotope ratio mass spectrometry.

Science.gov (United States)

Panetta, Robert J; Jahren, A Hope

2011-05-30

Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is increasingly applied to food and metabolic studies for stable isotope analysis (δ(13) C), with the quantification of analyte concentration often obtained via a second alternative method. We describe a rapid direct transesterification of triacylglycerides (TAGs) for fatty acid methyl ester (FAME) analysis by GC-C-IRMS demonstrating robust simultaneous quantification of amount of analyte (mean r(2) =0.99, accuracy ±2% for 37 FAMEs) and δ(13) C (±0.13‰) in a single analytical run. The maximum FAME yield and optimal δ(13) C values are obtained by derivatizing with 10% (v/v) acetyl chloride in methanol for 1 h, while lower levels of acetyl chloride and shorter reaction times skewed the δ(13) C values by as much as 0.80‰. A Bland-Altman evaluation of the GC-C-IRMS measurements resulted in excellent agreement for pure oils (±0.08‰) and oils extracted from French fries (±0.49‰), demonstrating reliable simultaneous quantification of FAME concentration and δ(13) C values. Thus, we conclude that for studies requiring both the quantification of analyte and δ(13) C data, such as authentication or metabolic flux studies, GC-C-IRMS can be used as the sole analytical method. Copyright © 2011 John Wiley & Sons, Ltd.

Determination of carbon isotope ratios for honey samples by means of a liquid chromatography/isotope ratio mass spectrometry system coupled with a post-column pump.

Science.gov (United States)

Kawashima, Hiroto; Suto, Momoka; Suto, Nana

2018-05-20

Liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) has been used to authenticate and trace products such as honey, wine, and lemon juice, and compounds such as caffeine and pesticides. However, LC/IRMS has several disadvantages, including the high cost of the CO 2 membrane and blocking by solidified sodium persulfate. Here, we developed an improved system for determining carbon isotope ratios by LC/IRMS. The main improvement was the use of a post-column pump. Using the improved system, we determined δ 13 C values for glucose with high accuracy and precision (0.1‰ and 0.1‰, respectively; n = 3). The glucose, fructose, disaccharide, trisaccharide, and organic acid constituents of the honey samples were analyzed by LC/IRMS. The δ 13 C values for glucose, fructose, disaccharides, trisaccharides, and organic acids ranged from -27.0 to -24.2‰, -26.8 to -24.0‰, -28.8 to -24.0‰, -27.8 to -22.8‰, and -30.6 to -27.4‰, respectively. The analysis time was 1/3-1/2 the times required for analysis by previously reported methods. The column flow rate could be arbitrarily adjusted with the post-column pump. We applied the improved method to 26 commercial honey samples. Our results can be expected to be useful for other researchers who use LC/IRMS. This article is protected by copyright. All rights reserved.

Fourier Transform Mass Spectrometry

Science.gov (United States)

Scigelova, Michaela; Hornshaw, Martin; Giannakopulos, Anastassios; Makarov, Alexander

2011-01-01

This article provides an introduction to Fourier transform-based mass spectrometry. The key performance characteristics of Fourier transform-based mass spectrometry, mass accuracy and resolution, are presented in the view of how they impact the interpretation of measurements in proteomic applications. The theory and principles of operation of two types of mass analyzer, Fourier transform ion cyclotron resonance and Orbitrap, are described. Major benefits as well as limitations of Fourier transform-based mass spectrometry technology are discussed in the context of practical sample analysis, and illustrated with examples included as figures in this text and in the accompanying slide set. Comparisons highlighting the performance differences between the two mass analyzers are made where deemed useful in assisting the user with choosing the most appropriate technology for an application. Recent developments of these high-performing mass spectrometers are mentioned to provide a future outlook. PMID:21742802

A comprehensive procedure based on gas chromatography-isotope ratio mass spectrometry following high performance liquid chromatography purification for the analysis of underivatized testosterone and its analogues in human urine

Energy Technology Data Exchange (ETDEWEB)

Torre, Xavier de la, E-mail: xavier.delatorre@gmail.com [Laboratorio Antidoping, Federazione Medico Sportiva Italiana, Largo Giulio Onesti 1, 00197 Rome (Italy); Colamonici, Cristiana; Curcio, Davide; Molaioni, Francesco [Laboratorio Antidoping, Federazione Medico Sportiva Italiana, Largo Giulio Onesti 1, 00197 Rome (Italy); Botre, Francesco [Laboratorio Antidoping, Federazione Medico Sportiva Italiana, Largo Giulio Onesti 1, 00197 Rome (Italy); Dipartimento di Management, ' Sapienza' Universita di Roma, Via del Castro Laurenziano 9, 00161 Rome (Italy)

2012-12-05

Highlights: Black-Right-Pointing-Pointer Overall approach for urine samples purification by HPLC for subsequent GC/C/IRMS analysis in doping control. Black-Right-Pointing-Pointer Detection of pseudo-endogenous androgenic steroids (i.e. testosterone, androstenedione) misuse in sports. Black-Right-Pointing-Pointer Routine analysis of steroids by GC/C/IRMS in sports drug testing. - Abstract: The confirmation by GC/C/IRMS of the exogenous origin of pseudo-endogenous steroids from human urine samples requires extracts of adequate purity. A strategy based on HPLC sample purification prior to the GC/C/IRMS analysis of human urinary endogenous androgens (i.e. testosterone, androsterone and/or androstenediols), is presented. A method without any additional derivatization step is proposed, allowing to simplify the urine pretreatment procedure, leading to extracts free of interferences permitting precise and accurate IRMS analysis, without the need of correcting the measured delta values for the contribution of the derivatizing agent. The HPLC extracts were adequately combined to both reduce the number of GC/C/IRMS runs and to have appropriate endogenous reference compounds (ERC; i.e. pregnanediol, 11-keto-etiocholanolone) on each GC-IRMS run. The purity of the extracts was assessed by their parallel analysis by gas chromatography coupled to mass spectrometry, with GC conditions identical to those of the GC/C/IRMS assay. The method has been validated according to ISO17025 requirements (within assay precision below 0.3 Per-Mille-Sign {sup 13}C delta units and between assay precision below 0.6 Per-Mille-Sign {sup 13}C delta units for most of the compounds investigated) fulfilling the World Anti-Doping Agency requirements.

Glycomics using mass spectrometry

OpenAIRE

Wuhrer, Manfred

2013-01-01

Mass spectrometry plays an increasingly important role in structural glycomics. This review provides an overview on currently used mass spectrometric approaches such as the characterization of glycans, the analysis of glycopeptides obtained by proteolytic cleavage of proteins and the analysis of glycosphingolipids. The given examples are demonstrating the application of mass spectrometry to study glycosylation changes associated with congenital disorders of glycosylation, lysosomal storage di...

Simultaneous determination of wine sugars, glycerol and organic acids 13C/12C isotopic ratio by ion chromatography-co-IRMS

Directory of Open Access Journals (Sweden)

Guyon Francois

2014-01-01

Full Text Available Ion chromatography (IC isotope ratio mass spectrometry (IRMS coupling is possible using a liquid interface allowing chemical oxidation (co of organic compounds. Synthetic solutions containing a mixture of glycerol, sugars (sucrose, glucose and fructose and organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric were elaborated to estimate analytical applications of two different IC systems. It appears that the use of carbonated solution in the eluting phase is a perturbation for 13C isotope measurements as it creates a δ13C deviation from the expected values. A sample of authentic sweet wine was analyzed by IC-co-IRMS using KOH gradient. Ratios of isotopic, ratios of organic acids and glycerol was found to be, in average, equal 1.01 ± 0.04 that is in accordance with our previous results.

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.

Mass Spectrometry-Based Biomarker Discovery.

Science.gov (United States)

Zhou, Weidong; Petricoin, Emanuel F; Longo, Caterina

2017-01-01

The discovery of candidate biomarkers within the entire proteome is one of the most important and challenging goals in proteomic research. Mass spectrometry-based proteomics is a modern and promising technology for semiquantitative and qualitative assessment of proteins, enabling protein sequencing and identification with exquisite accuracy and sensitivity. For mass spectrometry analysis, protein extractions from tissues or body fluids and subsequent protein fractionation represent an important and unavoidable step in the workflow for biomarker discovery. Following extraction of proteins, the protein mixture must be digested, reduced, alkylated, and cleaned up prior to mass spectrometry. The aim of our chapter is to provide comprehensible and practical lab procedures for sample digestion, protein fractionation, and subsequent mass spectrometry analysis.

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.

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

Ultra-sensitive radionuclide spectrometry. Radiometrics and mass spectrometry synergy

International Nuclear Information System (INIS)

Povinec, P.P.

2005-01-01

Recent developments in radiometrics and mass spectrometry techniques for ultra-sensitive analysis of radionuclides in the marine environment are reviewed. In the radiometrics sector the dominant development has been the utilization of large HPGe detectors in underground laboratories with anti-cosmic or anti-Compton shielding for the analysis of short and medium-lived radionuclides in the environment. In the mass spectrometry sector, applications of inductively coupled plasma mass spectrometry (ICP-MS) and accelerator mass spectrometry (AMS) for the analysis of long-lived radionuclides in the environment are the most important recent achievements. The recent developments do not only considerably decrease the detection limits for several radionuclides (up to several orders of magnitude), but they also enable to decrease sample volumes so that sampling, e.g., of the water column can be much easier and more effective. A comparison of radiometrics and mass spectrometry results for the analysis of radionuclides in the marine environment shows a reasonable agreement - within quoted uncertainties, for wide range of activities and different sample matrices analyzed. (author)

Development Of An In Situ Passive Sampler For The Detection And Remediation of Explosive Compounds

Science.gov (United States)

2016-06-07

including high performance liquid chromatography (HPLC), gas chromatography mass spectrometry (GCMS) and isotope ratio mass spectrometry ( IRMS ) as...GCMS) and isotope ratio mass spectrometry ( IRMS ) as summarized in St. George et al., 2010 and Smith et al., 2013, 2014. Depuration rates will be...TNT and RDX for the depuration compounds and unlabeled compounds in the ambient environment. These will be quantified as above by GCMS and IRMS . 2015

Laser ablation-combustion-GC-IRMS--a new method for online analysis of intra-annual variation of delta13C in tree rings.

Science.gov (United States)

Schulze, Brigit; Wirth, Christian; Linke, Petra; Brand, Willi A; Kuhlmann, Iris; Horna, Viviana; Schulze, Ernst-Detlef

2004-11-01

We present a new, rapid method for high-resolution online determination of delta13C in tree rings, combining laser ablation (LA), combustion (C), gas chromatography (GC) and isotope ratio mass spectrometry (IRMS) (LA-C-GC-IRMS). Sample material was extracted every 6 min with a UV-laser from a tree core, leaving 40-microm-wide holes. Ablated wood dust was combusted to CO2 at 700 degrees C, separated from other gases on a GC column and injected into an isotope ratio mass spectrometer after removal of water vapor. The measurements were calibrated against an internal and an external standard. The tree core remained intact and could be used for subsequent dendrochronological and dendrochemical analyses. Cores from two Scots pine trees (Pinus sylvestris spp. sibirica Lebed.) from central Siberia were sampled. Inter- and intra-annual patterns of delta13C in whole-wood and lignin-extracted cores were indistinguishable apart from a constant offset, suggesting that lignin extraction is unnecessary for our method. Comparison with the conventional method (microtome slicing, elemental analysis and IRMS) indicated high accuracy of the LA-C-GC-IRMS measurements. Patterns of delta13C along three parallel ablation lines on the same core showed high congruence. A conservative estimate of the precision was +/- 0.24 per thousand. Isotopic patterns of the two Scots pine trees were broadly similar, indicating a signal related to the forest stand's climate history. The maximum variation in delta13C over 22 years was about 5 per thousand, ranging from -27 to -22.3 per thousand. The most obvious pattern was a sharp decline in delta13C during latewood formation and a rapid increase with spring early growth. We conclude that the LA-C-GC-IRMS method will be useful in elucidating short-term climate effects on the delta13C signal in tree rings.

GC-C-IRMS in routine doping control practice: 3 years of drug testing data, quality control and evolution of the method.

Science.gov (United States)

Polet, Michael; Van Eenoo, Peter

2015-06-01

In order to detect the misuse of endogenous anabolic steroids, doping control laboratories require methods that allow differentiation between endogenous steroids and their synthetic copies. Gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) is capable of measuring the carbon isotope ratio of urinary steroids and this allows differentiation between both. GC-C-IRMS and its application to doping control has evolved a lot during the last decade and so have the World Anti-Doping Agency (WADA) technical documents that describe how GC-C-IRMS should be applied. Especially the WADA technical document of 2014 introduced a number of obligatory quality controls and a fixed methodology that should be used by all the doping control laboratories. This document imposed more uniform methods between the laboratories in order to decrease the interlaboratory standard deviation and acquire similar results for the analysis of the same urine samples. In this paper, 3 years of drug testing data of our GC-C-IRMS method in routine doping control practice is described, with an emphasis on the new WADA technical document and its implementation. Useful data for other doping control laboratories is presented focussing on general method setup, quality control and data collected from routine samples. The paper concentrates on how IRMS results shift or remain similar by switching to the 2014 WADA technical document and gives insight in a straightforward approach to calculate the measurement uncertainty.

Use of isotope ratio mass spectrometry to differentiate between endogenous steroids and synthetic homologues in cattle: A review

International Nuclear Information System (INIS)

Janssens, Geert; Courtheyn, Dirk; Mangelinckx, Sven; Prévost, Stéphanie; Bichon, Emmanuelle; Monteau, Fabrice; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

2013-01-01

Graphical abstract: Scheme: Representation of the observed isotope ratios and the relation to exogenous and endogenous natural steroids. AS stands for “amount of steroid”. Highlights: ► The difference between endogenous and exogenous steroids is thoroughly laid out. ► Factors influencing the carbon ratio and the use of Δ 13 C-values are explained. ► Implementation of GC/C/IRMS to detect steroid abuse in cattle is reviewed. ► Alternative methods and upcoming techniques are discussed. ► The differences and similarities with sports doping control are highlighted. -- Abstract: Although substantial technical advances have been achieved during the past decades to extend and facilitate the analysis of growth promoters in cattle, the detection of abuse of synthetic analogs of naturally occurring hormones has remained a challenging issue. When it became clear that the exogenous origin of steroid hormones could be traced based on the 13 C/ 12 C isotope ratio of the substances, GC/C/IRMS has been successfully implemented to this aim since the end of the past century. However, due to the costly character of the instrumental setup, the susceptibility of the equipment to errors and the complex and time consuming sample preparation, this method is up until now only applied by a limited number of laboratories. In this review, the general principles as well as the practical application of GC/C/IRMS to differentiate between endogenous steroids and exogenously synthesized homologous compounds in cattle will be discussed in detail, and will be placed next to other existing and to be developed methods based on isotope ratio mass spectrometry. Finally, the link will be made with the field of sports doping, where GC/C/IRMS has been established within the World Anti-Doping Agency (WADA) approved methods as the official technique to differentiate between exogenous and endogenous steroids over the past few years

A REVIEW ON MASS SPECTROMETRY DETECTORS

OpenAIRE

Khatri Neetu; Gupta Ankit; Taneja Ruchi; Bilandi Ajay; Beniwal Prashant

2012-01-01

Mass spectrometry is an analytical technique for "weighing" molecules. Obviously, this is not done with a conventional scale or balance. Instead, mass spectrometry is based upon the principle of the motion of a charged particle that is called an ion, in an electric or magnetic field. The mass to charge ratio (m/z) of the ion affects particles motion. Since the charge of an electron is known, the mass to charge ratio (m/z) is a measurement of mass of an ion. Mass spectrometry research focuses ...

Isotope ratio mass spectrometry (IRMS) versus laser-assisted ratio analyzer (LARA): a comparative study using two doses of.

Science.gov (United States)

Savarino, V; Landi, F; Dulbecco, P; Ricci, C; Tessieri, L; Biagini, R; Gatta, L; Miglioli, M; Celle, G; Vaira, D

2000-11-01

This study was carried out to compare the measurements and the diagnostic accuracy of the traditional expensive IRMS and the new economical LARA system using two doses of [13C]urea + two different test meals in patients undergoing upper gastrointestinal endoscopy, both before and after anti-Helicobacter treatment. A total of 354 dyspeptic patients underwent endoscopy with gastric biopsies to diagnose H. pylori infection by CLO-test and histology. No patients had taken antibiotics, bismuth, or antisecretory drugs in the 4 weeks before testing. After overnight fasting, breath samples were collected simultaneously in both plastic and glass tubes at baseline and at 30 and 60 min after urea ingestion. In 237 patients 100 mg [13C]urea + Ensure and in 117 patients 75 mg [13C]urea + citric acid were given. The test was also performed with the two urea dosages and meals in 67 and 64 infected patients, respectively, four weeks after anti-Helicobacter therapy. H. pylori was considered eradicated when both biopsy-based tests were negative. A delta value >5 per thousand was considered positive. Breath samples with insufficient CO2 levels at both 30 and 60 min were excluded from final analysis (N = 37 in pre- and N = 8 in posttreatment). There was excellent agreement between overall delta values of the two machines with both [13C]urea 100 mg + Ensure and [13C]urea 75 mg + citric acid. The 95% CI of the difference against the mean was wider with the former (mean -1.3, +6.3, and -9.4) than with the latter urea dosage and test meal (mean -1.2, +5.2 and -8.1). LARA and IRMS were equally effective (P = NS) in distinguishing infected from uninfected patients before therapy using both doses of [13C]urea and test meals (sensitivity ranged from 95% to 99% and specificity from 95% to 97%). This good performance was maintained in the posttreatment phase (sensitivity ranged from 90% to 100% and specificity from 90% to 97%), without any statistical difference among the various combinations

Mass spectrometry. [in organic chemistry

Science.gov (United States)

Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

1978-01-01

A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

Mass spectrometry of long-lived radionuclides

International Nuclear Information System (INIS)

Becker, Johanna Sabine.

2003-01-01

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated--therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of 129 Xe + for the determination of 129 I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass

Preface Miniaturization and Mass Spectrometry

NARCIS (Netherlands)

Unknown, [Unknown; le Gac, Severine; le Gac, S.; van den Berg, Albert; van den Berg, A.

2009-01-01

Miniaturization and Mass Spectrometry illustrates this trend and focuses on one particular analysis technique, mass spectrometry whose popularity has "dramatically" increased in the last two decades with the explosion of the field of biological analysis and the development of two "soft" ionization

Hepatoblastoma Biology Using Isotope Ratio Mass Spectrometry: Utility of a Unique Technique for the Analysis of Oncological Specimens.

Science.gov (United States)

Taran, Katarzyna; Frączek, Tomasz; Sitkiewicz, Anna; Sikora-Szubert, Anita; Kobos, Józef; Paneth, Piotr

2016-07-07

Hepatoblastoma is the most common primary liver tumor in children. However, it occurs rarely, with an incidence of 0.5-1.5 cases per million children. There is no clear explanation of the relationship between clinicopathologic features, therapy, and outcome in hepatoblastoma cases, so far. One of the most widely accepted prognostic factors in hepatoblastoma is histology of the tumor. The aim of the study was to determine the potential differences in biology of hepatoblastoma histological subtypes at the atomic level using the unique method of isotope ratio mass spectrometry, which is especially valuable in examination of small groups of biological samples. Twenty-four measurements of nitrogen stable isotope ratio, carbon stable isotope ratio and total carbon to nitrogen mass ratio in fetal and embryonal hepatoblastoma tissue were performed using a Sercon 20-22 Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS) coupled with a Sercon SL elemental analyzer for simultaneous carbon-nitrogen-sulfur (NCS) analysis. A difference of about 1.781‰ in stable nitrogen isotope 15N/14N ratio was found between examined hepatoblastoma histological subtypes. The prognosis in liver tumors cases in children may be challenging particularly because of the lack of versatile methods of its evaluation. Isotope ratio mass spectrometry allows one to determine the difference between hepatoblastoma histological subtypes and clearly indicates the cases with the best outcome.

Isotope ratio measurements with multiple collection inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Platzner, I.T.; Segal, I.; Halicz, L.

2003-01-01

In the studies summarized in this review, it has been shown that IRM of lead in silicates can be carried out without lead separation and purification. Because of time independent mass discrimination and lack of chemical interaction at high plasma temperatures, simple interference corrections are feasible. This data further support the observation that MC-ICP-MS provides data with superior precision comparing to TIMS. Furthermore, it should be noted that the multi collection instrumental configuration exhibits the capability to perform a single IRM with excellent precision and high accuracy for elements with a large number of isotopes. Four of the discussed elements have six (Er) and seven (Dy, Yb, Os) isotopes

Dose-dependent testosterone sensitivity of the steroidal passport and GC-C-IRMS analysis in relation to the UGT2B17 deletion polymorphism.

Science.gov (United States)

Strahm, Emmanuel; Mullen, Jenny E; Gårevik, Nina; Ericsson, Magnus; Schulze, Jenny J; Rane, Anders; Ekström, Lena

2015-01-01

The newly implemented Steroid Module of the Athlete Biological Passport has improved doping tests for steroids. A biomarker included in this passport is the urinary testosterone glucuronide to epitestosterone glucuronide (T/E) ratio, a ratio greatly affected by a deletion polymorphism in UGT2B17. Suspect urine doping tests are further analyzed with gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) to determine the origin of the androgen. In this study, we investigated the sensitivity of the steroidal module and the IRMS analysis, in subjects administered with three doses of testosterone enanthate (500, 250, and 125 mg), in relation to the UGT2B17 polymorphism. All subjects carrying the UGT2B17 enzyme reached the traditionally used threshold, a T/E ratio of 4, after all three administered doses, whereas none of the subjects devoid of this enzyme reached a T/E of 4. On the other hand, using the athlete biological passport and IRMS analysis, all three doses could be detected to a high degree of sensitivity. The concentrations of all steroids included in the steroidal module were dose dependently increased, except for epitestosterone which decreased independent of dose. The decrease in epitestosterone was significantly associated with circulatory levels of testosterone post dose (rs =0.60 and p=0.007). In conclusion, these results demonstrate that administration of a single dose of 125-500 mg testosterone enanthate could be detected using the athlete biological passport, together with IRMS. Since IRMS is sensitive to testosterone doping independent of UGT2B17 genotype, also very small changes in the steroidal passport should be investigated with IRMS. Copyright © 2015 John Wiley & Sons, Ltd.

Laboratory of acceleration mass spectrometry

International Nuclear Information System (INIS)

Hybler, P.; Chrapan, J.

2002-01-01

In this paper authors describe the principle of the method of acceleration mass spectrometry and the construction plans of this instrument at the Faculty of ecology and environmental sciences in Banska Stiavnica. Using of this instrument for radiocarbon dating is discussed. A review of laboratories with acceleration mass spectrometry is presented

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)

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...

Symposium on accelerator mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

None

1981-01-01

The area of accelerator mass spectrometry has expanded considerably over the past few years and established itself as an independent and interdisciplinary research field. Three years have passed since the first meeting was held at Rochester. A Symposium on Accelerator Mass Spectrometry was held at Argonne on May 11-13, 1981. In attendance were 96 scientists of whom 26 were from outside the United States. The present proceedings document the program and excitement of the field. Papers are arranged according to the original program. A few papers not presented at the meeting have been added to complete the information on the status of accelerator mass spectrometry. Individual papers were prepared separately for the data base.

Symposium on accelerator mass spectrometry

International Nuclear Information System (INIS)

1981-01-01

The area of accelerator mass spectrometry has expanded considerably over the past few years and established itself as an independent and interdisciplinary research field. Three years have passed since the first meeting was held at Rochester. A Symposium on Accelerator Mass Spectrometry was held at Argonne on May 11-13, 1981. In attendance were 96 scientists of whom 26 were from outside the United States. The present proceedings document the program and excitement of the field. Papers are arranged according to the original program. A few papers not presented at the meeting have been added to complete the information on the status of accelerator mass spectrometry. Individual papers were prepared separately for the data base

Fourier Transform Mass Spectrometry.

Science.gov (United States)

Gross, Michael L.; Rempel, Don L.

1984-01-01

Discusses the nature of Fourier transform mass spectrometry and its unique combination of high mass resolution, high upper mass limit, and multichannel advantage. Examines its operation, capabilities and limitations, applications (ion storage, ion manipulation, ion chemistry), and future applications and developments. (JN)

Implementation of AICAR analysis by GC-C-IRMS for anti-doping purposes.

Science.gov (United States)

Buisson, C; Frelat, C; Mongongu, C; Martinat, N; Audran, M

2017-11-01

AICAR (5-aminoimidazole-4-carboxamide-1-β-D-ribofuranoside), is a naturally occurring substance which is part to the World Anti-Doping Agency (WADA) Prohibited List. It is claimed to improve physical performance when administered as a supplement. As for other endogenous compounds such as steroids, the gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) analysis remains an efficient tool to differentiate endogenous substances from exogenous ones. A protocol was described in the literature for the analysis of AICAR by GC-C-IRMS. The aim of the present study was to implement this protocol in our laboratory and to propose solutions to avoid the difficulties encountered. The first point discussed in this study is the derivatization step. Due to the structure of the AICAR molecule, conventional derivatization for GC-C-IRMS such as acetylation could not be applied and silylation was preferred. The improvement of the derivatives stability was achieved thanks to several derivatization conditions tested. This adjustment led to a reproducible derivatization pattern with the 3-TMS form as major derivative product. The second point discussed in this study is the diminution of extracts' background noise. Indeed, the implementation of the published protocol was not easy due to high performance liquid chromatography (HPLC) problems encountered when concentrated urine was injected into our system. Also, too many interferences in the endogenous reference compound fractions were observed. The addition of both a wash step before the HPLC purification and a HPLC purification step for the endogenous reference compound (ERC) fraction allowed us to increase the robustness of the method. This study presents the modified protocol compared to the original protocol as well as the evaluation of the whole method performances. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Role of Mass Spectrometry in Clinical Endocrinology.

Science.gov (United States)

Ketha, Siva S; Singh, Ravinder J; Ketha, Hemamalini

2017-09-01

The advent of mass spectrometry into the clinical laboratory has led to an improvement in clinical management of several endocrine diseases. Liquid chromatography tandem mass spectrometry found some of its first clinical applications in the diagnosis of inborn errors of metabolism, in quantitative steroid analysis, and in drug analysis laboratories. Mass spectrometry assays offer analytical sensitivity and specificity that is superior to immunoassays for many analytes. This article highlights several areas of clinical endocrinology that have witnessed the use of liquid chromatography tandem mass spectrometry to improve clinical outcomes. Copyright © 2017 Elsevier Inc. All rights reserved.

Mass spectrometry

DEFF Research Database (Denmark)

Nyvang Hartmeyer, Gitte; Jensen, Anne Kvistholm; Böcher, Sidsel

2010-01-01

Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) is currently being introduced for the rapid and accurate identification of bacteria. We describe 2 MALDI-TOF MS identification cases - 1 directly on spinal fluid and 1 on grown bacteria. Rapidly obtained...

Compound-specific chlorine isotope ratios of TCE, PCE and DCE isomers by direct injection using CF-IRMS

International Nuclear Information System (INIS)

Shouakar-Stash, Orfan; Drimmie, Robert J.; Zhang Min; Frape, Shaun K.

2006-01-01

A method for determining compound-specific Cl isotopic compositions (δ 37 Cl) was developed for tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), trans-dichloroethene (trans-DCE) and 1,1-dichloroethene (1,1-DCE). The isotope ratio mass spectrometry (IRMS) used in this study has nine collectors, including two for m/z 50 and 52 (CH 3 Cl) and two for m/z 94 and 96 (CH 3 Br). The development of this method is based on the fact that fragments with mass ratios of 94/96, 95/97 and 96/98 are produced from PCE, TCE and DCE isomers during ion bombardment in the source of a mass spectrometer. Using continuous flow isotope ratio mass spectrometry coupled with gas chromatography (GC-CF-IRMS), it is possible to separate these compounds on-line and directly measure the Cl isotopic ratios of the fragments with the specific mass ratios. Both pure phase and aqueous samples were used for Cl isotopic analysis. For pure phase samples, a vapour phase of the chlorinated ethenes was injected directly into the GC, whereas the solid phase micro extraction (SPME) method was used to extract these compounds from aqueous solutions. The precisions of this analytical technique were ±0.12 per mille (1σ, n = 30), ±0.06 per mille (1σ, n = 30), and ±0.08 per mille (1σ, n = 15) for PCE, TCE and DCE isomers, respectively. The limits of quantification (LOQ) for analyzing Cl isotopic composition in aqueous solutions were 20, 5, and 5 μg/L for PCE, TCE and DCE isomers, respectively. This corresponds to 6-9 nano-mole of Cl, which is approximately 80 times lower than the most sensitive existing method. Compared to methods previously available, this new development offers the following advantages: (1) The much lower LOQ make it possible to extract these compounds directly from aqueous solutions using SPME without pre-concentration; (2) The linking of a GC with an IRMS eliminates off-line separation; and (3) Because the fragments used for isotopic ratio measurement are

Differentiation of partial acylglycerols derived from different animal fats by EA-IRMS and GCMS techniques

Directory of Open Access Journals (Sweden)

Nina Naquiah, A. N.

2016-06-01

Full Text Available A study was carried out to compare partial acylglycerols of lard with those of chicken fat, beef fat and mutton fat using Gas Chromatography Mass Spectrometry (GC-MS and Elemental Analysis–Isotope Ratio Mass Spectrometry (EA-IRMS. Mono- (MAG and di-(DAG acylglycerols of animal fats were prepared according to a chemical glycerolysis method and isolated using column chromatography. The fatty acid composition and δ13C carbon isotope ratio of MAG and DAG derived from individual animal fat were determined separately to establish their identity characteristics. The results showed that the δ13C values of MAG and DAG of lard were significantly different from those of MAG and DAG derived from chicken fat, beef fat and mutton fat. According to the loading plots based on a principle component analysis (PCA, fatty acids namely stearic, oleic and linoleic were the most discriminating parameters to distinctly identify MAG and DAG derived from different animal fats. This demonstrated that the EA-IRMS and the PCA of fatty acid data have considerable potential for discriminating MAG and DAG derived from lard from other animal fats for Halal authentication purposes.Se realizó un estudio para comparar acilgliceroles parciales de la manteca de cerdo con las de grasa de pollo, grasa de vacuno y grasa de cordero utilizando cromatografía de gases-espectrometría de masas (GC-MS y análisis elemental de Isótopos-Espectrometría de Masas (EA-IRMS. Los mono- (MAG y di- (DAG acilgliceroles de grasas animales se prepararon mediante un método de glicerolisis química y se aislaron mediante cromatografía en columna. La composición de ácidos grasos y la relación isotópica de carbono δ13C de los MAG y DAG de las grasas de animales se determinan por separado para establecer sus características de identidad. Los resultados mostraron que los valores de δ13C de MAG y DAG de la manteca de cerdo fue significativamente diferente de los de MAG y DAG derivados de grasa

Mass spectrometry with accelerators.

Science.gov (United States)

Litherland, A E; Zhao, X-L; Kieser, W E

2011-01-01

As one in a series of articles on Canadian contributions to mass spectrometry, this review begins with an outline of the history of accelerator mass spectrometry (AMS), noting roles played by researchers at three Canadian AMS laboratories. After a description of the unique features of AMS, three examples, (14)C, (10)Be, and (129)I are given to illustrate the methods. The capabilities of mass spectrometry have been extended by the addition of atomic isobar selection, molecular isobar attenuation, further ion acceleration, followed by ion detection and ion identification at essentially zero dark current or ion flux. This has been accomplished by exploiting the techniques and accelerators of atomic and nuclear physics. In 1939, the first principles of AMS were established using a cyclotron. In 1977 the selection of isobars in the ion source was established when it was shown that the (14)N(-) ion was very unstable, or extremely difficult to create, making a tandem electrostatic accelerator highly suitable for assisting the mass spectrometric measurement of the rare long-lived radioactive isotope (14)C in the environment. This observation, together with the large attenuation of the molecular isobars (13)CH(-) and (12)CH 2(-) during tandem acceleration and the observed very low background contamination from the ion source, was found to facilitate the mass spectrometry of (14)C to at least a level of (14)C/C ~ 6 × 10(-16), the equivalent of a radiocarbon age of 60,000 years. Tandem Accelerator Mass Spectrometry, or AMS, has now made possible the accurate radiocarbon dating of milligram-sized carbon samples by ion counting as well as dating and tracing with many other long-lived radioactive isotopes such as (10)Be, (26)Al, (36)Cl, and (129)I. The difficulty of obtaining large anion currents with low electron affinities and the difficulties of isobar separation, especially for the heavier mass ions, has prompted the use of molecular anions and the search for alternative

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

ITER Remote Maintenance System (IRMS) lifecycle management

Energy Technology Data Exchange (ETDEWEB)

Tesini, Alessandro, E-mail: alessandro.tesini@iter.org [ITER Organization, CS 90 046, 13067 St. Paul Lez Durance Cedex (France); Otto' , Bede [Oxford Technologies Ltd, 7, Nuffield Way, Abingdon, Oxon OX14 1RJ (United Kingdom); Blight, John [FAAST 31c Allee de la Granette, 13600 Ceyreste (France); Choi, Chang-Hwan; Friconneau, Jean-Pierre; Gotewal, Krishan Kumar; Hamilton, David [ITER Organization, CS 90 046, 13067 St. Paul Lez Durance Cedex (France); Heckendorn, Frank [FD Technologies, PO Box 6686, Aiken, SC (United States); Martins, Jean-Pierre [ITER Organization, CS 90 046, 13067 St. Paul Lez Durance Cedex (France); Marty, Thomas [Westinghouse, 122, avenue de Hambourg, 13008 Marseille (France); Nakahira, Masataka; Palmer, Jim; Subramanian, Rajendran [ITER Organization, CS 90 046, 13067 St. Paul Lez Durance Cedex (France)

2011-10-15

The availability of the ITER machine to perform its scientific program is strongly dependent on the performance of the different Remote Handling (RH) systems constituting the ITER Remote Maintenance System (IRMS). The lifecycle of the IRMS will largely exceed 40 years from initial concept design and proof testing through to machine decommissioning. Such a long lifecycle requires that a rigorous approach is put in place to guarantee the technical capabilities of the highly innovative IRMS, its efficiency and its availability. For this purpose, an IRMS System Engineering and IRMS lifecycle management approach has been adopted by ITER. The approach aims at ensuring the IRMS full operability and availability at an acceptable cost of ownership over the full ITER machine assembly and operations period. The IRMS lifecycle management method described in this paper covers such subjects as specific requirements for IRMS design reviews, monitoring during manufacture, factory and site acceptance testing, integrated commissioning, decontamination, maintenance and re-qualification strategies, requirements for Integrated Logistical Support during operations. The updating and implementation of the IRMS lifecycle strategy and this procedure will be managed and monitored by the Remote Handling Integrated Product Team (RH-IPT). Although developed for the IRMS, the basic principles and procedures of lifecycle management could be applied to other ITER plant systems whose reliability and availability will be essential for the continued operation of the ITER machine.

ITER Remote Maintenance System (IRMS) lifecycle management

International Nuclear Information System (INIS)

Tesini, Alessandro; Otto', Bede; Blight, John; Choi, Chang-Hwan; Friconneau, Jean-Pierre; Gotewal, Krishan Kumar; Hamilton, David; Heckendorn, Frank; Martins, Jean-Pierre; Marty, Thomas; Nakahira, Masataka; Palmer, Jim; Subramanian, Rajendran

2011-01-01

The availability of the ITER machine to perform its scientific program is strongly dependent on the performance of the different Remote Handling (RH) systems constituting the ITER Remote Maintenance System (IRMS). The lifecycle of the IRMS will largely exceed 40 years from initial concept design and proof testing through to machine decommissioning. Such a long lifecycle requires that a rigorous approach is put in place to guarantee the technical capabilities of the highly innovative IRMS, its efficiency and its availability. For this purpose, an IRMS System Engineering and IRMS lifecycle management approach has been adopted by ITER. The approach aims at ensuring the IRMS full operability and availability at an acceptable cost of ownership over the full ITER machine assembly and operations period. The IRMS lifecycle management method described in this paper covers such subjects as specific requirements for IRMS design reviews, monitoring during manufacture, factory and site acceptance testing, integrated commissioning, decontamination, maintenance and re-qualification strategies, requirements for Integrated Logistical Support during operations. The updating and implementation of the IRMS lifecycle strategy and this procedure will be managed and monitored by the Remote Handling Integrated Product Team (RH-IPT). Although developed for the IRMS, the basic principles and procedures of lifecycle management could be applied to other ITER plant systems whose reliability and availability will be essential for the continued operation of the ITER machine.

Mass spectrometry at the Pittsburgh conference

International Nuclear Information System (INIS)

Borman, S.

1987-01-01

Each year analytical chemists flock to the Pittsburgh Conference to learn about the latest trends in analytical instrumentation. In this Focus, a number of prominent mass spectroscopists who attended this year's meeting in Atlantic City, NJ, discuss their perceptions of current developments in the field of mass spectrometry (MS). In the June 1 issue of Analytical Chemistry, the authors coverage of the Pittsburgh Conferences continues with a follow-up article on specific developments in hyphenated mass spectrometry - primarily liquid chromatography - MS (LC/MS) and gas chromatography - infrared spectrometry MS (GC/IR/MS)

Chromatography–mass spectrometry in aerospace industry

International Nuclear Information System (INIS)

Buryak, Alexey K; Serduk, T M

2013-01-01

The applications of chromatography–mass spectrometry in aerospace industry are considered. The primary attention is devoted to the development of physicochemical grounds of the use of various chromatography–mass spectrometry procedures to solve topical problems of this industry. Various methods for investigation of the composition of rocket fuels, surfaces of structural materials and environmental media affected by aerospace activities are compared. The application of chromatography–mass spectrometry for the development and evaluation of processes for decontaminations of equipment, industrial wastes and soils from rocket fuel components is substantiated. The bibliography includes 135 references.

Negative chemical ionization mass spectrometry

International Nuclear Information System (INIS)

Smit, A.L.C.

1979-01-01

This thesis describes some aspects of Negative Chemical Ionization (NCI) mass spectrometry. The reasons for the growing interest in NCI are: (i) to extend the basic knowledge of negative ions and their reactions in the gas phase; (ii) to investigate whether or not this knowledge of negative ions can be used successfully to elucidate the structure of molecules by mass spectrometry. (Auth.)

Hepatoblastoma Biology Using Isotope Ratio Mass Spectrometry: Utility of a Unique Technique for the Analysis of Oncological Specimens

Directory of Open Access Journals (Sweden)

Katarzyna Taran

2016-07-01

Full Text Available Introduction: Hepatoblastoma is the most common primary liver tumor in children. However, it occurs rarely, with an incidence of 0.5-1.5 cases per million children. There is no clear explanation of the relationship between clinicopathologic features, therapy, and outcome in hepatoblastoma cases, so far. One of the most widely accepted prognostic factors in hepatoblastoma is histology of the tumor. The aim of the study was to determine the potential differences in biology of hepatoblastoma histological subtypes at the atomic level using the unique method of isotope ratio mass spectrometry, which is especially valuable in examination of small groups of biological samples.Material/Methods: Twenty-four measurements of nitrogen stable isotope ratio, carbon stable isotope ratio and total carbon to nitrogen mass ratio in fetal and embryonal hepatoblastoma tissue were performed using a Sercon 20-22 Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS coupled with a Sercon SL elemental analyzer for simultaneous carbon-nitrogen-sulfur (NCS analysis.Results: A difference of about 1.781‰ in stable nitrogen isotope 15N/14N ratio was found between examined hepatoblastoma histological subtypes.Conclusions: The prognosis in liver tumors cases in children may be challenging particularly because of the lack of versatile methods of its evaluation. Isotope ratio mass spectrometry allows one to determine the difference between hepatoblastoma histological subtypes and clearly indicates the cases with the best outcome.

Use of isotope ratio mass spectrometry to differentiate between endogenous steroids and synthetic homologues in cattle: A review

Energy Technology Data Exchange (ETDEWEB)

Janssens, Geert, E-mail: Geert.janssens@favv.be [Federal Agency for the Safety of the Food Chain, Directorate General Laboratories, Kruidtuinlaan 55, 1000 Brussels (Belgium); Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Courtheyn, Dirk [Federal Agency for the Safety of the Food Chain, Directorate General Laboratories, Kruidtuinlaan 55, 1000 Brussels (Belgium); Mangelinckx, Sven [Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Prévost, Stéphanie; Bichon, Emmanuelle; Monteau, Fabrice [LUNAM Université, Oniris, Laboratoire d’Etude des Résidus et Contaminants dans les Aliments (LABERCA), F-44307 Nantes (France); De Poorter, Geert [Federal Agency for the Safety of the Food Chain, Directorate General Laboratories, Kruidtuinlaan 55, 1000 Brussels (Belgium); De Kimpe, Norbert [Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Le Bizec, Bruno [LUNAM Université, Oniris, Laboratoire d’Etude des Résidus et Contaminants dans les Aliments (LABERCA), F-44307 Nantes (France)

2013-04-15

Graphical abstract: Scheme: Representation of the observed isotope ratios and the relation to exogenous and endogenous natural steroids. AS stands for “amount of steroid”. Highlights: ► The difference between endogenous and exogenous steroids is thoroughly laid out. ► Factors influencing the carbon ratio and the use of Δ{sup 13}C-values are explained. ► Implementation of GC/C/IRMS to detect steroid abuse in cattle is reviewed. ► Alternative methods and upcoming techniques are discussed. ► The differences and similarities with sports doping control are highlighted. -- Abstract: Although substantial technical advances have been achieved during the past decades to extend and facilitate the analysis of growth promoters in cattle, the detection of abuse of synthetic analogs of naturally occurring hormones has remained a challenging issue. When it became clear that the exogenous origin of steroid hormones could be traced based on the {sup 13}C/{sup 12}C isotope ratio of the substances, GC/C/IRMS has been successfully implemented to this aim since the end of the past century. However, due to the costly character of the instrumental setup, the susceptibility of the equipment to errors and the complex and time consuming sample preparation, this method is up until now only applied by a limited number of laboratories. In this review, the general principles as well as the practical application of GC/C/IRMS to differentiate between endogenous steroids and exogenously synthesized homologous compounds in cattle will be discussed in detail, and will be placed next to other existing and to be developed methods based on isotope ratio mass spectrometry. Finally, the link will be made with the field of sports doping, where GC/C/IRMS has been established within the World Anti-Doping Agency (WADA) approved methods as the official technique to differentiate between exogenous and endogenous steroids over the past few years.

Mass spectrometry-assisted protease substrate screening

DEFF Research Database (Denmark)

Schlüter, Hartmut; Rykl, Jana; Thiemann, Joachim

2007-01-01

-phase chromatography they are analyzed by tandem mass spectrometry and the substrates identified by database searching. The proof of principle in this study is demonstrated by incubating immobilized human plasma proteins with thrombin and by identifying by tandem mass spectrometry the fibrinopeptides, released...

Clinical Mass Spectrometry: Achieving Prominence in Laboratory Medicine

Energy Technology Data Exchange (ETDEWEB)

Annesley, Thomas M.; Cooks, Robert G.; Herold, David A.; Hoofnagle, Andrew N.

2016-01-04

Each year the journal Clinical Chemistry publishes a January special issue on a topic that is relevant to the laboratory medicine community. In January 2016 the topic is mass spectrometry, and the issue is entitled “Clinical Mass Spectrometry: Achieving Prominence in Laboratory Medicine”. One popular feature in our issues is a Q&A on a topic, clearly in this case mass spectrometry. The journal is assembling a panel of 5-6 experts from various areas of mass spectrometry ranging from instrument manufacturing to practicing clinical chemists. Dick Smith is one of the scientist requested to participate in this special issue Q&A on Mass Spectrometry. The Q&A Transcript is attached

Thermal ionisation mass spectrometry (TIMS): what, how and why?

International Nuclear Information System (INIS)

Aggarwal, S.K.

2002-01-01

Thermal ionisation mass spectrometry (TIMS) is one of the oldest mass spectrometric techniques, which has been used for determining the isotopic composition and concentration of different elements using isotope dilution. In spite of the introduction of many other inorganic mass spectrometric techniques like spark source mass spectrometry (SSMS), glow discharge mass spectrometry (GDMS), inductively coupled plasma-mass spectrometry (ICP-MS), secondary ion mass spectrometry (SIMS), the TIMS technique plays the role of a definitive analytical methodology and still occupies a unique position in terms of its capabilities with respect to precision and accuracy as well as sensitivity

Surface analysis by imaging mass spectrometry

Czech Academy of Sciences Publication Activity Database

Vidová, Veronika; Volný, Michael; Lemr, Karel; Havlíček, Vladimír

2009-01-01

Roč. 74, 7-8 (2009), s. 1101-1116 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z50200510 Keywords : secondary ion mass spectrometry * matrix assisted laser desorption ionization * mass spectrometry Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 0.856, year: 2009

Introduction to mass spectrometry-based proteomics

DEFF Research Database (Denmark)

Matthiesen, R.; Bunkenborg, J.

2013-01-01

Mass spectrometry has been widely applied to study biomolecules and one rapidly developing field is the global analysis of proteins, proteomics. Understanding and handling mass spectrometry data is a multifaceted task that requires many decisions to be made to get the most comprehensive informati...

Burnup determination of mass spectrometry for nuclear fuels

International Nuclear Information System (INIS)

Zhang Chunhua.

1987-01-01

The various methods currently being used in burnup determination of nuclear fuels are studied and reviewed. The mass spectrometry method of destructive testing is discussed emphatically. The burnup determination of mass spectrometry includes heavy isotopic abundance ratio method and isotope dilution mass spectrometry used as burnup indicator for the fission products. The former is applied to high burnup level, but the later to various burnup level. According to experiences, some problems which should be noticed in burnup determination of mass spectrometry are presented

Instrumentation for mass spectrometry: 1997

Energy Technology Data Exchange (ETDEWEB)

McLuckey, S.A.

1997-08-01

All mass spectrometry experiments involve the manipulation of material, an interface with the mass spectrometer, ionization, ion manipulation/analysis, detection and data collection/reduction. Each of these elements involve instrumentation. The wide range of species now amenable to mass spectrometry and the diverse areas of physical science in which it plays a role have led to a seemingly unlimited array of instrumental combinations. However, only a limited number of mass analyzers, and their combinations, dominate. The dominant analyzers include time-of-flight, Fourier transform ion cyclotron resonance, the Paul trap, the mass filter, and the sector mass spectrometer. Why there are so few (or so many, depending upon one`s point of view) can be understood upon consideration of a set of mass analyzer figures of merit. These include mass resolution, mass accuracy, mass range, dynamic range, abundance sensitivity, precision, efficiency, speed, MS{sup n} capability, compatibility with the ionizer, cost, and size. The most appropriate form of mass spectrometry is determined by the priorities of the particular measurement placed on the various mass analyzer characteristics and the relative strengths of the analyzers in meeting the requirements. Each of the analyzer types has a unique set of figures of merit that makes it optimally suited for particular applications. This paper discusses these figures of merit, provides data illustrating recent developments for each analyzer type, and gives the figures of merit of each type of analyzer as they stand in 1997. 101 refs., 24 figs.

Drug testing data from the 2007 Pan American Games: delta13C values of urinary androsterone, etiocholanolone and androstanediols determined by GC/C/IRMS.

Science.gov (United States)

Aguilera, Rodrigo; Chapman, Thomas E; Pereira, Henrique; Oliveira, Giselle C; Illanes, Renata P; Fernandes, Telma F; Azevedo, Débora A; Neto, Francisco Aquino

2009-07-01

The main purpose of this article is to show the application of the CG/C/IRMS in real time during competition in the steroid confirmation analysis. For this reason, this paper summarizes the results obtained from the doping control analysis during the period of the 2007 Pan American Games held in Rio de Janeiro, Brazil. Approximately 5600 athletes from 42 different countries competed in the games. Testing was performed in accordance to World Anti-Doping Agency (WADA) technical note for prohibited substances. This paper reports data where abnormal urinary steroid profiles, have been found with the screening procedures. One 8 mL urine sample was used for the analysis of five steroid metabolites with two separate analyses by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Urine samples were submitted to GC/C/IRMS for confirmation analysis to determine the (13)C/(12)C ratio of selected steroids. Fifty-seven urine samples were analyzed by GC/C/IRMS and the delta(13)C values ( per thousand) of androsterone, etiocholanolone, 5beta-androstane-3alpha, 17beta-diol (5beta-diol), 5alpha-androstane-3alpha, 17beta-diol (5alpha-diol) and 5beta-pregnane-3alpha, 20alpha-diol (5beta-pdiol), the endogenous reference compound are presented. One urine sample with a testosterone/epitestosterone (T/E) ratio of 4.7 was confirmed to be positive of doping by GC/C/IRMS analysis. The delta values of 5beta-diol and 5alpha-diol were 3.8 and 10.8, respectively, compared to the endogenous reference compound 5beta-pdiol, which exceeded the WADA limit of 3 per thousand. The results obtained by CG/C/IRMS confirmation analyses, in suspicious samples, were conclusive in deciding whether or not a doping steroid violation had occurred.

Silver nanostructures in laser desorption/ionization mass spectrometry and mass spectrometry imaging.

Science.gov (United States)

Sekuła, Justyna; Nizioł, Joanna; Rode, Wojciech; Ruman, Tomasz

2015-09-21

Silver nanoparticles have been successfully applied as a matrix replacement for the laser desorption/ionization time-of-flight mass spectrometry (LDI-ToF-MS). Nanoparticles, producing spectra with highly reduced chemical background in the low m/z region, are perfectly suited for low-molecular weight compound analysis and imaging. Silver nanoparticles (AgNPs) can efficiently absorb ultraviolet laser radiation, transfer energy to the analyte and promote analyte desorption, but also constitute a source of silver ions suitable for analyte cationisation. This review provides an overview of the literature on silver nanomaterials as non-conventional desorption and ionization promoters in LDI-MS and mass spectrometry imaging.

Tandem mass spectrometry at low kinetic energy

International Nuclear Information System (INIS)

Cooks, R.G.; Hand, O.W.

1987-01-01

Recent progress in mass spectrometry, as applied to molecular analysis, is reviewed with emphasis on tandem mass spectrometry. Tandem instruments use multiple analyzers (sector magnets, quadrupole mass filters and time-of-flight devices) to select particular molecules in ionic form, react them in the gas-phase and then record the mass, momenta or kinetic energies of their products. The capabilities of tandem mass spectrometry for identification of individual molecules or particular classes of compounds in complex mixtures are illustrated. Several different types of experiments can be run using a tandem mass spectrometer; all share the feature of sifting the molecular mixture being analyzed on the basis of chemical properties expressed in terms of ionic mass, kinetic energy or charge state. Applications of mass spectrometry to biological problems often depend upon desorption methods of ionization in which samples are bombarded with particle beams. Evaporation of preformed charged species from the condensed phase into the vacuum is a particularly effective method of ionization. It is suggested that the use of accelerator mass spectrometers be extended to include problems of molecular analysis. In such experiments, low energy tandem mass spectrometry conducted in the eV or keV range of energies, would be followed by further characterization of the production ion beam using high selective MeV collision processes

Stable isotope ratio mass spectrometry and physical comparison for the forensic examination of grip-seal plastic bags.

Science.gov (United States)

Taylor, Erica; Carter, James F; Hill, Jenny C; Morton, Carolyn; Daeid, Niamh Nic; Sleeman, Richard

2008-05-20

Plastic bags are frequently used to package drugs, explosives and other contraband. There exists, therefore, a requirement in forensic casework to compare bags found at different locations. This is currently achieved almost exclusively by the use of physical comparisons such as birefringence patterns. This paper discusses some of the advantages and shortcomings of this approach, and presents stable isotope ratio mass spectrometry (IRMS) as a supplementary tool for effecting comparisons of this nature. Carbon and hydrogen isotopic data are presented for sixteen grip-seal plastic bags from a wide range of sources, in order to demonstrate the range of values which is likely to be encountered. Both isotopic and physical comparison (specifically birefringence) techniques are then applied to the analysis of rolls of bags from different manufacturing lots from a leading manufacturer. Both approaches are able to associate bags from a common production batch. IRMS can be applied to small fragments which are not amenable to physical comparisons, and is able to discriminate bags which could be confused using birefringence patterns alone. Similarly, in certain cases birefringence patterns discriminate bags with similar isotopic compositions. The two approaches are therefore complementary. When more than one isotopically distinct region exists within a bag (e.g. the grip-seal is distinct from the body) the ability to discriminate and associate bags is greatly increased.

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.

Pyrolysis-gas chromatography-isotope ratio mass spectrometry for monitoring natural additives in polylactic acid active food packages.

Science.gov (United States)

Llana-Ruíz-Cabello, M; Pichardo, S; Jiménez-Morillo, N T; González-Vila, F J; Guillamón, E; Bermúdez, J M; Aucejo, S; Camean, A M; González-Pérez, J A

2017-11-24

Compound-specific isotope analysis (CSIA) usually requires preparative steps (pretreatments, extraction, derivatization) to get amenable chromatographic analytes from bulk geological, biological or synthetic materials. Analytical pyrolysis (Py-GC/MS) can help to overcome such sample manipulation. This communication describe the results obtained by hyphenating analytical pyrolysis (Py-GC) with carbon isotope-ratio mass spectrometry (IRMS) for the analysis of a polylactic acid (PLA) a based bio-plastic extruded with variable quantities of a natural plant extract or oregano essential oil. The chemical structural information of pyrolysates was first determined by conventional analytical pyrolysis and the measure of δ 13 C in specific compounds was done by coupling a pyrolysis unit to a gas chromatograph connected to a continuous flow IRMS unit (Py-GC-C-IRMS). Using this Py-CSIA device it was possible to trace natural additives with depleted δ 13 C values produced by C3 photosystem vegetation (cymene: -26.7‰±2.52; terpinene: -27.1‰±0.13 and carvacrol: -27.5‰±1.80 from oregano and two unknown structures: -23.3‰±3.32 and -24.4‰±1.70 and butyl valerate: -24.1‰±3.55 from Allium spp.), within the naturally isotopically enriched bio-plastic backbone derived from corn (C4 vegetation) starch (cyclopentanones: -14.2‰±2.11; lactide enantiomers: -9.2‰±1.56 and larger polymeric units: -17.2‰±1.71). This is the first application of Py-CSIA to characterize a bio-plastic and is shown as a promising tool to study such materials, providing not only a fingerprinting, but also valuable information about the origin of the materials, allowing the traceability of additives and minimizing sample preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

Science.gov (United States)

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

Ambient ionization mass spectrometry

International Nuclear Information System (INIS)

Lebedev, A T

2015-01-01

Ambient ionization mass spectrometry emerged as a new scientific discipline only about ten years ago. A considerable body of information has been reported since that time. Keeping the sensitivity, performance and informativity of classical mass spectrometry methods, the new approach made it possible to eliminate laborious sample preparation procedures and triggered the development of miniaturized instruments to work directly in the field. The review concerns the theoretical foundations and design of ambient ionization methods. Their advantages and drawbacks, as well as prospects for application in chemistry, biology, medicine, environmetal analysis, etc., are discussed. The bibliography includes 194 references

Discrimination of geographical origin of lentils (Lens culinaris Medik.) using isotope ratio mass spectrometry combined with chemometrics.

Science.gov (United States)

Longobardi, F; Casiello, G; Cortese, M; Perini, M; Camin, F; Catucci, L; Agostiano, A

2015-12-01

The aim of this study was to predict the geographic origin of lentils by using isotope ratio mass spectrometry (IRMS) in combination with chemometrics. Lentil samples from two origins, i.e. Italy and Canada, were analysed obtaining the stable isotope ratios of δ(13)C, δ(15)N, δ(2)H, δ(18)O, and δ(34)S. A comparison between median values (U-test) highlighted statistically significant differences (porigin but with overlapping zones; consequently, two supervised discriminant techniques, i.e. partial least squares discriminant analysis and k-nearest neighbours algorithm were used. Both models showed good performances with external prediction abilities of about 93% demonstrating the suitability of the methods developed. Subsequently, isotopic determinations were also performed on the protein and starch fractions and the relevant results are reported. Copyright © 2015 Elsevier Ltd. All rights reserved.

Um dia na vida de irmãos que cuidam de irmãos

Directory of Open Access Journals (Sweden)

Letícia Lovato Dellazzana

Full Text Available O objetivo deste artigo é descrever a rotina de adolescentes de baixa renda que cuidam de seus irmãos. Participaram do estudo 20 adolescentes de 12 a 16 anos. Foi utilizada uma ficha de dados sociodemográficos, genograma familiar e entrevista semiestruturada sobre um dia de suas vidas. Organizaram-se as atividades relatadas em cinco categorias: cuidado pessoal, cuidado dos irmãos, domésticas, escolares e de lazer. A partir dessas atividades dividiram-se os participantes em três grupos: responsáveis pelo cuidado dos irmãos, ajudam suas mães e sem essas atividades. Os resultados indicaram que adolescentes de ambos os sexos cuidam dos irmãos, mas são as meninas que mais assumem tarefas domésticas. Quando responsabilizados pelo cuidado, suas atividades escolares e de lazer são prejudicadas.

Imaging mass spectrometry in drug development and toxicology.

Science.gov (United States)

Karlsson, Oskar; Hanrieder, Jörg

2017-06-01

During the last decades, imaging mass spectrometry has gained significant relevance in biomedical research. Recent advances in imaging mass spectrometry have paved the way for in situ studies on drug development, metabolism and toxicology. In contrast to whole-body autoradiography that images the localization of radiolabeled compounds, imaging mass spectrometry provides the possibility to simultaneously determine the discrete tissue distribution of the parent compound and its metabolites. In addition, imaging mass spectrometry features high molecular specificity and allows comprehensive, multiplexed detection and localization of hundreds of proteins, peptides and lipids directly in tissues. Toxicologists traditionally screen for adverse findings by histopathological examination. However, studies of the molecular and cellular processes underpinning toxicological and pathologic findings induced by candidate drugs or toxins are important to reach a mechanistic understanding and an effective risk assessment strategy. One of IMS strengths is the ability to directly overlay the molecular information from the mass spectrometric analysis with the tissue section and allow correlative comparisons of molecular and histologic information. Imaging mass spectrometry could therefore be a powerful tool for omics profiling of pharmacological/toxicological effects of drug candidates and toxicants in discrete tissue regions. The aim of the present review is to provide an overview of imaging mass spectrometry, with particular focus on MALDI imaging mass spectrometry, and its use in drug development and toxicology in general.

Alpha spectrometry and secondary ion mass spectrometry of thorium

International Nuclear Information System (INIS)

Strisovska, Jana; Kuruc, Jozef; Galanda, Dusan; Matel, Lubomir; Velic, Dusan; Aranyosiova, Monika

2009-01-01

A sample of thorium content on steel discs was prepared by electrodeposition with a view to determining the natural thorium isotope. Thorium was determined by alpha spectrometry and by secondary ion mass spectrometry and the results of the two methods were compared

High-sensitivity mass spectrometry with a tandem accelerator

International Nuclear Information System (INIS)

Henning, W.

1984-01-01

The characteristic features of accelerator mass spectrometry are discussed. A short overview is given of the current status of mass spectrometry with high-energy (MeV/nucleon) heavy-ion accelerators. Emphasis is placed on studies with tandem accelerators and on future mass spectrometry of heavier isotopes with the new generation of higher-voltage tandems

Inorganic mass spectrometry of solid samples

International Nuclear Information System (INIS)

Adams, F.; Vertes, A.

1990-01-01

In this review some recent developments in the field of inorganic mass spectrometry of solids are described with special emphasis on the actual state of understanding of the ionization processes. It concentrates on the common characteristics of methods such as spark source-, laser-, secondary ion-, inductively coupled plasma- and glow discharge mass spectrometry. (orig.)

Mass spectrometry a versatile aid to inorganic analysis

International Nuclear Information System (INIS)

Stefani, Rene

1976-01-01

Several hundred publications have appeared in the last three years that deal with applications of Mass Spectrometry to inorganic analysis. Bulk and localized trace analysis, surface and thin film characterization and microstructure examination are currently performed by Secondary Ion Mass Spectrometry, Spark Source Mass Spectrometry and the newly developed Laser Probe Mass Spectrometry. Suitable experimental procedures allow insulators, biologic materials and microsamples to be analysed. In spite of the classification by techniques this review is essentially devoted to the most significant papers in analytical applications but instrumental and basic features are sometimes introduced to support the discussions

Comprehensive authentication of (E)-alpha(beta)-ionone from raspberries, using constant flow MDGC-C/P-IRMS and enantio-MDGC-MS.

Science.gov (United States)

Sewenig, Sabine; Bullinger, Dino; Hener, Uwe; Mosandl, Armin

2005-02-23

A new coupling system of GC-GC, connected via a Multi Column Switching Device MCS2 for measuring isotope ratios, is introduced. By means of several standard substances the precise and accurate measurement of isotopic values is proved. First applications concerning the authentication of raspberry aroma compounds are established. Consequently, the combination of constant flow multidimensional gas chromatography-combustion/pyrolysis-isotope ratio mass spectrometry (MDGC-C/P-IRMS) is applied to the authenticity assessment of (E)-alpha(beta)-ionone from six different raspberry cultivars. Furthermore, 12 commercially available raspberry products and samples of (E)-alpha(beta)-ionone, some declared to be natural, are investigated. delta(2)Eta(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values of (E)-alpha(beta)-ionone are determined, and characteristic authenticity ranges were concluded from raspberries by correlation of both delta(2)Eta(V)(-)(SMOW) and delta(13)C( V)(-)(PDB) values. The results are correlated with the determination of enantiomeric purities of (E)-alpha-ionone, using stir bar sorptive extraction enantio-multidimensional gas chromatography mass spectrometry (SBSE-enantio-MDGC-MS).

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

Science.gov (United States)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

(13)C/(12)C isotope ratios of organic acids, glucose and fructose determined by HPLC-co-IRMS for lemon juices authenticity.

Science.gov (United States)

Guyon, Francois; Auberger, Pauline; Gaillard, Laetita; Loublanches, Caroline; Viateau, Maryse; Sabathié, Nathalie; Salagoïty, Marie-Hélène; Médina, Bernard

2014-03-01

High performance liquid chromatography linked to isotope ratio mass spectrometry via an interface allowing the chemical oxidation of organic matter (HPLC-co-IRMS) was used to simultaneously determine carbon 13 isotope ratio (δ(13)C) of organic acids, glucose and fructose in lime and lemon juices. Because of the significant difference between organic acids and sugars concentrations, the experimental protocol was optimised by applying a "current jump" to the IRMS device. The filament current is increased of 300μA during elution in order to enhance IRMS sensitivity. Then, analysis were performed on 35 lemon and lime fruits from various geographical origins and squeezed in the laboratory. An overall average δ(13)C values of -25.40±1.62‰, -23.83±1.82‰ and -25.67±1.72‰ is found for organic acids mixture mainly made up of citric acid, glucose and fructose, respectively. These authentic samples allowed the definition of a confidence domain to which have been confronted 30 commercial juices (24 "pure juices" and 6 coming from concentrate). Among these 30 samples, 10 present δ(13)C values outside the defined range revealing an added "C4" type organic acids or sugars, addition not specified on the label that is not in agreement with EU regulation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mass spectrometry in nuclear science and technology

International Nuclear Information System (INIS)

Komori, Takuji

1985-01-01

Mass spectrometry has been widely used and playing a very important role in the field of nuclear science and technology. A major reason for this is that not only the types of element but also its isotopes have to be identified and measured in this field. Thus, some applications of this analytical method are reviewed and discussed in this article. Its application to analytical chemistry is described in the second section following an introductory section, which includes subsections for isotropic dilution mass spectrometry, resonance ionization mass spectrometry and isotopic correlation technique. The isotopic ratio measurement for hydrogen, uranium and plutonium as well as nuclear material control and safeguards are also reviewed in this section. In the third section, mass spectrometry is discussed in relation to nuclear reactors, with subsections on natural uranium reactor and neutron flux observation. Some techniques for measuring the burnup fraction, including the heavy isotopic ratio method and fission product monitoring, are also described. In the fourth section, application of mass spectrometry to measurement of nuclear constants, such as ratio of effective cross-sectional area for 235 U, half-life and fission yield is reviewed. (Nogami, K.)

Romanian wines characterization with CF-IRMS (Continuous Flow Isotope Ratio Mass Spectrometry) isotopic analysis

International Nuclear Information System (INIS)

Costinel, Diana; Ionete, Roxana Elena; Vremera, Raluca; Stanciu, Vasile

2007-01-01

Wine growing has been known for centuries long in Romania. The country has been favored by its geographical position in south-eastern Europe, by its proximity to the Black Sea, as well as by the specificity of the local soil and climate. Alongside France, Italy, Spain, Germany, countries in this area like Romania could also be called 'a vine homeland' in Europe. High quality wines produced in this region were object of trade ever since ancient times. Under current EU research projects, it is necessary to develop new methods of evidencing wine adulteration and safety. The use of mass spectrometry (MS) to determine the ratios of stable isotopes in bio-molecules now provides the means to prove the botanical and geographical origin of a wide variety of foodstuffs - and therefore, to authenticate and eliminate fraud. Isotope analysis has been officially adopted by the EU as a means of controlling adulteration of wine. Adulteration of wine can happen in many ways, e.g. addition of non-grape ethanol, addition of non-grape sugar, water or other unauthorized substances, undeclared mixing of wines from different wards, geographical areas or countries, mislabelling of variety and age. The present paper emphasize the isotopic analysis for D/H, 18 O/ 16 O, 13 C/ 12 C from wines, using a new generation Isotope Ratio MS, Finnigan Delta V Plus, coupling with a three flexible continuous flow preparation device (GasBench II, TC Elemental Analyser and GC-C/TC). Therefore authentication of wines is an important problem to which isotopic analysis has made a significant contribution. (authors)

Dual Si and O Isotope Measurement of Lunar Samples Using IRMS

Science.gov (United States)

Banerjee, N.; Hill, P. J. A.; Osinski, G. R.

2016-12-01

The use of isotopic systems and their associated theoretical models have become an increasingly sophisticated tool for investigating the origin of planetary bodies in the solar system. It was originally hypothesized that evidence for the impact origin of Moon would manifest itself as an isotopic heterogeneity between lunar and terrestrial samples; however, most isotope systems show no difference between the bulk Earth and Moon. The stable isotopes of both silicon (Si) and oxygen (O) have been essential in further understanding planetary processes including core formation. Historically the analysis of the Si and O isotope ratios in terrestrial and extraterrestrial material has primarily been measured independent of each other through three main techniques: isotope ratio mass spectrometry (IRMS), secondary ion mass spectrometry (SIMS), and multi-collector inductively coupled plasma mass-spectrometry (MC-ICPMS). Each technique has its own strength and weakness in regards to resolution and precision; however, one of the main limiting factors in all three of these techniques rests on the requirement of multiple aliquots. As most literature focuses on the measurement of oxygen or silicon isotopes, this unique line allows for the precise analysis of Si and O isotopes from the same aliquot of bulk sample, which cannot be done with SIMS or ICP-MS analysis. To deal with this problem a unique laser line system has been developed in the Laboratory for Stable Isotope Science at Western University, Canada, that simultaneously extracts SiF4 and O2 from the same 1-2 mg aliquot. We present the application of analyzing both isotopic systems from the sample aliquot to Apollo, meteoritic, and terrestrial samples and its implication for the formation of the Moon. Preliminary results from this line suggest that although the O isotopes ratios are consistent with a homogenous Moon-Earth system, a difference is observed in Si isotopes between Apollo and terrestrial samples compared to

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.

Mass Spectrometry Analyses of Multicellular Tumor Spheroids.

Science.gov (United States)

Acland, Mitchell; Mittal, Parul; Lokman, Noor A; Klingler-Hoffmann, Manuela; Oehler, Martin K; Hoffmann, Peter

2018-05-01

Multicellular tumor spheroids (MCTS) are a powerful biological in vitro model, which closely mimics the 3D structure of primary avascularized tumors. Mass spectrometry (MS) has established itself as a powerful analytical tool, not only to better understand and describe the complex structure of MCTS, but also to monitor their response to cancer therapeutics. The first part of this review focuses on traditional mass spectrometry approaches with an emphasis on elucidating the molecular characteristics of these structures. Then the mass spectrometry imaging (MSI) approaches used to obtain spatially defined information from MCTS is described. Finally the analysis of primary spheroids, such as those present in ovarian cancer, and the great potential that mass spectrometry analysis of these structures has for improved understanding of cancer progression and for personalized in vitro therapeutic testing is discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The emergence of mass spectrometry in biochemical research

OpenAIRE

1995-01-01

The initial steps toward routinely applying mass spectrometry in the biochemical laboratory have been achieved. In the past, mass spectrometry was confined to the realm of small, relatively stable molecules; large or thermally labile molecules did not survive the desorption and ionization processes intact. Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry allow for the analysis of both small and large biomolecules through "mild" desorption...

Testing of an automated online EA-IRMS method for fast and simultaneous carbon content and stable isotope measurement of aerosol samples

Science.gov (United States)

Major, István; Gyökös, Brigitta; Túri, Marianna; Futó, István; Filep, Ágnes; Hoffer, András; Molnár, Mihály

2016-04-01

Comprehensive atmospheric studies have demonstrated that carbonaceous aerosol is one of the main components of atmospheric particulate matter over Europe. Various methods, considering optical or thermal properties, have been developed for quantification of the accurate amount of both organic and elemental carbon constituents of atmospheric aerosol. The aim of our work was to develop an alternative fast and easy method for determination of the total carbon content of individual aerosol samples collected on prebaked quartz filters whereby the mass and surface concentration becomes simply computable. We applied the conventional "elemental analyzer (EA) coupled online with an isotope ratio mass spectrometer (IRMS)" technique which is ubiquitously used in mass spectrometry. Using this technique we are able to measure simultaneously the carbon stable isotope ratio of the samples, as well. During the developing process, we compared the EA-IRMS technique with an off-line catalytic combustion method worked out previously at Hertelendi Laboratory of Environmental Studies (HEKAL). We tested the combined online total carbon content and stable isotope ratio measurement both on standard materials and real aerosol samples. Regarding the test results the novel method assures, on the one hand, at least 95% of carbon recovery yield in a broad total carbon mass range (between 100 and 3000 ug) and, on the other hand, a good reproducibility of stable isotope measurements with an uncertainty of ± 0.2 per mill. Comparing the total carbon results obtained by the EA-IRMS and the off-line catalytic combustion method we found a very good correlation (R2=0.94) that proves the applicability of both preparation method. Advantages of the novel method are the fast and simplified sample preparation steps and the fully automated, simultaneous carbon stable isotope ratio measurement processes. Furthermore stable isotope ratio results can effectively be applied in the source apportionment

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

Science.gov (United States)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2010-01-01

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

Zero voltage mass spectrometry probes and systems

Science.gov (United States)

Cooks, Robert Graham; Wleklinski, Michael Stanley; Bag, Soumabha; Li, Yafeng

2017-10-10

The invention generally relates to zero volt mass spectrometry probes and systems. In certain embodiments, the invention provides a system including a mass spectrometry probe including a porous material, and a mass spectrometer (bench-top or miniature mass spectrometer). The system operates without an application of voltage to the probe. In certain embodiments, the probe is oriented such that a distal end faces an inlet of the mass spectrometer. In other embodiments, the distal end of the probe is 5 mm or less from an inlet of the mass spectrometer.

Mass spectrometry for biomarker development

Energy Technology Data Exchange (ETDEWEB)

Wu, Chaochao; Liu, Tao; Baker, Erin Shammel; Rodland, Karin D.; Smith, Richard D.

2015-06-19

Biomarkers potentially play a crucial role in early disease diagnosis, prognosis and targeted therapy. In the past decade, mass spectrometry based proteomics has become increasingly important in biomarker development due to large advances in technology and associated methods. This chapter mainly focuses on the application of broad (e.g. shotgun) proteomics in biomarker discovery and the utility of targeted proteomics in biomarker verification and validation. A range of mass spectrometry methodologies are discussed emphasizing their efficacy in the different stages in biomarker development, with a particular emphasis on blood biomarker development.

A new CF-IRMS system for quantifying stable isotopes of carbon monoxide from ice cores and small air samples

Directory of Open Access Journals (Sweden)

Z. Wang

2010-10-01

Full Text Available We present a new analysis technique for stable isotope ratios (δ¹³C and δ¹⁸O of atmospheric carbon monoxide (CO from ice core samples. The technique is an online cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS; it can also be used with small air samples. The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO₂, a cryogenic collection trap, a cryofocusing unit, gas chromatography purification, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰ (±1δ for δ¹³C and 0.6‰ (±1δ for δ¹⁸O can be obtained for 100 mL (STP air samples with CO mixing ratios ranging from 60 ppbv to 140 ppbv (~268–625 pmol CO. Six South Pole ice core samples from depths ranging from 133 m to 177 m were processed for CO isotope analysis after wet extraction. To our knowledge, this is the first measurement of stable isotopes of CO in ice core air.

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.

Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry

NARCIS (Netherlands)

Ruth, van S.M.; Floris, V.; Fayoux, S.

2006-01-01

The volatile profiles of 13 infant formulas were evaluated by proton transfer reaction-mass spectrometry (PTR-MS) and gas chromatography¿mass spectrometry (GC¿MS). The infant formulas varied in brand (Aptamil, Cow & Gate, SMA), type (for different infant target groups) and physical form

Analysis of 13C-mixed triacylglycerol in stool by bulk (EA-IRMS) and compound specific (GC/MS) methods.

Science.gov (United States)

Slater, C; Ling, S C; Preston, T; Weaver, L T

2002-06-01

This paper was presented in poster form at the 17th International Congress of Nutrition, August 27-31, Vienna, Austria (Annals of Nutrition & Metabolism 2001; 45(Suppl.1):349). Some of the data were also presented in poster form at the British Society of Gastroenterology Meeting, March 18-21, Glasgow, UK (Gut 2001; 48(Suppl.1):A91). The 13C-mixed triacylglycerol (MTG) breath test is used to measure intraluminal fat digestion. In normal digestion, 20-40% of the ingested 13C label is recovered in breath CO2. We aimed to identify the proportions of ingested label excreted in stool, as well as breath following ingestion of 13C-MTG by children with impaired exocrine pancreatic function and healthy controls. 13C enrichment of breath samples was measured by continuous flow isotope ratio mass spectrometry (IRMS) and cumulative percent dose recovered (cPDR) in 10 h was calculated. Total 13C of a faecal fat extract from each stool was measured by elemental analyser-IRMS, and 13C enrichment and concentration of the TBDMS derivative of octanoic acid was measured by GC/MS after hydrolysis of the fat extract. Stool 5-day cPDR was calculated. Mean breath cPDR was 35%. Mean cPDR in stool by combustion-IRMS and GC/ MS, respectively, was 0.8% and 1.0%. Therefore, the remaining 64% of the 13C label must remain in the body and variability in breath cPDR is due to postabsorptive rather than predigestive factors.

Emerging mass spectrometry techniques for the direct analysis of microbial colonies

OpenAIRE

Fang, Jinshu; Dorrestein, Pieter C.

2014-01-01

One of the emerging areas in microbiology is detecting specialized metabolites produced by microbial colonies and communities with mass spectrometry. In this review/perspective, we illustrate the emerging mass spectrometry methodologies that enable the interrogation of specialized metabolites directly from microbial colonies. Mass spectrometry techniques such as imaging mass spectrometry and real-time mass spectrometry allow two and three dimensional visualization of the distri...

Mass spectrometry in oceanography

International Nuclear Information System (INIS)

Aggarwal, Suresh K.

2000-01-01

Mass spectrometry plays an important role in oceanography for various applications. Different types of inorganic as well as organic mass spectrometric techniques are being exploited world-wide to understand the different aspects of marine science, for palaeogeography, palaeoclimatology and palaeoecology, for isotopic composition and concentrations of different elements as well as for speciation studies. The present paper reviews some of the applications of atomic mass spectrometric techniques in the area of oceanography

Characterizing the lipid and metabolite changes associated with placental function and pregnancy complications using ion mobility spectrometry-mass spectrometry and mass spectrometry imaging

Energy Technology Data Exchange (ETDEWEB)

Burnum-Johnson, Kristin E.; Baker, Erin S.; Metz, Thomas O.

2017-12-01

Successful pregnancy is dependent upon discrete biological events, which include embryo implantation, decidualization, and placentation. Problems associated with each of these events can cause infertility or conditions such as preeclampsia. A greater understanding of the molecular changes associated with these complex processes is necessary to aid in identifying treatments for each condition. Previous nuclear magnetic resonance spectroscopy and mass spectrometry studies have been used to identify metabolites and lipids associated with pregnancy-related complications. However, due to limitations associated with conventional implementations of both techniques, novel technology developments are needed to more fully understand the initiation and development of pregnancy related problems at the molecular level. In this perspective, we describe current analytical techniques for metabolomic and lipidomic characterization of pregnancy complications and discuss the potential for new technologies such as ion mobility spectrometry-mass spectrometry and mass spectrometry imaging to contribute to a better understanding of the molecular changes that affect the placenta and pregnancy outcomes.

Mass spectrometry in life science research.

Science.gov (United States)

Lehr, Stefan; Markgraf, Daniel

2016-12-01

Investigating complex signatures of biomolecules by mass spectrometry approaches has become indispensable in molecular life science research. Nowadays, various mass spectrometry-based omics technologies are available to monitor qualitative and quantitative changes within hundreds or thousands of biological active components, including proteins/peptides, lipids and metabolites. These comprehensive investigations have the potential to decipher the pathophysiology of disease development at a molecular level and to monitor the individual response of pharmacological treatment or lifestyle intervention.

Origin of Xylitol in Chewing Gum: A Compound-Specific Isotope Technique for the Differentiation of Corn- and Wood-Based Xylitol by LC-IRMS.

Science.gov (United States)

Köster, Daniel; Wolbert, Jens-Benjamin; Schulte, Marcel S; Jochmann, Maik A; Schmidt, Torsten C

2018-02-28

The sugar replacement compound xylitol has gained increasing attention because of its use in many commercial food products, dental-hygiene articles, and pharmaceuticals. It can be classified by the origin of the raw material used for its production. The traditional "birch xylitol" is considered a premium product, in contrast to xylitol produced from agriculture byproducts such as corn husks or sugar-cane straw. Bulk stable-isotope analysis (BSIA) and compound-specific stable-isotope analysis (CSIA) by liquid-chromatography isotope-ratio mass spectrometry (LC-IRMS) of chewing-gum extracts were used to determine the δ 13 C isotope signatures for xylitol. These were applied to elucidate the original plant type the xylitol was produced from on the basis of differences in isotope-fractionation processes of photosynthetic CO 2 fixation. For the LC-IRMS analysis, an organic-solvent-free extraction protocol and HPLC method for the separation of xylitol from different artificial sweeteners and sugar-replacement compounds was successfully developed and applied to the analysis of 21 samples of chewing gum, from which 18 could be clearly related to the raw-material plant class.

Phylogenetic Analysis Using Protein Mass Spectrometry.

Science.gov (United States)

Ma, Shiyong; Downard, Kevin M; Wong, Jason W H

2017-01-01

Through advances in molecular biology, comparative analysis of DNA sequences is currently the cornerstone in the study of molecular evolution and phylogenetics. Nevertheless, protein mass spectrometry offers some unique opportunities to enable phylogenetic analyses in organisms where DNA may be difficult or costly to obtain. To date, the methods of phylogenetic analysis using protein mass spectrometry can be classified into three categories: (1) de novo protein sequencing followed by classical phylogenetic reconstruction, (2) direct phylogenetic reconstruction using proteolytic peptide mass maps, and (3) mapping of mass spectral data onto classical phylogenetic trees. In this chapter, we provide a brief description of the three methods and the protocol for each method along with relevant tools and algorithms.

A history of mass spectrometry in Australia

Energy Technology Data Exchange (ETDEWEB)

Downard, K.M.; de Laeter, J.R. [University of Sydney, Sydney, NSW (Australia)

2005-09-01

An interest in mass spectrometry in Australia can be traced back to the 1920s with an early correspondence with Francis Aston who first visited these shores a decade earlier. The region has a rich tradition in both the development of the field and its application, from early measurements of ionization and appearance potentials by Jim Morrison at the Council for Scientific and Industrial Research (CSIR) around 1950 to the design and construction of instrumentation including the first use of a triple quadrupole mass spectrometer for tandem mass spectrometry, the first suite of programs to simulate ion optics (SIMION), the development of early TOF/TOF instruments and orthogonal acceleration and the local design and construction of several generations of a sensitive high-resolution ion microprobe (SHRIMP) instrument. Mass spectrometry has been exploited in the study and characterization of the constituents of this nation's unique flora and fauna from Australian apples, honey, tea plant and eucalyptus oil, snake, spider, fish and frog venoms, coal, oil, sediments and shale, environmental studies of groundwater to geochronological dating of limestone and granite, other terrestrial and meteoritic rocks and coral from the Great Barrier Reef. This article traces the history of mass spectrometry in its many guises and applications in the island continent of Australia. It focuses on contributions of scientists who played a major role in the early establishment of mass spectrometry in Australia. In general, those who are presently active in the field, and whose histories are incomplete, have been mentioned at best only briefly despite their important contributions to the field.

[Imaging Mass Spectrometry in Histopathologic Analysis].

Science.gov (United States)

Yamazaki, Fumiyoshi; Seto, Mitsutoshi

2015-04-01

Matrix-assisted laser desorption/ionization (MALDI)-imaging mass spectrometry (IMS) enables visualization of the distribution of a range of biomolecules by integrating biochemical information from mass spectrometry with positional information from microscopy. IMS identifies a target molecule. In addition, IMS enables global analysis of biomolecules containing unknown molecules by detecting the ratio of the molecular weight to electric charge without any target, which makes it possible to identify novel molecules. IMS generates data on the distribution of lipids and small molecules in tissues, which is difficult to visualize with either conventional counter-staining or immunohistochemistry. In this review, we firstly introduce the principle of imaging mass spectrometry and recent advances in the sample preparation method. Secondly, we present findings regarding biological samples, especially pathological ones. Finally, we discuss the limitations and problems of the IMS technique and clinical application, such as in drug development.

Information Resources Management (IRM): A Revolution in Progress.

Science.gov (United States)

Becker, Louise Giovane

1980-01-01

Discusses the emergence of information resources management (IRM) as a focus for managing information activities, particularly those related to federal administration. The IRM office and its manager are described within the context of an organization. Impact of the Paperwork Reduction Act of 1980 on IRM is discussed. (SW)

Cs+ ion source for secondary ion mass spectrometry

International Nuclear Information System (INIS)

Bentz, B.L.; Weiss, H.; Liebl, H.

1981-12-01

Various types of cesium ionization sources currently used in secondary ion mass spectrometry are briefly reviewed, followed by a description of the design and performance of a novel, thermal surface ionization Cs + source developed in this laboratory. The source was evaluated for secondary ion mass spectrometry applications using the COALA ion microprobe mass analyzer. (orig.)

Analysis of Nitro-aromatic and Nitramine Explosives by Atmospheric Pressure Chemical Ionization / High Performance Liquid Chromatography / Mass Spectrometry / Mass Spectrometry

International Nuclear Information System (INIS)

Hicks, B.J.; Han, W.; Robben, J.R.

2009-01-01

This procedure is capable of separating and quantifying twenty-nine high explosives and internal surrogates with a single injection. After the initial preparation step, the sample is introduced to the high performance liquid chromatograph for target separation, ionized by atmospheric pressure chemical ionization and the explosives of interest are isolated / quantified by mass spectrometry / mass spectrometry. Concentrations of the target explosives are measured relative to the response of both internal and external standard concentrations. A C-18 reverse phase high performance liquid chromatograph column is used for separation. Ionization is performed using both positive and negative atmospheric pressure chemical ionization resulting in a molecular ion with little fragmentation. These ions are isolated at the first quadrupole of the mass spectrometer, dissociated by collision with argon in the collision cell and the resulting daughter ions are isolated at the second quadrupole. These daughter ions then reach the detector where they are quantified. To date this procedure represents the most thorough high performance liquid chromatography / mass spectrometry / mass spectrometry explosives analysis available in the environmental chemistry market. (authors)

[Latest development in mass spectrometry for clinical application].

Science.gov (United States)

Takino, Masahiko

2013-09-01

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) has seen enormous growth in special clinical chemistry laboratories. It significantly increases the analytic potential in clinical chemistry, especially in the field of low molecular weight biomarker analysis. This review summarizes the state of the art in mass spectrometry and related techniques for clinical application with a main focus on recent developments in LC-MS. Current trends in ionization techniques, automated online sample preparation techniques coupled with LC-MS, and ion mobility spectrometry are discussed. Emerging mass spectrometric approaches complementary to LC-MS are discussed as well.

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.

Mass spectrometry: a revolution in clinical microbiology?

Science.gov (United States)

Lavigne, Jean-Philippe; Espinal, Paula; Dunyach-Remy, Catherine; Messad, Nourredine; Pantel, Alix; Sotto, Albert

2013-02-01

Recently, different bacteriological laboratory interventions that decrease reporting time have been developed. These promising new broad-based techniques have merit, based on their ability to identify rapidly many bacteria, organisms difficult to grow or newly emerging strains, as well as their capacity to track disease transmission. The benefit of rapid reporting of identification and/or resistance of bacteria can greatly impact patient outcomes, with an improvement in the use of antibiotics, in the reduction of the emergence of multidrug resistant bacteria and in mortality rates. Different techniques revolve around mass spectrometry (MS) technology: matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), PCR combined with electrospray ionization-mass spectrometry (PCR/ESIMS), iPLEX MassArray system and other new evolutions combining different techniques. This report emphasizes the (r)evolution of these technologies in clinical microbiology.

NICHD Biomedical Mass Spectrometry Core Facility

Data.gov (United States)

Federal Laboratory Consortium — The NICHD Biomedical Mass Spectrometry Core Facility was created under the auspices of the Office of the Scientific Director to provide high-end mass-spectrometric...

Mass spectrometry for real-time quantitative breath analysis

Czech Academy of Sciences Publication Activity Database

Smith, D.; Španěl, Patrik; Herbig, J.; Beauchamp, J.

2014-01-01

Roč. 8, č. 2 (2014), 027101 ISSN 1752-7155 Institutional support: RVO:61388955 Keywords : breath analysis * proton transfer reaction mass spectrometry * selected ion flow tube mass spectrometry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.631, year: 2014

High-efficiency thermal ionization sources for mass spectrometry

International Nuclear Information System (INIS)

Olivares, Jose A.

1996-01-01

A version of the thermal ionization cavity (TIC) source developed specifically for use in mass spectrometry is presented. The performance of this ion source has been characterized extensively both with the use of an isotope separator and a quadrupole mass spectrometer. A detailed description of the TIC source for mass spectrometry is given along with the performance characteristics observed

Analytical mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

1990-01-01

This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

The allure of mass spectrometry: From an earlyday chemist's perspective.

Science.gov (United States)

Tőkés, László

2017-07-01

This reminiscing review article is an account of the author's fascination and involvements with mass spectrometry from the perspective of an organic chemist with an interest in natural product chemistry. It covers a period from 1961 through the mid 1990s as mass spectrometry evolved form a novelty technique to become a most widely used analytical technique. Following a brief synopsis of my pathway to mass spectrometry, my research efforts in this field are presented with a focus mainly on evolving principles and technologies which I had personal involvements with. To provide historical perspectives, discussions of these developments are accompanied by brief outlines of the relevant state-of-the-art, shedding light on the technical and conceptual challenges encountered during those early days in mass spectrometry. Examples are presented of my involvements with basic and applied research in mass spectrometry during graduate studies at Stanford University and close to three decade tenure in pharmaceutical research at Syntex Research. My basic research interests focused mainly on principles of electron ionization induced fragmentation mechanisms, with an emphasis on steroids and other model compounds. Extensive deuterium labeling evidence was used to determine the fragmentation mechanisms of the diagnostically significant ions in the spectra of numerous model compounds, uncovering examples of wide-ranging hydrogen transfers, skeletal rearrangements, methyl and phenyl migrations, stereoselective fragmentations and low and high energy fragmentation processes. Depiction of the industrial research phase of my career includes comments on the pivotal role mass spectrometry played on advancing modern pharmaceutical research. Examples are presented of involvements with instrumental developments and a few select cases of applied research, including studies of bile mechanisms in vertebrates, identification of bisphenol-A leaching from sterilized polycarbonate containers, high

Statistical methods for mass spectrometry-based clinical proteomics

NARCIS (Netherlands)

Kakourou, A.

2018-01-01

The work presented in this thesis focuses on methods for the construction of diagnostic rules based on clinical mass spectrometry proteomic data. Mass spectrometry has become one of the key technologies for jointly measuring the expression of thousands of proteins in biological samples.

Sampling and analyte enrichment strategies for ambient mass spectrometry.

Science.gov (United States)

Li, Xianjiang; Ma, Wen; Li, Hongmei; Ai, Wanpeng; Bai, Yu; Liu, Huwei

2018-01-01

Ambient mass spectrometry provides great convenience for fast screening, and has showed promising potential in analytical chemistry. However, its relatively low sensitivity seriously restricts its practical utility in trace compound analysis. In this review, we summarize the sampling and analyte enrichment strategies coupled with nine modes of representative ambient mass spectrometry (desorption electrospray ionization, paper vhspray ionization, wooden-tip spray ionization, probe electrospray ionization, coated blade spray ionization, direct analysis in real time, desorption corona beam ionization, dielectric barrier discharge ionization, and atmospheric-pressure solids analysis probe) that have dramatically increased the detection sensitivity. We believe that these advances will promote routine use of ambient mass spectrometry. Graphical abstract Scheme of sampling stretagies for ambient mass spectrometry.

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

Fourier transform ion cyclotron resonance mass spectrometry

Science.gov (United States)

Marshall, Alan G.

1998-06-01

As for Fourier transform infrared (FT-IR) interferometry and nuclear magnetic resonance (NMR) spectroscopy, the introduction of pulsed Fourier transform techniques revolutionized ion cyclotron resonance mass spectrometry: increased speed (factor of 10,000), increased sensitivity (factor of 100), increased mass resolution (factor of 10,000-an improvement not shared by the introduction of FT techniques to IR or NMR spectroscopy), increased mass range (factor of 500), and automated operation. FT-ICR mass spectrometry is the most versatile technique for unscrambling and quantifying ion-molecule reaction kinetics and equilibria in the absence of solvent (i.e., the gas phase). In addition, FT-ICR MS has the following analytically important features: speed (~1 second per spectrum); ultrahigh mass resolution and ultrahigh mass accuracy for analysis of mixtures and polymers; attomole sensitivity; MSn with one spectrometer, including two-dimensional FT/FT-ICR/MS; positive and/or negative ions; multiple ion sources (especially MALDI and electrospray); biomolecular molecular weight and sequencing; LC/MS; and single-molecule detection up to 108 Dalton. Here, some basic features and recent developments of FT-ICR mass spectrometry are reviewed, with applications ranging from crude oil to molecular biology.

Mass Spectrometry Imaging, an Emerging Technology in Neuropsychopharmacology

Science.gov (United States)

Shariatgorji, Mohammadreza; Svenningsson, Per; Andrén, Per E

2014-01-01

Mass spectrometry imaging is a powerful tool for directly determining the distribution of proteins, peptides, lipids, neurotransmitters, metabolites and drugs in neural tissue sections in situ. Molecule-specific imaging can be achieved using various ionization techniques that are suited to different applications but which all yield data with high mass accuracies and spatial resolutions. The ability to simultaneously obtain images showing the distributions of chemical species ranging from metal ions to macromolecules makes it possible to explore the chemical organization of a sample and to correlate the results obtained with specific anatomical features. The imaging of biomolecules has provided new insights into multiple neurological diseases, including Parkinson's and Alzheimer's disease. Mass spectrometry imaging can also be used in conjunction with other imaging techniques in order to identify correlations between changes in the distribution of important chemical species and other changes in the properties of the tissue. Here we review the applications of mass spectrometry imaging in neuroscience research and discuss its potential. The results presented demonstrate that mass spectrometry imaging is a useful experimental method with diverse applications in neuroscience. PMID:23966069

Mass spectrometry imaging, an emerging technology in neuropsychopharmacology.

Science.gov (United States)

Shariatgorji, Mohammadreza; Svenningsson, Per; Andrén, Per E

2014-01-01

Mass spectrometry imaging is a powerful tool for directly determining the distribution of proteins, peptides, lipids, neurotransmitters, metabolites and drugs in neural tissue sections in situ. Molecule-specific imaging can be achieved using various ionization techniques that are suited to different applications but which all yield data with high mass accuracies and spatial resolutions. The ability to simultaneously obtain images showing the distributions of chemical species ranging from metal ions to macromolecules makes it possible to explore the chemical organization of a sample and to correlate the results obtained with specific anatomical features. The imaging of biomolecules has provided new insights into multiple neurological diseases, including Parkinson's and Alzheimer's disease. Mass spectrometry imaging can also be used in conjunction with other imaging techniques in order to identify correlations between changes in the distribution of important chemical species and other changes in the properties of the tissue. Here we review the applications of mass spectrometry imaging in neuroscience research and discuss its potential. The results presented demonstrate that mass spectrometry imaging is a useful experimental method with diverse applications in neuroscience.

Atom counting with accelerator mass spectrometry

International Nuclear Information System (INIS)

Kutschera, Walter

1995-01-01

A brief review of the current status and some recent applications of accelerator mass spectrometry (AMS) are presented. Some connections to resonance ionization mass spectroscopy (RIS) as the alternate atom counting method are discussed

Mass Spectrometry Instrumentation in Proteomics

DEFF Research Database (Denmark)

Sprenger, Richard Remko; Roepstorff, Peter

2012-01-01

Mass spectrometry has evolved into a crucial technology for the field of proteomics, enabling the comprehensive study of proteins in biological systems. Innovative developments have yielded flexible and versatile mass spectrometric tools, including quadrupole time-of-flight, linear ion trap......, Orbitrap and ion mobility instruments. Together they offer various and complementary capabilities in terms of ionization, sensitivity, speed, resolution, mass accuracy, dynamic range and methods of fragmentation. Mass spectrometers can acquire qualitative and quantitative information on a large scale...

Guideline on Isotope Dilution Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Gaffney, Amy [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2017-05-19

Isotope dilution mass spectrometry is used to determine the concentration of an element of interest in a bulk sample. It is a destructive analysis technique that is applicable to a wide range of analytes and bulk sample types. With this method, a known amount of a rare isotope, or ‘spike’, of the element of interest is added to a known amount of sample. The element of interest is chemically purified from the bulk sample, the isotope ratio of the spiked sample is measured by mass spectrometry, and the concentration of the element of interest is calculated from this result. This method is widely used, although a mass spectrometer required for this analysis may be fairly expensive.

Statistical analysis of proteomics, metabolomics, and lipidomics data using mass spectrometry

CERN Document Server

Mertens, Bart

2017-01-01

This book presents an overview of computational and statistical design and analysis of mass spectrometry-based proteomics, metabolomics, and lipidomics data. This contributed volume provides an introduction to the special aspects of statistical design and analysis with mass spectrometry data for the new omic sciences. The text discusses common aspects of design and analysis between and across all (or most) forms of mass spectrometry, while also providing special examples of application with the most common forms of mass spectrometry. Also covered are applications of computational mass spectrometry not only in clinical study but also in the interpretation of omics data in plant biology studies. Omics research fields are expected to revolutionize biomolecular research by the ability to simultaneously profile many compounds within either patient blood, urine, tissue, or other biological samples. Mass spectrometry is one of the key analytical techniques used in these new omic sciences. Liquid chromatography mass ...

Mass spectrometry for characterizing plant cell wall polysaccharides

Directory of Open Access Journals (Sweden)

Stefan eBauer

2012-03-01

Full Text Available Mass spectrometry is a selective and powerful technique to obtain identification and structural information on compounds present in complex mixtures. Since it requires only small sample amount it is an excellent tool for researchers interested in detecting changes in composition of complex carbohydrates of plants. This mini-review gives an overview of common mass spectrometry techniques applied to the analysis of plant cell wall carbohydrates. It presents examples in which mass spectrometry has been used to elucidate the structure of oligosaccharides derived from hemicelluloses and pectins and illustrates how information on sequence, linkages, branching and modifications are obtained from characteristic fragmentation patterns.

Proteomic Mass Spectrometry Imaging for Skin Cancer Diagnosis.

Science.gov (United States)

Lazova, Rossitza; Seeley, Erin H

2017-10-01

Mass spectrometry imaging can be successfully used for skin cancer diagnosis, particularly for the diagnosis of challenging melanocytic lesions. This method analyzes proteins within benign and malignant melanocytic tumor cells and, based on their differences, which constitute a unique molecular signature of 5 to 20 proteins, can render a diagnosis of benign nevus versus malignant melanoma. Mass spectrometry imaging may assist in the differentiation between metastases and nevi as well as between proliferative nodules in nevi and melanoma arising in a nevus. In the difficult area of atypical Spitzoid neoplasms, mass spectrometry diagnosis can predict clinical outcome better than histopathology. Copyright © 2017 Elsevier Inc. All rights reserved.

Mass Spectrometry in the Home and Garden

Science.gov (United States)

Pulliam, Christopher J.; Bain, Ryan M.; Wiley, Joshua S.; Ouyang, Zheng; Cooks, R. Graham

2015-02-01

Identification of active components in a variety of chemical products used directly by consumers is described at both trace and bulk levels using mass spectrometry. The combination of external ambient ionization with a portable mass spectrometer capable of tandem mass spectrometry provides high chemical specificity and sensitivity as well as allowing on-site monitoring. These experiments were done using a custom-built portable ion trap mass spectrometer in combination with the ambient ionization methods of paper spray, leaf spray, and low temperature plasma ionization. Bactericides, garden chemicals, air fresheners, and other products were examined. Herbicide applied to suburban lawns was detected in situ on single leaves 5 d after application.

Quantitative Thin-Layer Chromatography/Mass Spectrometry Analysis of Caffeine Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

Energy Technology Data Exchange (ETDEWEB)

Ford, Michael J [ORNL; Deibel, Michael A. [Earlham College; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

2005-01-01

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

High-accuracy mass spectrometry for fundamental studies.

Science.gov (United States)

Kluge, H-Jürgen

2010-01-01

Mass spectrometry for fundamental studies in metrology and atomic, nuclear and particle physics requires extreme sensitivity and efficiency as well as ultimate resolving power and accuracy. An overview will be given on the global status of high-accuracy mass spectrometry for fundamental physics and metrology. Three quite different examples of modern mass spectrometric experiments in physics are presented: (i) the retardation spectrometer KATRIN at the Forschungszentrum Karlsruhe, employing electrostatic filtering in combination with magnetic-adiabatic collimation-the biggest mass spectrometer for determining the smallest mass, i.e. the mass of the electron anti-neutrino, (ii) the Experimental Cooler-Storage Ring at GSI-a mass spectrometer of medium size, relative to other accelerators, for determining medium-heavy masses and (iii) the Penning trap facility, SHIPTRAP, at GSI-the smallest mass spectrometer for determining the heaviest masses, those of super-heavy elements. Finally, a short view into the future will address the GSI project HITRAP at GSI for fundamental studies with highly-charged ions.

Proceedings of the twelfth ISMAS triennial international conference on mass spectrometry

International Nuclear Information System (INIS)

Aggarwal, S.K.; Jaison, P.G.; Telmore, V.M.

2013-03-01

These Workshops are aimed at introducing the subject of Mass Spectrometry to novices, updating the Mass Spectrometrists with the latest developments in the field, exposing the participants to innumerable applications of Mass Spectrometry and providing a common forum for discussing the day-to-day problems when working with a Mass Spectrometer. The programme of these Workshops consists of Tutorials, Panel Discussions, Research Scholars' Presentations, Poster Presentations and Invited Lectures. The lectures include fundamentals of Mass Spectrometry, qualitative and quantitative aspects and data interpretation, maintenance of Mass Spectrometers, selection of a mass spectrometer, applications in various branches of science as well as recent advances in Mass Spectrometry. Papers relevant to INIS are indexed separately

Miniaturization and Mass Spectrometry

NARCIS (Netherlands)

le Gac, S.; le Gac, Severine; van den Berg, Albert; van den Berg, A.; Unknown, [Unknown

2009-01-01

With this book we want to illustrate how two quickly growing fields of instrumentation and technology, both applied to life sciences, mass spectrometry and microfluidics (or microfabrication) naturally came to meet at the end of the last century and how this marriage impacts on several types of

IRMS to study a common cocaine cutting agent: phenacetin.

Science.gov (United States)

Ladroue, Virginie; Dujourdy, Laurence; Besacier, Fabrice; Jame, Patrick

2017-03-01

Phenacetin is a pharmaceutical closely related to acetaminophen that has been banned in France for a long time due to its nephritic and carcinogenic adverse effects. It frequently appears in cocaine seizures as a cutting agent. Following both sanitary and intelligence motivations, this molecule was chosen for this study, and stable isotopes seemed to be the most appropriate tool. A total of 228 seized samples were collected over a 6-year period, and 8 standards of known origin were purchased. They were submitted to gas chromatography (GC) or elemental analysis - isotope ratio mass spectrometry (EA-IRMS) measurements, depending on their complexity. Stable isotope ratios of carbon, hydrogen, and nitrogen for a part of the sample set, were acquired. The isotopic values of phenacetin standards acquired from various providers located worldwide are quite spread, which indicates that stable isotopes could be used to discriminate manufacturers. However, the measured values of most of the seized samples are concentrated in a narrow range, tending to demonstrate that phenacetin is smuggled from a single source or similar ones. Consequently, stable isotopes could only be used to exclude that several samples come from a common source. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry.

Science.gov (United States)

Srivastava, Abneesh; Michael Verkouteren, R

2018-05-25

Isotope ratio measurements have been conducted on a series of isotopically distinct pure CO 2 gas samples using the technique of dual-inlet isotope ratio mass spectrometry (DI-IRMS). The influence of instrumental parameters, data normalization schemes on the metrological traceability and uncertainty of the sample isotope composition have been characterized. Traceability to the Vienna PeeDee Belemnite(VPDB)-CO 2 scale was realized using the pure CO 2 isotope reference materials(IRMs) 8562, 8563, and 8564. The uncertainty analyses include contributions associated with the values of iRMs and the repeatability and reproducibility of our measurements. Our DI-IRMS measurement system is demonstrated to have high long-term stability, approaching a precision of 0.001 parts-per-thousand for the 45/44 and 46/44 ion signal ratios. The single- and two-point normalization bias for the iRMs were found to be within their published standard uncertainty values. The values of 13 C/ 12 C and 18 O/ 16 O isotope ratios are expressed relative to VPDB-CO 2 using the [Formula: see text] and [Formula: see text] notation, respectively, in parts-per-thousand (‰ or per mil). For the samples, value assignments between (-25 to +2) ‰ and (-33 to -1) ‰ with nominal combined standard uncertainties of (0.05, 0.3) ‰ for [Formula: see text] and [Formula: see text], respectively were obtained. These samples are used as laboratory reference to provide anchor points for value assignment of isotope ratios (with VPDB traceability) to pure CO 2 samples. Additionally, they serve as potential parent isotopic source material required for the development of gravimetric based iRMs of CO 2 in CO 2 -free dry air in high pressure gas cylinder packages at desired abundance levels and isotopic composition values. Graphical abstract CO 2 gas isotope ratio metrology.

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.

Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

Science.gov (United States)

Wu, Langping; Kümmel, Steffen; Richnow, Hans H

2017-04-01

Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

Mass Spectrometry Imaging under Ambient Conditions

Science.gov (United States)

Wu, Chunping; Dill, Allison L.; Eberlin, Livia S.; Cooks, R. Graham; Ifa, Demian R.

2012-01-01

Mass spectrometry imaging (MSI) has emerged as an important tool in the last decade and it is beginning to show potential to provide new information in many fields owing to its unique ability to acquire molecularly specific images and to provide multiplexed information, without the need for labeling or staining. In MSI, the chemical identity of molecules present on a surface is investigated as a function of spatial distribution. In addition to now standard methods involving MSI in vacuum, recently developed ambient ionization techniques allow MSI to be performed under atmospheric pressure on untreated samples outside the mass spectrometer. Here we review recent developments and applications of MSI emphasizing the ambient ionization techniques of desorption electrospray ionization (DESI), laser ablation electrospray ionization (LAESI), probe electrospray ionization (PESI), desorption atmospheric pressure photoionization (DAPPI), femtosecond laser desorption ionization (fs-LDI), laser electrospray mass spectrometry (LEMS), infrared laser ablation metastable-induced chemical ionization (IR-LAMICI), liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS), nanospray desorption electrospray ionization (nano-DESI), and plasma sources such as the low temperature plasma (LTP) probe and laser ablation coupled to flowing atmospheric-pressure afterglow (LA-FAPA). Included are discussions of some of the features of ambient MSI including the ability to implement chemical reactions with the goal of providing high abundance ions characteristic of specific compounds of interest and the use of tandem mass spectrometry to either map the distribution of targeted molecules with high specificity or to provide additional MS information in the structural identification of compounds. We also describe the role of bioinformatics in acquiring and interpreting the chemical and spatial information obtained through MSI, especially in biological applications for tissue

MPAI (mass probes aided ionization) method for total analysis of biomolecules by mass spectrometry.

Science.gov (United States)

Honda, Aki; Hayashi, Shinichiro; Hifumi, Hiroki; Honma, Yuya; Tanji, Noriyuki; Iwasawa, Naoko; Suzuki, Yoshio; Suzuki, Koji

2007-01-01

We have designed and synthesized various mass probes, which enable us to effectively ionize various molecules to be detected with mass spectrometry. We call the ionization method using mass probes the "MPAI (mass probes aided ionization)" method. We aim at the sensitive detection of various biological molecules, and also the detection of bio-molecules by a single mass spectrometry serially without changing the mechanical settings. Here, we review mass probes for small molecules with various functional groups and mass probes for proteins. Further, we introduce newly developed mass probes for proteins for highly sensitive detection.

Analysis of mass spectrometry data in proteomics

DEFF Research Database (Denmark)

Matthiesen, Rune; Jensen, Ole N

2008-01-01

The systematic study of proteins and protein networks, that is, proteomics, calls for qualitative and quantitative analysis of proteins and peptides. Mass spectrometry (MS) is a key analytical technology in current proteomics and modern mass spectrometers generate large amounts of high-quality data...... that in turn allow protein identification, annotation of secondary modifications, and determination of the absolute or relative abundance of individual proteins. Advances in mass spectrometry-driven proteomics rely on robust bioinformatics tools that enable large-scale data analysis. This chapter describes...... some of the basic concepts and current approaches to the analysis of MS and MS/MS data in proteomics....

Accelerator mass spectrometry-current status in techniques and applications

International Nuclear Information System (INIS)

Imamura, Mineo; Nagai, Hisao; Kobayashi, Koichi.

1991-01-01

Accelerator mass spectrometry (AMS) is the mass spectrometry by incorporating an accelerator. After samples are ionized, they are accelerated to a certain energy, and mass, energy, nuclear charge (atomic number) are distinguished, and ion counting is made one by one with a heavy ion detector. For the measurement of long half-life radioisotopes, mass spectrometry has been used because of the high sensitivity, but in low energy mass spectrometry, there are the difficulties due to the mixing of the molecular ions having nearly same mass and the existence of isobars. One of the methods solving these difficulties is an accelerator which enables background-free measurement. The progress of AMS is briefly described, and at present, it is carried out in about 30 facilities in the world. In AMS, the analysis is carried out in the order of the ionization of samples, the acceleration of beam, the electron stripping with a thin film, the sorting of the momentum and energy of beam and the identification of particles. The efficiency, sensitivity and accuracy of detection and the application are reported. (K.I.)

[Advances in mass spectrometry-based approaches for neuropeptide analysis].

Science.gov (United States)

Ji, Qianyue; Ma, Min; Peng, Xin; Jia, Chenxi; Ji, Qianyue

2017-07-25

Neuropeptides are an important class of endogenous bioactive substances involved in the function of the nervous system, and connect the brain and other neural and peripheral organs. Mass spectrometry-based neuropeptidomics are designed to study neuropeptides in a large-scale manner and obtain important molecular information to further understand the mechanism of nervous system regulation and the pathogenesis of neurological diseases. This review summarizes the basic strategies for the study of neuropeptides using mass spectrometry, including sample preparation and processing, qualitative and quantitative methods, and mass spectrometry imagining.

A continuous flow isotope ratio mass spectrometry method for high precision determination of dissolved gas ratios and isotopic composition

DEFF Research Database (Denmark)

Charoenpong, C. N.; Bristow, L. A.; Altabet, M. A.

2014-01-01

ratio mass spectrometer (IRMS). A continuous flow of He carrier gas completely degasses the sample, and passes through the preparation and purification system before entering the IRMS for analysis. The use of this continuous He carrier permits short analysis times (less than 8 min per sample......) as compared with current high-precision methods. In addition to reference gases, calibration is achieved using air-equilibrated water standards of known temperature and salinity. Assessment of reference gas injections, air equilibrated standards, as well as samples collected in the field shows the accuracy...

Identification of Fatty Acids, Phospholipids, and Their Oxidation Products Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry and Electrospray Ionization Mass Spectrometry

Science.gov (United States)

Harmon, Christopher W.; Mang, Stephen A.; Greaves, John; Finlayson-Pitts, Barbara J.

2010-01-01

Electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) have found increasing application in the analysis of biological samples. Using these techniques to solve problems in analytical chemistry should be an essential component of the training of undergraduate chemists. We…

Preliminary study to characterize plastic polymers using elemental analyser/isotope ratio mass spectrometry (EA/IRMS).

Science.gov (United States)

Berto, Daniela; Rampazzo, Federico; Gion, Claudia; Noventa, Seta; Ronchi, Francesca; Traldi, Umberto; Giorgi, Giordano; Cicero, Anna Maria; Giovanardi, Otello

2017-06-01

Plastic waste is a growing global environmental problem, particularly in the marine ecosystems, in consideration of its persistence. The monitoring of the plastic waste has become a global issue, as reported by several surveillance guidelines proposed by Regional Sea Conventions (OSPAR, UNEP) and appointed by the EU Marine Strategy Framework Directive. Policy responses to plastic waste vary at many levels, ranging from beach clean-up to bans on the commercialization of plastic bags and to Regional Plans for waste management and recycling. Moreover, in recent years, the production of plant-derived biodegradable plastic polymers has assumed increasing importance. This study reports the first preliminary characterization of carbon stable isotopes (δ 13 C) of different plastic polymers (petroleum- and plant-derived) in order to increase the dataset of isotopic values as a tool for further investigation in different fields of polymers research as well as in the marine environment surveillance. The δ 13 C values determined in different packaging for food uses reflect the plant origin of "BIO" materials, whereas the recycled plastic materials displayed a δ 13 C signatures between plant- and petroleum-derived polymers source. In a preliminary estimation, the different colours of plastic did not affect the variability of δ 13 C values, whereas the abiotic and biotic degradation processes that occurred in the plastic materials collected on beaches and in seawater, showed less negative δ 13 C values. A preliminary experimental field test confirmed these results. The advantages offered by isotope ratio mass spectrometry with respect to other analytical methods used to characterize the composition of plastic polymers are: high sensitivity, small amount of material required, rapidity of analysis, low cost and no limitation in black/dark samples compared with spectroscopic analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of posttranslational modifications of proteins by tandem mass spectrometry

DEFF Research Database (Denmark)

Larsen, Martin Røssel; Trelle, Morten B; Thingholm, Tine E

2006-01-01

-temporal distribution in cells and tissues. Most PTMs can be detected by protein and peptide analysis by mass spectrometry (MS), either as a mass increment or a mass deficit relative to the nascent unmodified protein. Tandem mass spectrometry (MS/MS) provides a series of analytical features that are highly useful...

Imaging Mass Spectrometry in Neuroscience

Science.gov (United States)

2013-01-01

Imaging mass spectrometry is an emerging technique of great potential for investigating the chemical architecture in biological matrices. Although the potential for studying neurobiological systems is evident, the relevance of the technique for application in neuroscience is still in its infancy. In the present Review, a principal overview of the different approaches, including matrix assisted laser desorption ionization and secondary ion mass spectrometry, is provided with particular focus on their strengths and limitations for studying different neurochemical species in situ and in vitro. The potential of the various approaches is discussed based on both fundamental and biomedical neuroscience research. This Review aims to serve as a general guide to familiarize the neuroscience community and other biomedical researchers with the technique, highlighting its great potential and suitability for comprehensive and specific chemical imaging. PMID:23530951

Quantification of steroid conjugates using fast atom bombardment mass spectrometry

International Nuclear Information System (INIS)

Gaskell, S.J.

1990-01-01

Fast atom bombardment/mass spectrometry or liquid secondary ion mass spectrometry provides the capability for direct analysis of steroid conjugates (sulfates, glucuronides) without prior hydrolysis or derivatization. During the analysis of biologic extracts, limitations on the sensitivity of detection arise from the presence of co-extracted material which may suppress or obscure the analyte signal. A procedure is described for the quantitative determination of dehydroepiandrosterone sulfate in serum which achieved selective isolation of the analyte using immunoadsorption extraction and highly specific detection using tandem mass spectrometry. A stable isotope-labeled analog [( 2H2]dehydroepiandrosterone sulfate) was used as internal standard. Fast atom bombardment of dehydroepiandrosterone sulfate yielded abundant [M-H]- ions that fragmented following collisional activation to give HSO4-; m/z 97. During fast atom bombardment/tandem mass spectrometry of serum extracts, a scan of precursor ions fragmenting to give m/z 97 detected dehydroepiandrosterone sulfate and the [2H2]-labeled analog with a selectivity markedly superior to that observed using conventional mass spectrometry detection. Satisfactory agreement was observed between quantitative data obtained in this way and data obtained by gas chromatography/mass spectrometry of the heptafluorobutyrates of dehydroepiandrosterone sulfate and [2H2]dehydroepiandrosterone sulfate obtained by direct derivatization. 21 refs

Quantitative mass spectrometry: an overview

Science.gov (United States)

Urban, Pawel L.

2016-10-01

Mass spectrometry (MS) is a mainstream chemical analysis technique in the twenty-first century. It has contributed to numerous discoveries in chemistry, physics and biochemistry. Hundreds of research laboratories scattered all over the world use MS every day to investigate fundamental phenomena on the molecular level. MS is also widely used by industry-especially in drug discovery, quality control and food safety protocols. In some cases, mass spectrometers are indispensable and irreplaceable by any other metrological tools. The uniqueness of MS is due to the fact that it enables direct identification of molecules based on the mass-to-charge ratios as well as fragmentation patterns. Thus, for several decades now, MS has been used in qualitative chemical analysis. To address the pressing need for quantitative molecular measurements, a number of laboratories focused on technological and methodological improvements that could render MS a fully quantitative metrological platform. In this theme issue, the experts working for some of those laboratories share their knowledge and enthusiasm about quantitative MS. I hope this theme issue will benefit readers, and foster fundamental and applied research based on quantitative MS measurements. This article is part of the themed issue 'Quantitative mass spectrometry'.

Structural analyses of sucrose laurate regioisomers by mass spectrometry techniques

DEFF Research Database (Denmark)

Lie, Aleksander; Stensballe, Allan; Pedersen, Lars Haastrup

2015-01-01

6- And 6′-O-lauroyl sucrose were isolated and analyzed by matrix-assisted laser desorption/ionisation (MALDI) time-of-flight (TOF) mass spectrometry (MS), Orbitrap high-resolution (HR) MS, and electrospray-ionization (ESI) tandem mass spectrometry (MS/MS). The analyses aimed to explore the physic......6- And 6′-O-lauroyl sucrose were isolated and analyzed by matrix-assisted laser desorption/ionisation (MALDI) time-of-flight (TOF) mass spectrometry (MS), Orbitrap high-resolution (HR) MS, and electrospray-ionization (ESI) tandem mass spectrometry (MS/MS). The analyses aimed to explore.......8, respectively, and Orbitrap HRMS confirmed the mass of [M+Na]+ (m/z 547.2712). ESI-MS/MS on the precursor ion [M+Na]+ resulted in product ion mass spectra showing two high-intensity signals for each sample. 6-O-Lauroyl sucrose produced signals located at m/z 547.27 and m/z 385.21, corresponding to the 6-O...

Development and validation of a GC-C-IRMS method for the confirmation analysis of pseudo-endogenous glucocorticoids in doping control.

Science.gov (United States)

de la Torre, Xavier; Curcio, Davide; Colamonici, Cristiana; Molaioni, Francesco; Cilia, Marta; Botrè, Francesco

2015-01-01

Glucocorticoids are included in the S9 section of the World Anti-doping Agency (WADA) prohibited list international standard. Some among them are pseudo-endogenous steroids, like cortisol and cortisone, which present the same chemical structure as endogenously produced steroids. We are proposing an analytical method based on gas chromatography coupled to isotope ratio mass spectrometry (GC-C-IRMS) which allows discrimination between endogenous and synthetic origin of the urinary metabolites of the pseudo-endogenous glucocorticoids. A preliminary purification treatment by high-performance liquid chromatography (HPLC) of the target compounds (TC) (i.e., cortisol, tetrahydrocortisone (THE) 5α-tetrahydrocortisone (aTHE), tetrahydrocortisol (THF), and 5α-tetrahydrocortisol (aTHF)) allows collection of extracts with adequate purity for the subsequent analysis by IRMS. A population of 40 urine samples was analyzed for the TC and for the endogenous reference compounds (ERC: i.e., 11-desoxy-tetrahydrocortisol (THS) or pregnanediol). For each sample, the difference between the delta values of the ERCs and TCs (Δδ values) were calculated and based on that, some decision limits for atypical findings are proposed. The limits are below 3% units except for cortisol. The fit to purpose of the method has been confirmed by the analysis of urine samples collected in two patients under treatment with 25 mg of cortisone acetate (p.o). The samples showed Δδ values higher than 3 for at least 24 h following administration depending on the TC considered. The method can easily be integrated into existing procedures already used for the HPLC purification and IRMS analysis of pseudo-endogenous steroids with androgenic/anabolic activity. Copyright © 2015 John Wiley & Sons, Ltd.

Absorption Mode FT-ICR Mass Spectrometry Imaging

Energy Technology Data Exchange (ETDEWEB)

Smith, Donald F.; Kilgour, David P.; Konijnenburg, Marco; O' Connor, Peter B.; Heeren, Ronald M.

2013-12-03

Fourier transform ion cyclotron resonance mass spectrometry offers the highest mass resolving power for molecular imaging experiments. This high mass resolving power ensures that closely spaced peaks at the same nominal mass are resolved for proper image generation. Typically higher magnetic fields are used to increase mass resolving power. However, a gain in mass resolving power can also be realized by phase correction of the data for absorption mode display. In addition to mass resolving power, absorption mode offers higher mass accuracy and signal-to-noise ratio over the conventional magnitude mode. Here we present the first use of absorption mode for Fourier transform ion cyclotron resonance mass spectrometry imaging. The Autophaser algorithm is used to phase correct each spectrum (pixel) in the image and then these parameters are used by the Chameleon work-flow based data processing software to generate absorption mode ?Datacubes? for image and spectral viewing. Absorption mode reveals new mass and spatial features that are not resolved in magnitude mode and results in improved selected ion image contrast.

Sequencing Cyclic Peptides by Multistage Mass Spectrometry

Science.gov (United States)

Mohimani, Hosein; Yang, Yu-Liang; Liu, Wei-Ting; Hsieh, Pei-Wen; Dorrestein, Pieter C.; Pevzner, Pavel A.

2012-01-01

Some of the most effective antibiotics (e.g., Vancomycin and Daptomycin) are cyclic peptides produced by non-ribosomal biosynthetic pathways. While hundreds of biomedically important cyclic peptides have been sequenced, the computational techniques for sequencing cyclic peptides are still in their infancy. Previous methods for sequencing peptide antibiotics and other cyclic peptides are based on Nuclear Magnetic Resonance spectroscopy, and require large amount (miligrams) of purified materials that, for most compounds, are not possible to obtain. Recently, development of mass spectrometry based methods has provided some hope for accurate sequencing of cyclic peptides using picograms of materials. In this paper we develop a method for sequencing of cyclic peptides by multistage mass spectrometry, and show its advantages over single stage mass spectrometry. The method is tested on known and new cyclic peptides from Bacillus brevis, Dianthus superbus and Streptomyces griseus, as well as a new family of cyclic peptides produced by marine bacteria. PMID:21751357

Isotope analysis of lithium by thermionic mass spectrometry

International Nuclear Information System (INIS)

Kakazu, M.H.; Sarkis, J.E.S.

1991-04-01

An analytical mass spectrometric method for the isotope analysis of lithium has been studied. The analysis were carried out by using a single focusing thermoionic mass spectrometer Varian Mat TH5 with 90 sup(0) magnetic sector field and 21.4 cm deflection radius, equipped with a dual Re-filament thermal ionization ion source. The effect of different lithium chemical forms, such as, carbonate, chloride, nitrate and sulfate upon the isotopic ratios sup(6)Li/ sup(7)Li has been studied. Isotopic fractionation of lithium was studied in terms of the time of analysis. The results obtained with lithium carbonate yielded a precision of ±0.1% and an accuracy of ± 0.6%, whereas with other chemical forms yielded precisions of ±0.5% and accuracies of ±2%. A fractionation correction factor, K=1.005, was obtained for different samples of lithium carbonate isotopic standard CBNM IRM 016, which has been considered constant. (author)

Boundaries of mass resolution in native mass spectrometry

NARCIS (Netherlands)

Lössl, Philip|info:eu-repo/dai/nl/371559693; Snijder, Joost|info:eu-repo/dai/nl/338018328; Heck, Albert J R|info:eu-repo/dai/nl/105189332

Over the last two decades, native mass spectrometry (MS) has emerged as a valuable tool to study intact proteins and noncovalent protein complexes. Studied experimental systems range from small-molecule (drug)-protein interactions, to nanomachineries such as the proteasome and ribosome, to even

OBT measurement of vegetation by mass spectrometry and radiometry

International Nuclear Information System (INIS)

Tamari, T.; Kakiuchi, H.; Momoshima, N.; Sugihara, S.; Baglan, N.; Uda, T.

2011-01-01

We carried out OBT (organically bound tritium) measurement by two different methods those are radiometry and mass spectrometry and compared the applicability of these methods for environmental tritium analysis. The dried grass sample was used for the experiments. To eliminate the exchangeable OBT, the sample was washed with tritium free water before analysis. Three times washing reduced the tritium activity in the labile sites below the detectable level. In radiometry the sample was combusted to convert the OBT as well as other hydrogen isotopes to. water and tritium activity in the water was measured by liquid scintillation counting (LSC). In mass spectrometry, the sample was kept in a glass container and 3 He produced by tritium decay was measured by mass spectrometry. The results were in good agreement suggesting applicability of these methods for environmental tritium analysis. The mass spectrometry is more suitable for environmental tritium research because of a lower detection limit than that of the LSC. (authors)

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...

Development of stereotactic mass spectrometry for brain tumor surgery.

Science.gov (United States)

Agar, Nathalie Y R; Golby, Alexandra J; Ligon, Keith L; Norton, Isaiah; Mohan, Vandana; Wiseman, Justin M; Tannenbaum, Allen; Jolesz, Ferenc A

2011-02-01

Surgery remains the first and most important treatment modality for the majority of solid tumors. Across a range of brain tumor types and grades, postoperative residual tumor has a great impact on prognosis. The principal challenge and objective of neurosurgical intervention is therefore to maximize tumor resection while minimizing the potential for neurological deficit by preserving critical tissue. To introduce the integration of desorption electrospray ionization mass spectrometry into surgery for in vivo molecular tissue characterization and intraoperative definition of tumor boundaries without systemic injection of contrast agents. Using a frameless stereotactic sampling approach and by integrating a 3-dimensional navigation system with an ultrasonic surgical probe, we obtained image-registered surgical specimens. The samples were analyzed with ambient desorption/ionization mass spectrometry and validated against standard histopathology. This new approach will enable neurosurgeons to detect tumor infiltration of the normal brain intraoperatively with mass spectrometry and to obtain spatially resolved molecular tissue characterization without any exogenous agent and with high sensitivity and specificity. Proof of concept is presented in using mass spectrometry intraoperatively for real-time measurement of molecular structure and using that tissue characterization method to detect tumor boundaries. Multiple sampling sites within the tumor mass were defined for a patient with a recurrent left frontal oligodendroglioma, World Health Organization grade II with chromosome 1p/19q codeletion, and mass spectrometry data indicated a correlation between lipid constitution and tumor cell prevalence. The mass spectrometry measurements reflect a complex molecular structure and are integrated with frameless stereotaxy and imaging, providing 3-dimensional molecular imaging without systemic injection of any agents, which can be implemented for surgical margins delineation of

Mass Spectrometry of Halopyrazolium Salts

DEFF Research Database (Denmark)

Larsen, Elfinn; Egsgaard, Helge; Pande, U. C.

1983-01-01

Eleven halogen substituted 1-methyl-2-phenylpyrazolium bromides or chlorides were investigated by field desorption, field ionization, and electron impact mass spectrometry. Dealkylation was found to be the predominant thermal decomposition. An exchange between covalent and ionic halogen prior...

Analytical mass spectrometry. Abstracts

Energy Technology Data Exchange (ETDEWEB)

1990-12-31

This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

Use of mass spectrometry for study of coordination compounds

International Nuclear Information System (INIS)

Gehrbehlehu, N.V.; Indrichan, K.M.

1981-01-01

A review on mass-spectrometry of coordination compounds including the works published up to 1979 inclusive is provided. Mainly the products of metals with bi- and tetradentate ligands are considered using the method. Mo and Be carboxylates for which molecular ions lines are found in mass-spectra are studied. The study of mass-spectra for VO chelates with thiosemicarbazone of salicyl aldehyde is carried out. Application of the mass-spectrometry method permits to establish the mass of coordination compounds, the structure of complexes, dentate structure and the way of ligand coordination, the bond strength [ru

New experiments in organic, fast-atom-bomdardment, and secondary-ion mass spectrometry

International Nuclear Information System (INIS)

DiDonato, G.C.

1987-01-01

The goal of research presented in this dissertation is the creative use of new ionization and instrumental techniques in mass spectrometry. This goal manifests itself in three areas of mass spectrometry. In the first portion, modern, state-of-the-art instrumentation and new experiments were used to re-examine the mass spectra of transition-metal acetates and acetylacetonates. High resolution, chemical ionization, negative chemical ionization, and extended-mass-range mass spectrometry uncovered a wealth of new gas-phase ionic species. Energy-resolved mass spectrometry/mass spectrometry was applied to the characterization of molecular and fragment ion first-row transition-metal acetylacetonates, and comprises the second portion of the thesis. Studies in fast-atom-bombardment mass spectrometry are the subject of the third portion of the dissertation. Since fast-atom bombardment samples a liquid matrix, absolute and relative abundances of sputtered secondary ions are influenced by solution chemistry. The design and construction of an imaging secondary-ion mass spectrometer is the subject of the final portion of the thesis. This instrument provides for direct mass-spectrometric analysis of thin-layer and paper chromatograms and electrophoretograms

Applications of mass spectrometry in the trace element analysis of biological materials

International Nuclear Information System (INIS)

Moens, L.

1997-01-01

The importance of mass spectrometry for the analysis of biological material is illustrated by reviewing the different mass spectrometric methods applied and describing some typical applications published recently. Though atomic absorption spectrometry is used in the majority of analyses of biological material, most mass spectrometric methods have been used to some extent for trace element determination in biomedical research. The relative importance of the different methods is estimated by reviewing recent research papers. It is striking that especially inductively coupled plasma mass spectrometry is increasingly being applied, partly because the method can be used on-line after chromatographic separation, in speciation studies. Mass spectrometric methods prove to offer unique possibilities in stable isotope tracer studies and for this purpose also experimentally demanding methods such as thermal ionization mass spectrometry and accelerator mass spectrometry are frequently used. (orig.)

Indigenous instrumentation for mass spectrometry: Part II - development of plasma source mass spectrometers. PD-5-3

International Nuclear Information System (INIS)

Nataraju, V.

2007-01-01

The growing demands from analytical community, for a precise isotope ratio and ultra trace concentration measurements, has lead to significant improvement in mass spectrometer instrumentation development with respect to sensitivity, detection limits, precision and accuracy. Among the many analytical techniques available, plasma source mass spectrometers like Inductively Coupled Plasma Mass Spectrometry (ICPMS), multi collector (MC) ICPMS and Glow Discharge Mass Spectrometry (GDMS), have matured into reliable tools for the above applications. Where as ICPMS is by far the most successful method for aqueous solutions, GDMS is being applied for bulk and impurity analysis of conducting as well non-conducting solids. VPID, BARC has been developing mass spectrometers for different inorganic applications of DAE users. Over the years expertise has been developed in all the aspects of mass spectrometry instrumentation. Part 1 of this indigenous instrumentation on mass spectrometry gives details of magnetic sector instruments with either EI or TI source for isotopic ratio analysis. The present paper is a continuation of that on plasma source and quadrupole mass spectrometers. This paper covers i) ICP-QMS, ii) MC-ICPMS, iii) GDMS and iv) QMS

A Review of the Emerging Field of Underwater Mass Spectrometry

Directory of Open Access Journals (Sweden)

Emily Chua

2016-11-01

Full Text Available Mass spectrometers are versatile sensor systems, owing to their high sensitivity and ability to simultaneously measure multiple chemical species. Over the last two decades, traditional laboratory-based membrane inlet mass spectrometers have been adapted for underwater use. Underwater mass spectrometry has drastically improved our capability to monitor a broad suite of gaseous compounds (e.g., dissolved atmospheric gases, light hydrocarbons, and volatile organic compounds in the aquatic environment. Here we provide an overview of the progress made in the field of underwater mass spectrometry since its inception in the 1990s to the present. In particular, we discuss the approaches undertaken by various research groups in developing in situ mass spectrometers. We also provide examples to illustrate how underwater mass spectrometers have been used in the field. Finally, we present future trends in the field of in situ mass spectrometry. Most of these efforts are aimed at improving the quality and spatial and temporal scales of chemical measurements in the ocean. By providing up-to-date information on underwater mass spectrometry, this review offers guidance for researchers interested in adapting this technology as well as goals for future progress in the field.

Correcting mass shifts: A lock mass-free recalibration procedure for mass spectrometry imaging data

Czech Academy of Sciences Publication Activity Database

Kulkarni, P.; Kaftan, F.; Kynast, P.; Svatoš, Aleš; Böcker, S.

2015-01-01

Roč. 407, č. 25 (2015), s. 7603-7613 ISSN 1618-2642 Institutional support: RVO:61388963 Keywords : mass spectrometry imaging * recalibration * mass shift correction * data processing Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 3.125, year: 2015

Mass spectrometry in epigenetic research

DEFF Research Database (Denmark)

Beck, Hans Christian

2010-01-01

cancers has gained tremendous interest in recent years, and many of these inhibitors are currently undergoing clinical trials. Despite intense research, however, the exact molecular mechanisms of action of these molecules remain, to a wide extent, unclear. The recent application of mass spectrometry...

Liquid chromatography-mass spectrometry in forensic toxicology.

Science.gov (United States)

Van Bocxlaer, J F; Clauwaert, K M; Lambert, W E; Deforce, D L; Van den Eeckhout, E G; De Leenheer, A P

2000-01-01

Liquid chromatography-mass spectrometry has evolved from a topic of mainly research interest into a routinely usable tool in various application fields. With the advent of new ionization approaches, especially atmospheric pressure, the technique has established itself firmly in many areas of research. Although many applications prove that LC-MS is a valuable complementary analytical tool to GC-MS and has the potential to largely extend the application field of mass spectrometry to hitherto "MS-phobic" molecules, we must recognize that the use of LC-MS in forensic toxicology remains relatively rare. This rarity is all the more surprising because forensic toxicologists find themselves often confronted with the daunting task of actually searching for evidence materials on a scientific basis without any indication of the direction in which to search. Through the years, mass spectrometry, mainly in the GC-MS form, has gained a leading role in the way such quandaries are tackled. The advent of robust, bioanalytically compatible combinations of liquid chromatographic separation with mass spectrometric detection really opens new perspectives in terms of mass spectrometric identification of difficult molecules (e.g., polar metabolites) or biopolymers with toxicological relevance, high throughput, and versatility. Of course, analytical toxicologists are generally mass spectrometry users rather than mass spectrometrists, and this difference certainly explains the slow start of LC-MS in this field. Nevertheless, some valuable applications have been published, and it seems that the introduction of the more universal atmospheric pressure ionization interfaces really has boosted interests. This review presents an overview of what has been realized in forensic toxicological LC-MS. After a short introduction into LC-MS interfacing operational characteristics (or limitations), it covers applications that range from illicit drugs to often abused prescription medicines and some

Atmospheric pressure photo ionization hydrogen/deuterium exchange mass spectrometry--a method to differentiate isomers by mass spectrometry.

Science.gov (United States)

Ahmed, Arif; Kim, Sunghwan

2013-12-01

In this report, a method for in-source hydrogen/deuterium (H/D) exchange at atmospheric pressure is reported. The method was named atmospheric pressure photo ionization hydrogen/deuterium exchange mass spectrometry (APPI HDX MS). H/D exchange was performed by mixing samples dissolved in toluene with CH3OD solvent and analyzing the mixture using atmospheric pressure photo ionization mass spectrometry (APPI-MS). The APPI HDX spectra obtained with contact times between the analyte solution and methanol-OD (CH3OD) of atmospheric pressure. H/D exchange can be performed in any laboratory with a mass spectrometer and a commercial APPI source. Using this method, multiple H/D exchanges of aromatic hydrogen and/or H/D exchange of active hydrogen were observed. These results demonstrated that H/D exchange can be used to distinguish between isomers containing primary, secondary, and tertiary amines, as well as pyridine and pyrrole functional groups.

Mass spectrometry with particle accelerator

International Nuclear Information System (INIS)

Anon.

1983-01-01

The heavy ion accelerator use is renewing the ultrasensitive mass spectrometry in extending the detection limits. These new devices allow the measurement of rare isotope ratio, as 10 Be, 14 C, 26 Al, 36 Cl or 41 Ca, from the earth natural reservoirs [fr

Accelerator mass spectrometry: state of the art

Energy Technology Data Exchange (ETDEWEB)

Tuniz, C. [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia)

1996-12-31

Accelerator Mass Spectrometry (AMS) is the analytical technique of choice for the detection of long-lived radionuclides which cannot be practically analysed with decay counting or conventional mass spectrometry. The main use of AMS has been in the analysis of radiocarbon and other cosmogenic radionuclides for archaeological, geological and environmental applications. In addition, AMS has been recently applied in biomedicine to study exposure of human tissues to chemicals and biomolecules at attomole levels. There is also a world-wide effort to analyse rare nuclides of heavier masses, such as long-lived actinides, with important applications in safeguards and nuclear waste disposal. The use of AMS is limited by the expensive accelerator technology required and there are several attempts to develop smaller and cheaper AMS spectrometers. 5 refs.

Accelerator mass spectrometry: state of the art

Energy Technology Data Exchange (ETDEWEB)

Tuniz, C [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia)

1997-12-31

Accelerator Mass Spectrometry (AMS) is the analytical technique of choice for the detection of long-lived radionuclides which cannot be practically analysed with decay counting or conventional mass spectrometry. The main use of AMS has been in the analysis of radiocarbon and other cosmogenic radionuclides for archaeological, geological and environmental applications. In addition, AMS has been recently applied in biomedicine to study exposure of human tissues to chemicals and biomolecules at attomole levels. There is also a world-wide effort to analyse rare nuclides of heavier masses, such as long-lived actinides, with important applications in safeguards and nuclear waste disposal. The use of AMS is limited by the expensive accelerator technology required and there are several attempts to develop smaller and cheaper AMS spectrometers. 5 refs.

Radiation Biomarker Research Using Mass Spectrometry

National Research Council Canada - National Science Library

Bach, Stephan B; Hubert, Walter

2007-01-01

.... This review is intended to give an overview of mass spectrometry and its application to biological systems and biomarker discovery and how that might relate to relevant radiation dosimetry studies...

Synthesis of 1-octacosanol and GC-C-IRMS discrimination of samples from different origin.

Science.gov (United States)

Cravotto, Giancarlo; Calcio Gaudino, Emanuela; Barge, Alessandro; Binello, Arianna; Albertino, Andrea; Aghemo, Costanza

2010-03-01

Lately, long-chain primary alcohols have been investigated in depth on account of their biological activities. In particular, 1-octacosanol (C(28)H(57)OH), the main component of policosanol, the hypolipidaemic fatty alcohol mixture obtained from sugar cane wax, has been the subject of a multitude of pharmacological studies. The aim of this work was to search a convenient synthetic protocol for the preparation of 1-octacosanol in a gram scale. The key step was a Wittig reaction between the octadecyltriphenylphosphonium ylide and the methyl 10-oxodecanoate. Some steps were further improved by power ultrasound and microwave irradiation, either alone or in combination. Our methodology is suitable for a rapid generation of homologues by varying the chain length in the alkyl halide. Due to the high commercial value, a series of 1-octacosanol samples, either isolated from natural sources or from synthesis (different origin and suppliers), were analysed by gas chromatography-combustion-isotopic ratio mass spectrometry (GC-C-IRMS) and according to the carbon isotopic content, classified on the basis of their origin.

Inorganic trace analysis by laser ionization mass spectrometry

International Nuclear Information System (INIS)

Becker, S.; Dietze, H.J.

1991-01-01

Among the different spectrometric techniques for trace analysis Laser Ionization Mass Spectrometry (LIMS) is well established as a trace analytic method with a wide coverage. In the LIMS the sample material is evaporated and ionized by means of a focused pulsed laser beam in a laser microplasma, which is formed in the spot area of the irradiated sample. All chemical elements in the sample materials are evaporated and ionized in the laser plasma. The formed ions are separated according to mass and energy by a time-of-flight, quadrupole or double focusing mass spectrometer. In this review the characteristics and analytical features, some recent developments, and applications of laser ionization mass spectrometry in inorganic trace analysis are described. (orig.)

Laser ionization mass spectrometry in inorganic trace analysis

International Nuclear Information System (INIS)

Becker, J.S.; Dietze, H.J.

1992-01-01

Among the different spectrometric techniques for trace analysis Laser Ionization Mass Spectrometry (LIMS) is well established as a trace analytical method. With the LIMS technique the sample material is evaporated and ionized by means of a focused pulsed laser in a laser microplasma, which is formed in the spot area of the irradiated sample. All chemical elements in the sample materials are evaporated and ionized in the laser plasma. The ions formed are separated according to their mass and energy by a time-of-flight, quadrupole or double focusing mass spectrometer. In this review the characteristics and analytical features, some recent developments and applications of laser ionization mass spectrometry in inorganic trace analysis are described. (orig.)

Hands-on Electrospray Ionization-Mass Spectrometry for Upper-Level Undergraduate and Graduate Students

Science.gov (United States)

Stock, Naomi L.; March, Raymond E.

2014-01-01

Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

Science.gov (United States)

Julien, Maxime; Nun, Pierrick; Höhener, Patrick; Parinet, Julien; Robins, Richard J; Remaud, Gérald S

2016-01-15

In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Identification of chemical components in Baidianling Capsule based on gas chromatography-mass spectrometry and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

Science.gov (United States)

Wu, Wenying; Chen, Yu; Wang, Binjie; Sun, Xiaoyang; Guo, Ping; Chen, Xiaohui

2017-08-01

Baidianling Capsule, which is made from 16 Chinese herbs, has been widely used for treating vitiligo clinically. In this study, the sensitive and rapid method has been developed for the analysis of chemical components in Baidianling Capsule by gas chromatography-mass spectrometry in combination with retention indices and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Firstly, a total of 110 potential volatile compounds obtained from different extraction procedures including alkanes, alkenes, alkynes, ketones, ethers, aldehydes, alcohols, phenols, organic acids, esters, furans, pyrrole, acid amides, heterocycles, and oxides were detected from Baidianling Capsule by gas chromatography-mass spectrometry, of which 75 were identified by mass spectrometry in combination with the retention index. Then, a total of 124 components were tentatively identified by high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Fifteen constituents from Baidianling Capsule were accurately identified by comparing the retention times with those of reference compounds, others were identified by comparing the retention times and mass spectrometry data, as well as retrieving the reference literature. This study provides a practical strategy for rapidly screening and identifying the multiple constituents of a complex traditional Chinese medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass Spectrometry Applications for Toxicology.

Science.gov (United States)

Mbughuni, Michael M; Jannetto, Paul J; Langman, Loralie J

2016-12-01

Toxicology is a multidisciplinary study of poisons, aimed to correlate the quantitative and qualitative relationships between poisons and their physiological and behavioural effects in living systems. Other key aspects of toxicology focus on elucidation of the mechanisms of action of poisons and development of remedies and treatment plans for associated toxic effects. In these endeavours, Mass spectrometry (MS) has become a powerful analytical technique with a wide range of application used in the Toxicological analysis of drugs, poisons, and metabolites of both. To date, MS applications have permeated all fields of toxicology which include; environmental, clinical, and forensic toxicology. While many different analytical applications are used in these fields, MS and its hyphenated applications such as; gas chromatography MS (GC-MS), liquid chromatography MS (LC-MS), inductively coupled plasma ionization MS (ICP-MS), tandem mass spectrometry (MS/MS and MS n ) have emerged as powerful tools used in toxicology laboratories. This review will focus on these hyphenated MS technologies and their applications for toxicology.

Mass Spectrometry Applications for Toxicology

Science.gov (United States)

Mbughuni, Michael M.; Jannetto, Paul J.

2016-01-01

Toxicology is a multidisciplinary study of poisons, aimed to correlate the quantitative and qualitative relationships between poisons and their physiological and behavioural effects in living systems. Other key aspects of toxicology focus on elucidation of the mechanisms of action of poisons and development of remedies and treatment plans for associated toxic effects. In these endeavours, Mass spectrometry (MS) has become a powerful analytical technique with a wide range of application used in the Toxicological analysis of drugs, poisons, and metabolites of both. To date, MS applications have permeated all fields of toxicology which include; environmental, clinical, and forensic toxicology. While many different analytical applications are used in these fields, MS and its hyphenated applications such as; gas chromatography MS (GC-MS), liquid chromatography MS (LC-MS), inductively coupled plasma ionization MS (ICP-MS), tandem mass spectrometry (MS/MS and MSn) have emerged as powerful tools used in toxicology laboratories. This review will focus on these hyphenated MS technologies and their applications for toxicology. PMID:28149262

Identifying modifications in RNA by MALDI mass spectrometry

DEFF Research Database (Denmark)

Douthwaite, Stephen; Kirpekar, Finn

2007-01-01

as RNA modifications added in cell-free in vitro systems. MALDI-MS is particularly useful in cases in which other techniques such as those involving primer extension or chromatographic analyses are not practicable. To date, MALDI-MS has been used to localize rRNA modifications that are involved......Posttranscriptional modifications on the base or sugar of ribonucleosides generally result in mass increases that can be measured by mass spectrometry. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a direct and accurate means of determining the masses of RNAs. Mass...... spectra produced by MALDI are relatively straightforward to interpret, because they are dominated by singly charged ions, making it possible to analyze complex mixtures of RNA oligonucleotides ranging from trinucleotides up to 20-mers. Analysis of modifications within much longer RNAs, such as ribosomal...

Application of Laser Mass Spectrometry to Art and Archaeology

Science.gov (United States)

Gulian, Lase Lisa E.; Callahan, Michael P.; Muliadi, Sarah; Owens, Shawn; McGovern, Patrick E.; Schmidt, Catherine M.; Trentelman, Karen A.; deVries, Mattanjah S.

2011-01-01

REMPI laser mass spectrometry is a combination of resonance enhanced multiphoton ionization spectroscopy and time of flight mass spectrometry, This technique enables the collection of mass specific optical spectra as well as of optically selected mass spectra. Analytes are jet-cooled by entrainment in a molecular beam, and this low temperature gas phase analysis has the benefit of excellent vibronic resolution. Utilizing this method, mass spectrometric analysis of historically relevant samples can be simplified and improved; Optical selection of targets eliminates the need for chromatography while knowledge of a target's gas phase spectroscopy allows for facile differentiation of molecules that are in the aqueous phase considered spectroscopically indistinguishable. These two factors allow smaller sample sizes than commercial MS instruments, which in turn will require less damage to objects of antiquity. We have explored methods to optimize REMPI laser mass spectrometry as an analytical tool to archaeology using theobromine and caffeine as molecular markers in Mesoamerican pottery, and are expanding this approach to the field of art to examine laccaic acid in shellacs.

Applications of accelerator mass spectrometry to nuclear physics and astrophysics

International Nuclear Information System (INIS)

Guo Zhiyu; Zhang Chuan

2002-01-01

As an ultra high sensitive analyzing method, accelerator mass spectrometry is playing an important role in the studies of nuclear physics and astrophysics. The accelerator mass spectrometry (AMS) applications in searching for violation of Pauli exclusion principle and study on supernovae are discussed as examples

Quantitation of Acrylamide in Foods by High-Resolution Mass Spectrometry

NARCIS (Netherlands)

Troise, A.D.; Fogliano, Vincenzo

2016-01-01

The use of liquid chromatography high-resolution mass spectrometry (LC-HRMS) and direct analysis real-time high-resolution mass spectrometry (DART-HRMS) defines a new scenario in the analysis of thermal-induced toxicants, such as acrylamide. Several factors contribute to the definition of the

Practical aspects of trapped ion mass spectrometry, 5 applications of ion trapping devices

CERN Document Server

March, Raymond E

2009-01-01

Examines ion/neutral and ion/ion reactions, ion spectroscopy, and the structural characterization of proteins and peptides using quadropole ion trap mass spectrometry, Fourier transform - ion cyclotron resonance (FT-ICR) mass spectrometry, and traveling wave ion mobility mass spectrometry.

Hydrogen/deuterium exchange in mass spectrometry.

Science.gov (United States)

Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

2018-03-30

The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

Elucidating rhizosphere processes by mass spectrometry – A review

International Nuclear Information System (INIS)

Rugova, Ariana; Puschenreiter, Markus; Koellensperger, Gunda; Hann, Stephan

2017-01-01

The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. - Highlights: • State-of-the-art mass spectrometry methods developed and applied in rhizosphere research are reviewed. • Elemental and molecular mass spectrometry emphasizing different separation techniques (GC, LC or CE) are discussed. • Case studies on metal detoxification and

Elucidating rhizosphere processes by mass spectrometry – A review

Energy Technology Data Exchange (ETDEWEB)

Rugova, Ariana [Division of Analytical Chemistry, Department of Chemistry, University of Natural Resources and Life Sciences-BOKU, Vienna (Austria); Puschenreiter, Markus [Department of Forest and Soil Sciences, Rhizosphere Ecology and Biogeochemistry Group, University of Natural Resources and Life Sciences-BOKU, Vienna (Austria); Koellensperger, Gunda [Institute of Analytical Chemistry, Faculty of Chemistry, University of Vienna, Vienna (Austria); Hann, Stephan, E-mail: stephan.hann@boku.ac.at [Division of Analytical Chemistry, Department of Chemistry, University of Natural Resources and Life Sciences-BOKU, Vienna (Austria)

2017-03-01

The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. - Highlights: • State-of-the-art mass spectrometry methods developed and applied in rhizosphere research are reviewed. • Elemental and molecular mass spectrometry emphasizing different separation techniques (GC, LC or CE) are discussed. • Case studies on metal detoxification

Towards airborne nanoparticle mass spectrometry with nanomechanical string resonators

DEFF Research Database (Denmark)

Schmid, Silvan; Kurek, Maksymilian; Boisen, Anja

2013-01-01

airborne nanoparticle sensors. Recently, nanomechanical mass spectrometry was established. One of the biggest challenges of nanomechanical sensors is the low efficiency of diffusion-based sampling. We developed an inertial-based sampling method that enables the efficient sampling of airborne nanoparticles...... mode. Mass spectrometry of airborne nanoparticles requires the simultaneous operation in the first and second mode, which can be implemented in the transduction scheme of the resonator. The presented results lay the cornerstone for the realization of a portable airborne nanoparticle mass spectrometer....

Easy Extraction Method To Evaluate δ13C Vanillin by Liquid Chromatography-Isotopic Ratio Mass Spectrometry in Chocolate Bars and Chocolate Snack Foods.

Science.gov (United States)

Bononi, Monica; Quaglia, Giancarlo; Tateo, Fernando

2015-05-20

An easy extraction method that permits the use of a liquid chromatography-isotopic ratio mass spectrometry (LC-IRMS) system to evaluate δ(13)C of vanillin in chocolate products and industrial flavorings is presented. The method applies the determination of stable isotopes of carbon to discriminate between natural vanillin from vanilla beans and vanillin from other sources (mixtures from beans, synthesis, or biotechnology). A series of 13 chocolate bars and chocolate snack foods available on the Italian market and 8 vanilla flavorings derived from industrial quality control processes were analyzed. Only 30% of products considered in this work that declared "vanilla" on the label showed data that permitted the declaration "vanilla" according to European Union (EU) Regulation 1334/2008. All samples not citing "vanilla" or "natural flavoring" on the label gave the correct declaration. The extraction method is presented with data useful for statistical evaluation.

Detection of sputtered molecular doubly charged anions: a comparison of secondary-ion mass spectrometry (SIMS) and accelerator mass spectrometry (AMS)

International Nuclear Information System (INIS)

Gnaser, Hubert; Golser, Robin; Kutschera, Walter; Priller, Alfred; Steier, Peter; Vockenhuber, Christof

2004-01-01

The detection of small molecular dianions by secondary-ion mass spectrometry (SIMS) and by accelerator mass spectrometry (AMS) is compared. In SIMS, the existence of these dianions can be identified safely if the total mass number of the molecule is odd and the dianion is hence detected at a half-integral mass number. The occurrence of fragmentation processes which may interfere with this scheme, is illustrated by means of the energy spectra of singly and doubly charged negative cluster ions. As compared to SIMS, AMS can rely, in addition, on the break-up of molecular species in the stripping process: this allows to monitor the simultaneous arrival of several atomic constituents with a clear energetic pattern in coincidence at the detector. This feature is exemplified for the C 10 2- dianion

Applications of Isotope Ratio Mass Spectrometry in Sports Drug Testing Accounting for Isotope Fractionation in Analysis of Biological Samples.

Science.gov (United States)

Piper, Thomas; Thevis, Mario

2017-01-01

The misuse of anabolic-androgenic steroids (AAS) in sports aiming at enhancing athletic performance has been a challenging matter for doping control laboratories for decades. While the presence of a xenobiotic AAS or its metabolite(s) in human urine immediately represents an antidoping rule violation, the detection of the misuse of endogenous steroids such as testosterone necessitates comparably complex procedures. Concentration thresholds and diagnostic analyte ratios computed from urinary steroid concentrations of, e.g., testosterone and epitestosterone have aided identifying suspicious doping control samples in the past. These ratios can however also be affected by confounding factors and are therefore not sufficient to prove illicit steroid administrations. Here, carbon and, in rare cases, hydrogen isotope ratio mass spectrometry (IRMS) has become an indispensable tool. Importantly, the isotopic signatures of pharmaceutical steroid preparations commonly differ slightly but significantly from those found with endogenously produced steroids. By comparing the isotope ratios of endogenous reference compounds like pregnanediol to that of testosterone and its metabolites, the unambiguous identification of the urinary steroids' origin is accomplished. Due to the complex urinary matrix, several steps in sample preparation are inevitable as pure analyte peaks are a prerequisite for valid IRMS determinations. The sample cleanup encompasses steps such as solid phase or liquid-liquid extraction that are presumably not accompanied by isotopic fractionation processes, as well as more critical steps like enzymatic hydrolysis, high-performance liquid chromatography fractionation, and derivatization of analytes. In order to exclude any bias of the analytical results, each step of the analytical procedure is optimized and validated to exclude, or at least result in constant, isotopic fractionation. These efforts are explained in detail. © 2017 Elsevier Inc. All rights reserved.

Laser mass spectrometry for DNA sequencing, disease diagnosis, and fingerprinting

Energy Technology Data Exchange (ETDEWEB)

Winston Chen, C.H.; Taranenko, N.I.; Zhu, Y.F.; Chung, C.N.; Allman, S.L.

1997-03-01

Since laser mass spectrometry has the potential for achieving very fast DNA analysis, the authors recently applied it to DNA sequencing, DNA typing for fingerprinting, and DNA screening for disease diagnosis. Two different approaches for sequencing DNA have been successfully demonstrated. One is to sequence DNA with DNA ladders produced from Snager`s enzymatic method. The other is to do direct sequencing without DNA ladders. The need for quick DNA typing for identification purposes is critical for forensic application. The preliminary results indicate laser mass spectrometry can possibly be used for rapid DNA fingerprinting applications at a much lower cost than gel electrophoresis. Population screening for certain genetic disease can be a very efficient step to reducing medical costs through prevention. Since laser mass spectrometry can provide very fast DNA analysis, the authors applied laser mass spectrometry to disease diagnosis. Clinical samples with both base deletion and point mutation have been tested with complete success.

A mass spectrometry proteomics data management platform.

Science.gov (United States)

Sharma, Vagisha; Eng, Jimmy K; Maccoss, Michael J; Riffle, Michael

2012-09-01

Mass spectrometry-based proteomics is increasingly being used in biomedical research. These experiments typically generate a large volume of highly complex data, and the volume and complexity are only increasing with time. There exist many software pipelines for analyzing these data (each typically with its own file formats), and as technology improves, these file formats change and new formats are developed. Files produced from these myriad software programs may accumulate on hard disks or tape drives over time, with older files being rendered progressively more obsolete and unusable with each successive technical advancement and data format change. Although initiatives exist to standardize the file formats used in proteomics, they do not address the core failings of a file-based data management system: (1) files are typically poorly annotated experimentally, (2) files are "organically" distributed across laboratory file systems in an ad hoc manner, (3) files formats become obsolete, and (4) searching the data and comparing and contrasting results across separate experiments is very inefficient (if possible at all). Here we present a relational database architecture and accompanying web application dubbed Mass Spectrometry Data Platform that is designed to address the failings of the file-based mass spectrometry data management approach. The database is designed such that the output of disparate software pipelines may be imported into a core set of unified tables, with these core tables being extended to support data generated by specific pipelines. Because the data are unified, they may be queried, viewed, and compared across multiple experiments using a common web interface. Mass Spectrometry Data Platform is open source and freely available at http://code.google.com/p/msdapl/.

Simultaneous mass detection for direct inlet mass spectrometry

International Nuclear Information System (INIS)

Gordon, R.L.

1979-05-01

The evolution of analytical techniques for application in trace analysis has led to interest in practical methods for real-time monitoring. Direct inlet mass spectrometry (DIMS) has been the subject of considerable activity in recent years. A DIMS instrument is described which consists of an inlet system designed to permit particles entrained in the inlet air stream to strike a hot, oxidized rhenium filament which serves as a surface ionization source. A mass analyzer and detection system then permits identification of the elemental composition of particulates which strike the filament

Probing the Composition, Assembly and Activity of Protein Molecular Machines using Native Mass Spectrometry

NARCIS (Netherlands)

van de Waterbeemd, M.J.

2017-01-01

Native mass spectrometry and mass spectrometry in general, are powerful analytical tools for studying proteins and protein complexes. Native mass spectrometry may provide accurate mass measurements of large macromolecular assemblies enabling the investigation of their composition and stoichiometry.

Focusing procedures in time-of-flight mass spectrometry

International Nuclear Information System (INIS)

Ioanoviciu, D.

2002-01-01

Time-of-flight mass spectrometry is a fast growing field due to its ability to handle very fast processes and due to its theoretically unlimited mass range. The performances of the time-of-flight mass analysers are heavily dependent on the progress in ion optics, a periodically reviewed field. In this presentation the various focusing procedures in time-of-flight mass spectrometry are reviewed. For ions of the same charge and mass flight time differences result from different potentials at the location of formation and from the initial velocity spread. There is no simultaneous space and velocity focusing in time-of-flight mass spectrometry. Space focusing of first and second order can be reached in time-of-flight mass analysers having two homogeneous electric field ion sources followed by a field free space in front of the detector. Single and double stage homogeneous electric field mirrors can focus in time ions of different energies. These different energies result when ions leaving different initial sites and arriving simultaneously to an intermediate space focus. Convenient mass dispersion can be obtained by including a mirror. Initial velocity focusing is obtained by the delayed extraction procedure in drift space and mirror time-of-flight mass analysers. Post source pulse focusing aims at the same purpose. Ion source electrodes of hyperbolic shape, operated by high voltage pulses can bring major improvements of the resolution, especially at high masses. For each focusing procedure the geometric and/or electric conditions are given as well as the aberrations allowing the mass resolution determination. The various focusing procedures are compared and a prediction of their future performances was tempted. (author)

Quantitative correlations between collision induced dissociation mass spectrometry coupled with electrospray ionization or atmospheric pressure chemical ionization mass spectrometry - Experiment and theory

Science.gov (United States)

Ivanova, Bojidarka; Spiteller, Michael

2018-04-01

The problematic that we consider in this paper treats the quantitative correlation model equations between experimental kinetic and thermodynamic parameters of coupled electrospray ionization (ESI) mass spectrometry (MS) or atmospheric pressure chemical ionization (APCI) mass spectrometry with collision induced dissociation mass spectrometry, accounting for the fact that the physical phenomena and mechanisms of ESI- and APCI-ion formation are completely different. There are described forty two fragment reactions of three analytes under independent ESI- and APCI-measurements. The developed new quantitative models allow us to study correlatively the reaction kinetics and thermodynamics using the methods of mass spectrometry, which complementary application with the methods of the quantum chemistry provide 3D structural information of the analytes. Both static and dynamic quantum chemical computations are carried out. The object of analyses are [2,3-dimethyl-4-(4-methyl-benzoyl)-2,3-di-p-tolyl-cyclobutyl]-p-tolyl-methanone (1) and the polycyclic aromatic hydrocarbons derivatives of dibenzoperylen (2) and tetrabenzo [a,c,fg,op]naphthacene (3), respectively. As far as (1) is known to be a product of [2π+2π] cycloaddition reactions of chalcone (1,3-di-p-tolyl-propenone), however producing cyclic derivatives with different stereo selectivity, so that the study provide crucial data about the capability of mass spectrometry to provide determine the stereo selectivity of the analytes. This work also first provides quantitative treatment of the relations '3D molecular/electronic structures'-'quantum chemical diffusion coefficient'-'mass spectrometric diffusion coefficient', thus extending the capability of the mass spectrometry for determination of the exact 3D structure of the analytes using independent measurements and computations of the diffusion coefficients. The determination of the experimental diffusion parameters is carried out within the 'current monitoring method

Hydrogen Exchange Mass Spectrometry

Science.gov (United States)

Mayne, Leland

2018-01-01

Hydrogen exchange (HX) methods can reveal much about the structure, energetics, and dynamics of proteins. The addition of mass spectrometry (MS) to an earlier fragmentation-separation HX analysis now extends HX studies to larger proteins at high structural resolution and can provide information not available before. This chapter discusses experimental aspects of HX labeling, especially with respect to the use of MS and the analysis of MS data. PMID:26791986

Mass spectrometry applied to high temperature chemistry, (2)

International Nuclear Information System (INIS)

Asano, Mitsuru; Kato, Eiichi; Sata, Toshiyuki.

1980-01-01

The application of mass spectrometry to high temperature chemistry is reviewed. As a blanket material for fusion reactors, the behavior of lithium has been investigated by using mass analysers. The enthalpies of the chemical reactions of metallic lithium were obtained. The enthalpies of isomolecular exchange reactions and the derived atomization energies of LiD, Li 2 D and Li 2 D 2 were also obtained by mass spectrometry. The thermomechanical character of lithium oxide was studied. The vaporization behaviors of LiCrO 2 and Li 5 FeO 4 were studied with a quadrupole mass analyser. The vaporization of cobalt from nickel alloy was studied. The evaporated ions were analysed with a mass analyser. The measurement of the vaporized molecules of metals and fused silicate was made by mass spectrometry. The activities of Fe-V system were determined by measuring the ion current ratio. The activities of Fe-V-Cr system were also obtained. The vapor pressure of phosphor from Fe-P alloys can be measured. The activity coefficients and interaction parameters for the dilute solutions of elements, such as Mn, Al, Cu, Cr, Co, Ni, Si, Ti, V, B, Zr, Mo, C, S, and P, dissolved in liquid iron are shown in a table. The activities of NaCl-KCl system were derived by measuring the ion current ratio and by monomer-dimer method. (Kato, T.)

Protein Analysis by Mass Spectrometry

Directory of Open Access Journals (Sweden)

Cindic, M.

2008-04-01

Full Text Available Soft ionization techniques, electrospray (ESI and matrix-assisted laser desorption/ionization (MALDI make the analysis of biomolecules by mass spectrometry (MS possible. MS is used for determination of the molecular weight of peptides and protein, sequence analysis, characterization of protein-ligand interactions etc. The detection limit, resolution and mass accuracy depend on instrument used (Table 1. Impurities (buffers, salts, detergents can reduce the ion intensities or even totally suppress them, so a separation method (chromatography, 2D-gel electrophoresis must be used for purification of the sample.Molecular mass of intact protein can be determined by ESI or MALDI MS. Multiply charged ions are produced by ESI MS, while singly charged ions are predominant in MALDI spectra (Fig. 2.Sequence analysis of proteins by MS can be performed using peptide mass fingerprint. In this method, proteins are separated by 2-D gel electrophoresis and digested with specific protease (Table 2 or digested and then separated by two-dimensional chromatography (Fig. 1. The obtained peptide mixtures are analyzed by MS or MALDI-TOF technique. The masses determined by MS are compared with calculated masses from database entries. Different algorithms have been developed for protein identification. Example of posttranslational modifications (N- and O-glycosylation and protein sequence complex analysis after dual digestion (endoproteinase digestion followed by endoglycosidase digestion is shown in Fig. 3.It is known that detection of peptides by MS is influenced by intrinsic properties like amino acid composition, the basicity of the C-terminal amino acid, hydrophobicity, etc. Arginine-containing peptides dominate in MS spectra of tryptic digest, so the chemical derivatization of lysine terminal residue by O-methilisourea or 2-methoxy-4,5-1H-imidazole was suggested (Fig. 4.The peptide mass fingerprint method can be improved further by peptide fragmentation using tandem

IRM Concepts: Building Blocks for the 1990s.

Science.gov (United States)

Owen, Darrell E.

1989-01-01

Presents a conceptual overview of information resources management (IRM) by synthesizing concepts put forward during the 1980s and charts opportunities to move these concepts into practice. It is argued that the reorganization required by IRM is justified by better use of resources, better decision making, and an improved corporate structure. (21…

A new combined nanoSIMS and continuous-flow IRMS approach to measure hydrogen isotopes from water in hydrated rhyolitic glass

Science.gov (United States)

Gatti, E.; Kitchen, N.; Newman, S.; Guan, Y.; Westgate, J.; Pearce, N. J. G.; Nikolic, D.; Eiler, J. M.

2016-12-01

The hydrogen-isotope value of water of hydration (or secondary water) preserved in rhyolitic glasses may provide significant insights regarding the climate at the time of their deposition and the impact of super-eruptions upon the environment. However, the ability of the glass to retain the environmental D/H isotopic signal after hydration needs to be tested, since modifications to the D/H systematics may result from the continuous exchange of D/H with the atmosphere or condensed water after initial glass hydration. Ideal geological archives to test whether the glass retains its original hydrogen signal are sediments in natural waters and ice cores, which preserve tephra in constrained horizons that can be independently isotopically characterised. However, tephra in marine and fresh water sediments and ice cores are often present in concentrations of the order of 1000 grains/cm3 (IRMS methods require much more material ( 100-500 mg) and therefore cannot be applied. We present here a new integrated nanoSIMS and continuous flow IRMS approach to understand how water is distributed within single glass grains (diffusion profiles), quantify the time of hydration of young (Holocene) and old (Miocene) already well-characterised rhyolitic glasses, and measure the D/H ratio of the hydration water on single grains and bulk material consisting of only approximately 0.1-1 mg. The IRMS method measures the absolute abundance of hydrogen released from the sample by continuous-flow mass spectrometry. Current data indicates that the method can accurately measure a hydrogen signal from a rock sample containing at least 400 nanomoles of H2, corresponding to 70 µg of water, which translates to 1 mg of hydrous glass (>3 wt%) or 15 mg of dry ( 0.5 wt%) obsidian chips. The method can be improved by reducing the blank to IRMS method will be compared to sub-micron mapping of single-grains using a high-resolution ion microprobe, the CAMECA NanoSIMS 50L, in the Microanalysis Center for

Identification of keratinocyte specific markers using phage display and mass spectrometry

DEFF Research Database (Denmark)

Jensen, K.B.; Jensen, O.N.; Ravn, P.

2003-01-01

and mass spectrometry that allows identification of cell type-specific protein markers. The most important features of the method are (i) reduction of experimental noise originating from background binding of phage particles and (ii) isolation of affinity binders after a single round of selection, which...... antigens were subsequently identified by mass spectrometry as laminin-5, plectin, and fibronectin. The combination of phage display technology with mass spectrometry methods for protein identification is a general and promising approach for proteomic analysis of cell surface complexity....

Mass spectrometry of large molecules

International Nuclear Information System (INIS)

Facchetti, S.

1985-01-01

The lectures in this volume were given at a course on mass spectrometry of large molecules, organized within the framework of the Training and Education programme of the Joint Research Centre of the European Communities. Although first presented in 1983, most of the lectures have since been updated by their authors. (orig.)

Methods for recalibration of mass spectrometry data

Science.gov (United States)

Tolmachev, Aleksey V [Richland, WA; Smith, Richard D [Richland, WA

2009-03-03

Disclosed are methods for recalibrating mass spectrometry data that provide improvement in both mass accuracy and precision by adjusting for experimental variance in parameters that have a substantial impact on mass measurement accuracy. Optimal coefficients are determined using correlated pairs of mass values compiled by matching sets of measured and putative mass values that minimize overall effective mass error and mass error spread. Coefficients are subsequently used to correct mass values for peaks detected in the measured dataset, providing recalibration thereof. Sub-ppm mass measurement accuracy has been demonstrated on a complex fungal proteome after recalibration, providing improved confidence for peptide identifications.

Parsimonious Charge Deconvolution for Native Mass Spectrometry

Science.gov (United States)

2018-01-01

Charge deconvolution infers the mass from mass over charge (m/z) measurements in electrospray ionization mass spectra. When applied over a wide input m/z or broad target mass range, charge-deconvolution algorithms can produce artifacts, such as false masses at one-half or one-third of the correct mass. Indeed, a maximum entropy term in the objective function of MaxEnt, the most commonly used charge deconvolution algorithm, favors a deconvolved spectrum with many peaks over one with fewer peaks. Here we describe a new “parsimonious” charge deconvolution algorithm that produces fewer artifacts. The algorithm is especially well-suited to high-resolution native mass spectrometry of intact glycoproteins and protein complexes. Deconvolution of native mass spectra poses special challenges due to salt and small molecule adducts, multimers, wide mass ranges, and fewer and lower charge states. We demonstrate the performance of the new deconvolution algorithm on a range of samples. On the heavily glycosylated plasma properdin glycoprotein, the new algorithm could deconvolve monomer and dimer simultaneously and, when focused on the m/z range of the monomer, gave accurate and interpretable masses for glycoforms that had previously been analyzed manually using m/z peaks rather than deconvolved masses. On therapeutic antibodies, the new algorithm facilitated the analysis of extensions, truncations, and Fab glycosylation. The algorithm facilitates the use of native mass spectrometry for the qualitative and quantitative analysis of protein and protein assemblies. PMID:29376659

Nanostructure-initiator mass spectrometry biometrics

Science.gov (United States)

Leclerc, Marion; Bowen, Benjamin; Northen, Trent

2015-09-08

Several embodiments described herein are drawn to methods of identifying an analyte on a subject's skin, methods of generating a fingerprint, methods of determining a physiological change in a subject, methods of diagnosing health status of a subject, and assay systems for detecting an analyte and generating a fingerprint, by nanostructure-initiator mass spectrometry (NIMS).

Functional genomics by mass spectrometry

DEFF Research Database (Denmark)

Andersen, Jens S.; Mann, M

2000-01-01

Systematic analysis of the function of genes can take place at the oligonucleotide or protein level. The latter has the advantage of being closest to function, since it is proteins that perform most of the reactions necessary for the cell. For most protein based ('proteomic') approaches to gene f...... numbers of intact proteins by mass spectrometry directly. Examples from this laboratory illustrate biological problem solving by modern mass spectrometric techniques. These include the analysis of the structure and function of the nucleolus and the analysis of signaling complexes....

Determination of ultra-low levels of uranium using resonance ionization mass spectrometry

International Nuclear Information System (INIS)

Kiran Kumar, P.V.; Acharyulu, G.V.S.G.

2015-01-01

The determination of isotopic composition of actinides like U and Pu is important, due to their distribution in the environment as a result of nuclear weapons testing, fuel reprocessing, reactor operations and to a smaller extent from accidental releases. The analytical methods like fission track analysis (FTA), thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS) and resonance ionization mass spectrometry (RIMS) have evolved as sensitive techniques. Resonance Ionization Mass Spectrometry yields rapid isotopic signature data for material containing actinides without requiring time-consuming sample preparation and chemical separation procedures. In this paper, authors presented the details of the methodology and results for low-level detection of uranium using RIMS

Membrane introduction proton-transfer-reaction mass spectrometry

International Nuclear Information System (INIS)

Alexander, M.; Boscaini, E.; Maerk, T.; Lindinger, W.

2002-01-01

Proton-transfer-reaction mass spectrometry (PTR-MS) is a rapidly expanding field with multiple applications in ion physics, atmospheric chemistry, food chemistry, volatile organic compounds monitoring and biology. Initial studies that combine PTR-MS and membrane introduction mass spectrometry (MIMS) were researched and outlined. First using PTR-MS, certain fundamental physical properties of a poly-dimethylsiloxane (PDMS) membrane including solubilities and diffusion coefficients were measured. Second, it was shown how the chemical selectivity of the (PDMS) can be used to extend the capabilities of the PTR-MS instrument by eliminating certain isobaric interferences and excluding water from volatile organic compounds (VOCs). Experiments with mixtures of several VOCs (toluene, benzene, acetone, propanal, methanol) are presented. (nevyjel)

Optimization Of A Mass Spectrometry Process

International Nuclear Information System (INIS)

Lopes, Jose; Alegria, F. Correa; Redondo, Luis; Barradas, N. P.; Alves, E.; Rocha, Jorge

2011-01-01

In this paper we present and discuss a system developed in order to optimize the mass spectrometry process of an ion implanter. The system uses a PC to control and display the mass spectrum. The operator interacts with the I/O board, that interfaces with the computer and the ion implanter by a LabVIEW code. Experimental results are shown and the capabilities of the system are discussed.

The use of IRMS, (1)H NMR and chemical analysis to characterise Italian and imported Tunisian olive oils.

Science.gov (United States)

Camin, Federica; Pavone, Anita; Bontempo, Luana; Wehrens, Ron; Paolini, Mauro; Faberi, Angelo; Marianella, Rosa Maria; Capitani, Donatella; Vista, Silvia; Mannina, Luisa

2016-04-01

Isotope Ratio Mass Spectrometry (IRMS), (1)H Nuclear Magnetic Resonance ((1)H NMR), conventional chemical analysis and chemometric elaboration were used to assess quality and to define and confirm the geographical origin of 177 Italian PDO (Protected Denomination of Origin) olive oils and 86 samples imported from Tunisia. Italian olive oils were richer in squalene and unsaturated fatty acids, whereas Tunisian olive oils showed higher δ(18)O, δ(2)H, linoleic acid, saturated fatty acids β-sitosterol, sn-1 and 3 diglyceride values. Furthermore, all the Tunisian samples imported were of poor quality, with a K232 and/or acidity values above the limits established for extra virgin olive oils. By combining isotopic composition with (1)H NMR data using a multivariate statistical approach, a statistical model able to discriminate olive oil from Italy and those imported from Tunisia was obtained, with an optimal differentiation ability arriving at around 98%. Copyright © 2015 Elsevier Ltd. All rights reserved.

Spatially resolved δ13C analysis using laser ablation isotope ratio mass spectrometry

Science.gov (United States)

Moran, J.; Riha, K. M.; Nims, M. K.; Linley, T. J.; Hess, N. J.; Nico, P. S.

2014-12-01

Inherent geochemical, organic matter, and microbial heterogeneity over small spatial scales can complicate studies of carbon dynamics through soils. Stable isotope analysis has a strong history of helping track substrate turnover, delineate rhizosphere activity zones, and identifying transitions in vegetation cover, but most traditional isotope approaches are limited in spatial resolution by a combination of physical separation techniques (manual dissection) and IRMS instrument sensitivity. We coupled laser ablation sampling with isotope measurement via IRMS to enable spatially resolved analysis over solid surfaces. Once a targeted sample region is ablated the resulting particulates are entrained in a helium carrier gas and passed through a combustion reactor where carbon is converted to CO2. Cyrotrapping of the resulting CO2 enables a reduction in carrier gas flow which improves overall measurement sensitivity versus traditional, high flow sample introduction. Currently we are performing sample analysis at 50 μm resolution, require 65 ng C per analysis, and achieve measurement precision consistent with other continuous flow techniques. We will discuss applications of the laser ablation IRMS (LA-IRMS) system to microbial communities and fish ecology studies to demonstrate the merits of this technique and how similar analytical approaches can be transitioned to soil systems. Preliminary efforts at analyzing soil samples will be used to highlight strengths and limitations of the LA-IRMS approach, paying particular attention to sample preparation requirements, spatial resolution, sample analysis time, and the types of questions most conducive to analysis via LA-IRMS.

Paradigms in isotope dilution mass spectrometry for elemental speciation analysis

International Nuclear Information System (INIS)

Meija, Juris; Mester, Zoltan

2008-01-01

Isotope dilution mass spectrometry currently stands out as the method providing results with unchallenged precision and accuracy in elemental speciation. However, recent history of isotope dilution mass spectrometry has shown that the extent to which this primary ratio measurement method can deliver accurate results is still subject of active research. In this review, we will summarize the fundamental prerequisites behind isotope dilution mass spectrometry and discuss their practical limits of validity and effects on the accuracy of the obtained results. This review is not to be viewed as a critique of isotope dilution; rather its purpose is to highlight the lesser studied aspects that will ensure and elevate current supremacy of the results obtained from this method

Steroid Profiling by Gas Chromatography–Mass Spectrometry and High Performance Liquid Chromatography–Mass Spectrometry for Adrenal Diseases

Science.gov (United States)

McDonald, Jeffrey G.; Matthew, Susan

2012-01-01

The ability to measure steroid hormone concentrations in blood and urine specimens is central to the diagnosis and proper treatment of adrenal diseases. The traditional approach has been to assay each steroid hormone, precursor, or metabolite using individual aliquots of serum, each with a separate immunoassay. For complex diseases, such as congenital adrenal hyperplasia and adrenocortical cancer, in which the assay of several steroids is essential for management, this approach is time consuming and costly, in addition to using large amounts of serum. Gas chromatography/mass spectrometry profiling of steroid metabolites in urine has been employed for many years but only in a small number of specialized laboratories and suffers from slow throughput. The advent of commercial high-performance liquid chromatography instruments coupled to tandem mass spectrometers offers the potential for medium- to high-throughput profiling of serum steroids using small quantities of sample. Here, we review the physical principles of mass spectrometry, the instrumentation used for these techniques, the terminology used in this field and applications to steroid analysis. PMID:22170384

Development and validation of an universal interface for compound-specific stable isotope analysis of chlorine (37Cl/35Cl) by GC-high-temperature conversion (HTC)-MS/IRMS.

Science.gov (United States)

Renpenning, Julian; Hitzfeld, Kristina L; Gilevska, Tetyana; Nijenhuis, Ivonne; Gehre, Matthias; Richnow, Hans-Hermann

2015-03-03

A universal application of compound-specific isotope analysis of chlorine was thus far limited by the availability of suitable analysis techniques. In this study, gas chromatography in combination with a high-temperature conversion interface (GC-HTC), converting organic chlorine in the presence of H2 to gaseous HCl, was coupled to a dual-detection system, combining an ion trap mass spectrometer (MS) and isotope-ratio mass spectrometer (IRMS). The combination of the MS/IRMS detection enabled a detailed characterization, optimization, and online monitoring of the high-temperature conversion process via ion trap MS as well as a simultaneous chlorine isotope analysis by the IRMS. Using GC-HTC-MS/IRMS, chlorine isotope analysis at optimized conversion conditions resulted in very accurate isotope values (δ(37)Cl(SMOC)) for measured reference material with known isotope composition, including chlorinated ethylene, chloromethane, hexachlorocyclohexane, and trichloroacetic acids methyl ester. Respective detection limits were determined to be <15 nmol Cl on column with achieved precision of <0.3‰.

Incorporating Biological Mass Spectrometry into Undergraduate Teaching Labs, Part 2: Peptide Identification via Molecular Mass Determination

Science.gov (United States)

Arnquist, Isaac J.; Beussman, Douglas J.

2009-01-01

Mass spectrometry has become a routine analytical tool in the undergraduate curriculum in the form of GC-MS. While relatively few undergraduate programs have incorporated biological mass spectrometry into their programs, the importance of these techniques, as demonstrated by their recognition with the 2002 Nobel Prize, will hopefully lead to…

Multidimensional chromatography coupled to mass spectrometry in analysing complex proteomics samples

NARCIS (Netherlands)

Horvatovich, Peter; Hoekman, Berend; Govorukhina, Natalia; Bischoff, Rainer

Multidimensional chromatography coupled to mass spectrometry (LC(n)-MS) provides more separation power and an extended measured dynamic concentration range to analyse complex proteomics samples than one dimensional liquid chromatography coupled to mass spectrometry (1D-LC-MS). This review gives an

Boundaries of mass resolution in native mass spectrometry.

Science.gov (United States)

Lössl, Philip; Snijder, Joost; Heck, Albert J R

2014-06-01

Over the last two decades, native mass spectrometry (MS) has emerged as a valuable tool to study intact proteins and noncovalent protein complexes. Studied experimental systems range from small-molecule (drug)-protein interactions, to nanomachineries such as the proteasome and ribosome, to even virus assembly. In native MS, ions attain high m/z values, requiring special mass analyzers for their detection. Depending on the particular mass analyzer used, instrumental mass resolution does often decrease at higher m/z but can still be above a couple of thousand at m/z 5000. However, the mass resolving power obtained on charge states of protein complexes in this m/z region is experimentally found to remain well below the inherent instrument resolution of the mass analyzers employed. Here, we inquire into reasons for this discrepancy and ask how native MS would benefit from higher instrumental mass resolution. To answer this question, we discuss advantages and shortcomings of mass analyzers used to study intact biomolecules and biomolecular complexes in their native state, and we review which other factors determine mass resolving power in native MS analyses. Recent examples from the literature are given to illustrate the current status and limitations.

High-Performance Liquid Chromatography-Mass Spectrometry.

Science.gov (United States)

Vestal, Marvin L.

1984-01-01

Reviews techniques for online coupling of high-performance liquid chromatography with mass spectrometry, emphasizing those suitable for application to nonvolatile samples. Also summarizes the present status, strengths, and weaknesses of various techniques and discusses potential applications of recently developed techniques for combined liquid…

Symposium on fast atom and ion induced mass spectrometry of nonvolatile organic solids

International Nuclear Information System (INIS)

McNeal, C.J.

1982-01-01

The mechanisms of molecular and fragment ion production and the various parameters affecting ion yields were discussed by 6 invited speakers from Europe, Canada, and the US at this symposium. The work reported was almost equally divided between that using low-energy (keV) primary ion (or atom) beams, e.g. fast atom bombardment mass spectrometry (FABMS) and secondary ion mass spectrometry (SIMS) and that using high energy (MeV) particles, e.g. heavy ion induced mass spectrometry (HIIDMS) and 252 Cf-plasma desorption mass spectrometry ( 252 Cf-PDMS). Both theoretical foundations and observed experimental results for both techniques are included

Technical and economical aspects of mass spectrometry in food and agricultural industries

International Nuclear Information System (INIS)

Cornu, Ayme

1975-01-01

Mass spectrometry proved to be very useful for solving analytical problems in food and agricultural industries. Its essential properties are: high resolution mass spectrometry allows to find the molecular structure of an isolated compound, even with a very small sample; associated with on line gas chromatographic separation, it gives the possibility to identify a great number of components in a small complex extract; isotope determinations by mass spectrometry give an essential contribution to follow kinetic mechanisms of formation of natural molecules in plant-growing, photosynthesis, fertilization, ..., leading to identification of the origin of foods and beverages. The economical aspect of mass spectrometry is characterized by the cost of investment in instrumentation and the necessary high level of competence of the technicians [fr

Subcellular analysis by laser ablation electrospray ionization mass spectrometry

Science.gov (United States)

Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

2014-12-02

In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

Determination of isotope ratios of metals (and metalloids) by means of inductively coupled plasma-mass spectrometry for provenancing purposes - A review

International Nuclear Information System (INIS)

Balcaen, L.; Moens, L.; Vanhaecke, F.

2010-01-01

Since considerable time, isotopic analysis of different elements present in a sample, material or object (such as the 'light' elements H, C, N, O and S and 'heavy' elements, such as Sr and Pb), has been used in provenancing studies, as several factors - defined by 'the environment' or origin of the sample - can lead to measurable differences in their isotopic composition. For the light elements, traditionally, (gas source) isotope ratio mass spectrometry (IR-MS) is used, while for a long period of time, thermal ionization mass spectrometry (TIMS) was considered as the only technique capable of detecting subtle variations in the isotopic composition of the 'heavier' elements. However, since the introduction of the first inductively coupled plasma mass spectrometers (ICP-MS), considerable attention has been devoted to the development of methodologies and strategies to perform isotopic analysis by means of ICP-MS. While the relatively modest isotope ratio precision offered by single-collector ICP-MS may already be fit-for-purpose under some circumstances, especially the introduction of multi-collector ICP-MS instruments, equipped with an array of Faraday detectors instead of a single electron multiplier, has lead to tremendous improvements in the field of isotopic analysis. As a result, MC-ICP-MS can be seen as a very strong competitor of TIMS nowadays, while it even provides information on the small isotopic variations shown by some elements, that are not or hardly accessible by means of TIMS (e.g., elements with a high ionization energy). Owing to these new instrumental developments, the application field of isotopic analysis by means of ICP-MS is continuously growing, also in the field of provenance determination. This paper is intended as a review of the developments in and the recent applications of isotopic analysis by means of ICP-MS in this specific research field.

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

Science.gov (United States)

Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert‐Jan

2016-01-01

Rationale Analyses of stable carbon isotope ratios (δ 13C 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 samples containing at least several μg of carbon. Methods Here we present a setup combining laser ablation, nano combustion gas chromatography and isotope ratio mass spectrometry (LA/nC/GC/IRMS). A deep UV (193 nm) laser is used for optimal fragmentation of organic matter with minimum fractionation effects and an exceptionally small ablation chamber and combustion oven are used to reduce the minimum sample mass requirement compared with previous studies. Results Analyses of the international IAEA CH‐7 polyethylene standard show optimal accuracy, and precision better than 0.5‰, when measuring at least 42 ng C. Application to untreated modern Eucalyptus globulus (C3 plant) and Zea mays (C4 plant) pollen grains shows a ~ 16‰ offset between these species. Within each single Z. mays pollen grain, replicate analyses show almost identical δ 13C values. Conclusions Isotopic offsets between individual pollen grains exceed analytical uncertainties, therefore probably reflecting interspecimen variability of ~0.5–0.9‰. These promising results set the stage for investigating both δ 13C values and natural carbon isotopic variability between single specimens of a single population of all kinds of organic particles yielding tens of nanograms of carbon. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd. PMID:27766694

Mass spectrometry in identification of ecotoxicants including chemical and biological warfare agents

International Nuclear Information System (INIS)

Lebedev, Albert T.

2005-01-01

Mass spectrometry is a unique tool to detect and identify trace levels of organic and bioorganic compounds as well as microorganisms in the environment. The range of potential chemical warfare (CW) and biological warfare (BW) agents is very broad. An important advantage of mass spectrometry over other techniques involves potential for full spectrum detection of chemical and biological agents including mid-spectrum materials (i.e. bioactive peptides, toxins, etc.) for which biological approaches are inadequate. Being very fast (seconds and minutes), extremely sensitive (zeptomoles 10 -21 ), and informative (detailed qualitative and quantitative composition of mixtures containing hundreds of chemicals), mass spectrometry is a principal analytical tool at the sites of destruction of CW. Due to its unique features, mass spectrometry is applied not only for the detection of CW agents, but for the analysis of products of metabolism and degradation of these agents in organisms or environment as well. The present paper deals with some examples of successful application of mass spectrometry for the analyses of ecotoxicants, chemical warfare agents, explosives, and microorganisms including biology warfare agents

Interpretation of Tandem Mass Spectrometry (MSMS) Spectra for Peptide Analysis

DEFF Research Database (Denmark)

Hjernø, Karin; Højrup, Peter

2015-01-01

The aim of this chapter is to give a short introduction to peptide analysis by mass spectrometry (MS) and interpretation of fragment mass spectra. Through examples and guidelines we demonstrate how to understand and validate search results and how to perform de novo sequencing based on the often...... very complex fragmentation pattern obtained by tandem mass spectrometry (also referred to as MSMS). The focus is on simple rules for interpretation of MSMS spectra of tryptic as well as non-tryptic peptides....

Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Perdian, David C. [Iowa State Univ., Ames, IA (United States)

2009-01-01

Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

Plutonium determination in urine by techniques of mass spectrometry

International Nuclear Information System (INIS)

Hernandez M, H.; Yllera de Ll, A.

2013-10-01

The objective of this study was to develop an analytic method for quantification and plutonium reappraisal in plane tables of alpha spectrometry be means of the mass spectrometry technique of high resolution with plasma source inductively coupled and desolvator Aridus (Aridus-Hr-Icp-Ms) and mass spectrometry with accelerator (AMS). The obtained results were, the recovery percentage of Pu in the plane table was of ∼ 90% and activity minimum detectable obtained with Aridus-Hr-Icp-Ms and AMS was of ∼ 3 and ∼ 0.4 f g of 239 Pu, respectively. Conclusion, the results demonstrate the aptitude of the Aridus-Hr-Icp-Ms and AMS techniques in the Pu reappraisal in plane tables with bigger speed and precision, improving the values notably of the activity minimum detectable that can be obtained with the alpha spectrometry (∼ 50 f g of 239 Pu). (author)

Surface ionization mass spectrometry of opiates

International Nuclear Information System (INIS)

Usmanov, D.T.

2009-07-01

Key words: surface ionization, adsorption, heterogeneous reactions, surface ionization mass spectrometry, thermodesorption surface ionization spectroscopy, thermoemitter, opiates, extracts of biosamples. Subjects of study. The mass - spectrometric study of thermal - ion emission: surface ionization of opiates by on the surface of oxidized refractory metals. Purpose of work is to establish the regularities of surface ionization (SI) of multi-atomic molecule opiates and their mixtures develop the scientific base of SI methods for high sensitive and selective detection and analysis of these substances in the different objects, including biosamples. Methods of study: surface ionization mass spectrometry, thermodesorption surface ionization spectroscopy. The results obtained and their novelty. For the first time, SI of molecule opiates on the oxidized tungsten surface has been studied and their SI mass-spectra and temperature dependences of ion currents have been obtained, the characteristic heterogeneous reactions of an adsorbed molecules and the channels of monomolecular decays vibrationally-excited ions on their way in mass-spectrometry have been revealed, sublimation energy has been defined, the activation energy of E act , of these decays has been estimated for given period of time. Additivity of the SI mass-spectra of opiate mixtures of has been established under conditions of joint opiate adsorption. High selectivity of SI allows the extracts of biosamples to be analyzed without their preliminary chromatographic separation. The opiates are ionized by SI with high efficiency (from 34 C/mol to 112 C/mol), which provides high sensitivity of opiate detection by SI/MS and APTDSIS methods from - 10 -11 g in the samples under analysis. Practical value. The results of these studies create the scientific base for novel SI methods of high sensitive detection and analysis of the trace amounts of opiates in complicated mixtures, including biosamples without their preliminary

Quantitating subcellular metabolism with multi-isotope imaging mass spectrometry

OpenAIRE

Steinhauser, Matthew L.; Bailey, Andrew; Senyo, Samuel E.; Guillermier, Christelle; Perlstein, Todd S.; Gould, Alex P.; Lee, Richard T.; Lechene, Claude P.

2012-01-01

Mass spectrometry with stable isotope labels has been seminal in discovering the dynamic state of living matter 1,2 but is limited to bulk tissues or cells. We developed multi-isotope imaging mass spectrometry (MIMS) that allowed us to view and measure stable isotope incorporation with sub-micron resolution 3,4 . Here we apply MIMS to diverse organisms, including Drosophila, mice, and humans. We test the “immortal strand hypothesis,” which predicts that during asymmetric stem cell division ch...

Analysis of chirality by femtosecond laser ionization mass spectrometry.

Science.gov (United States)

Horsch, Philipp; Urbasch, Gunter; Weitzel, Karl-Michael

2012-09-01

Recent progress in the field of chirality analysis employing laser ionization mass spectrometry is reviewed. Emphasis is given to femtosecond (fs) laser ionization work from the author's group. We begin by reviewing fundamental aspects of determining circular dichroism (CD) in fs-laser ionization mass spectrometry (fs-LIMS) discussing an example from the literature (resonant fs-LIMS of 3-methylcyclopentanone). Second, we present new data indicating CD in non-resonant fs-LIMS of propylene oxide. Copyright © 2012 Wiley Periodicals, Inc., A Wiley Company.

ISMAS international discussion meet on elemental mass spectrometry in health and environmental sciences

International Nuclear Information System (INIS)

Aggarwal, S.K.; Jaison, P.G.; Telmore, V.M.

2011-04-01

Mass spectrometry is an indispensable analytical tool associated with almost all branches of science including biology, chemistry, earth sciences, nuclear science, physics, etc. The technique holds tremendous potential owing to its high sensitivity, selectivity and its ability to measure small changes in the isotopic abundances of different elements. Innovations in mass spectrometry instrumentation are further widening the scope by making it possible to handle very large bio-molecules and polymers. New techniques for mass analysis, novel designs for ionization and developments in electronic accessories have contributed to elevate mass spectrometry to a position of prime importance in research. Development in mass spectrometry has revolutionized the study of micro-nutrient metabolism, of biologically active compounds and for drug discovery in pharmaceutical research. Elemental mass spectrometry is making major contributions to food toxicology, food forensics, and study of metabolism of nutrient minerals including Fe, Zn, Ca, Cu and Se. The area of speciation analysis using hyphenated techniques as well as electro-spray ionization have undergone a phenomenal evolution and development in the recent past. Impressive progress in mass spectrometry towards lower detection limits, higher resolution and molecule-specific detection at trace levels in complex matrices allows new frontiers to be crossed. Papers relevant to INIS are indexed separately

Mass Spectrometry Market: Value chain and stakeholder analysis up to 2024

OpenAIRE

Smita Deshmukh

2016-01-01

Transparency Market Research Reports incorporated a definite business overview and investigation inclines on "Mass Spectrometry Market". This report likewise incorporates more illumination about fundamental review of the business including definitions, requisitions and worldwide business sector industry structure. Read Full Report: http://www.transparencymarketresearch.com/mass-spectrometry-market.html

Mass Spectrometry-Based Proteomics for Pre-Eclampsia and Preterm Birth

Directory of Open Access Journals (Sweden)

Kai P. Law

2015-05-01

Full Text Available Pregnancy-related complications such as pre-eclampsia and preterm birth now represent a notable burden of adverse health. Pre-eclampsia is a hypertensive disorder unique to pregnancy. It is an important cause of maternal death worldwide and a leading cause of fetal growth restriction and iatrogenic prematurity. Fifteen million infants are born preterm each year globally, but more than one million of those do not survive their first month of life. Currently there are no predictive tests available for diagnosis of these pregnancy-related complications and the biological mechanisms of the diseases have not been fully elucidated. Mass spectrometry-based proteomics have all the necessary attributes to provide the needed breakthrough in understanding the pathophysiology of complex human diseases thorough the discovery of biomarkers. The mass spectrometry methodologies employed in the studies for pregnancy-related complications are evaluated in this article. Top-down proteomic and peptidomic profiling by laser mass spectrometry, liquid chromatography or capillary electrophoresis coupled to mass spectrometry, and bottom-up quantitative proteomics and targeted proteomics by liquid chromatography mass spectrometry have been applied to elucidate protein biomarkers and biological mechanism of pregnancy-related complications. The proteomes of serum, urine, amniotic fluid, cervical-vaginal fluid, placental tissue, and cytotrophoblastic cells have all been investigated. Numerous biomarkers or biomarker candidates that could distinguish complicated pregnancies from healthy controls have been proposed. Nevertheless, questions as to the clinically utility and the capacity to elucidate the pathogenesis of the pre-eclampsia and preterm birth remain to be answered.

Mass Spectrometry-Based Proteomics for Pre-Eclampsia and Preterm Birth

Science.gov (United States)

Law, Kai P.; Han, Ting-Li; Tong, Chao; Baker, Philip N.

2015-01-01

Pregnancy-related complications such as pre-eclampsia and preterm birth now represent a notable burden of adverse health. Pre-eclampsia is a hypertensive disorder unique to pregnancy. It is an important cause of maternal death worldwide and a leading cause of fetal growth restriction and iatrogenic prematurity. Fifteen million infants are born preterm each year globally, but more than one million of those do not survive their first month of life. Currently there are no predictive tests available for diagnosis of these pregnancy-related complications and the biological mechanisms of the diseases have not been fully elucidated. Mass spectrometry-based proteomics have all the necessary attributes to provide the needed breakthrough in understanding the pathophysiology of complex human diseases thorough the discovery of biomarkers. The mass spectrometry methodologies employed in the studies for pregnancy-related complications are evaluated in this article. Top-down proteomic and peptidomic profiling by laser mass spectrometry, liquid chromatography or capillary electrophoresis coupled to mass spectrometry, and bottom-up quantitative proteomics and targeted proteomics by liquid chromatography mass spectrometry have been applied to elucidate protein biomarkers and biological mechanism of pregnancy-related complications. The proteomes of serum, urine, amniotic fluid, cervical-vaginal fluid, placental tissue, and cytotrophoblastic cells have all been investigated. Numerous biomarkers or biomarker candidates that could distinguish complicated pregnancies from healthy controls have been proposed. Nevertheless, questions as to the clinically utility and the capacity to elucidate the pathogenesis of the pre-eclampsia and preterm birth remain to be answered. PMID:26006232

Automated, parallel mass spectrometry imaging and structural identification of lipids

DEFF Research Database (Denmark)

Ellis, Shane R.; Paine, Martin R.L.; Eijkel, Gert B.

2018-01-01

We report a method that enables automated data-dependent acquisition of lipid tandem mass spectrometry data in parallel with a high-resolution mass spectrometry imaging experiment. The method does not increase the total image acquisition time and is combined with automatic structural assignments....... This lipidome-per-pixel approach automatically identified and validated 104 unique molecular lipids and their spatial locations from rat cerebellar tissue....

Mass Spectrometry Imaging of Drugs of Abuse in Hair.

Science.gov (United States)

Flinders, Bryn; Cuypers, Eva; Porta, Tiffany; Varesio, Emmanuel; Hopfgartner, Gérard; Heeren, Ron M A

2017-01-01

Hair testing is a powerful tool routinely used for the detection of drugs of abuse. The analysis of hair is highly advantageous as it can provide prolonged drug detectability versus that in biological fluids and chronological information about drug intake based on the average growth of hair. However, current methodology requires large amounts of hair samples and involves complex time-consuming sample preparation followed by gas or liquid chromatography coupled with mass spectrometry. Mass spectrometry imaging is increasingly being used for the analysis of single hair samples, as it provides more accurate and visual chronological information in single hair samples.Here, two methods for the preparation of single hair samples for mass spectrometry imaging are presented.The first uses an in-house built cutting apparatus to prepare longitudinal sections, the second is a method for embedding and cryo-sectioning hair samples in order to prepare cross-sections all along the hair sample.

Analytical applications of resonance ionization mass spectrometry (RIMS)

International Nuclear Information System (INIS)

Fassett, J.D.; Travis, J.C.

1988-01-01

A perspective on the role of resonance ionization mass spectrometry (RIMS) in the field of analytical chemistry is presented. RIMS provides new, powerful, and complementary capabilities relative to traditional methods of inorganic mass spectrometry. Much of the initial work in RIMS has been to illustrate these capabilities and define the potential of RIMS in the generalized field of chemical analysis. Three areas of application are reviewed here: (1) noble gas measurements; (2) materials analysis using isotope dilution (IDMS); and, (3) solids analysis using direct sampling. The role of RIMS is discussed relative to the more traditional mass spectrometric methods of analysis in these areas. The applications are meant to illustrate the present state-of-the-art as well as point to the future state-of-the-art of RIMS in chemical analysis. (author)

Analysis of organic compounds by secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS)

International Nuclear Information System (INIS)

Ewinger, H.P.

1993-05-01

This study is about the use of secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS) as analytical techniques with depth resolution in determining organic components in environmental solid microparticles. The first application of plasma SNMS to organic compounds revealed the spectra to be composed mainly of signals from the atoms of all participating elements, such as C, H, O, N, S, P, and Cl. In addition, signals produced by multi-atomic clusters can be detected, such as CH, C 2 , CH 2 , C 2 H, and C 3 , as well as signals indicating the presence of organic compounds with hetero elements, such as OH, NH, and CN. Their intensity decreases very markedly with increasing numbers of atoms. Among the signals from bi-atomic clusters, those coming from elements with large mass differences are most intense. The use of plasma SNMS with organic compounds has shown that, except for spurious chemical reactions induced by ion bombardment and photodesorption by the photons of the plasma, it is possible to analyze with resolution in depth, elements of organic solids. A more detailed molecular characterization of organic compounds is possible by means of SIMS on the basis of multi-atomic fragments and by comparison with suitable signal patterns. (orig./BBR) [de

Impact of automation on mass spectrometry.

Science.gov (United States)

Zhang, Yan Victoria; Rockwood, Alan

2015-10-23

Mass spectrometry coupled to liquid chromatography (LC-MS and LC-MS/MS) is an analytical technique that has rapidly grown in popularity in clinical practice. In contrast to traditional technology, mass spectrometry is superior in many respects including resolution, specificity, multiplex capability and has the ability to measure analytes in various matrices. Despite these advantages, LC-MS/MS remains high cost, labor intensive and has limited throughput. This specialized technology requires highly trained personnel and therefore has largely been limited to large institutions, academic organizations and reference laboratories. Advances in automation will be paramount to break through this bottleneck and increase its appeal for routine use. This article reviews these challenges, shares perspectives on essential features for LC-MS/MS total automation and proposes a step-wise and incremental approach to achieve total automation through reducing human intervention, increasing throughput and eventually integrating the LC-MS/MS system into the automated clinical laboratory operations. Copyright © 2015 Elsevier B.V. All rights reserved.

Mass Spectrometry on Future Mars Landers

Science.gov (United States)

Brinckerhoff, W. B.; Mahaffy, P. R.

2011-01-01

Mass spectrometry investigations on the 2011 Mars Science Laboratory (MSL) and the 2018 ExoMars missions will address core science objectives related to the potential habitability of their landing site environments and more generally the near-surface organic inventory of Mars. The analysis of complex solid samples by mass spectrometry is a well-known approach that can provide a broad and sensitive survey of organic and inorganic compounds as well as supportive data for mineralogical analysis. The science value of such compositional information is maximized when one appreciates the particular opportunities and limitations of in situ analysis with resource-constrained instrumentation in the context of a complete science payload and applied to materials found in a particular environment. The Sample Analysis at Mars (SAM) investigation on MSL and the Mars Organic Molecule Analyzer (MOMA) investigation on ExoMars will thus benefit from and inform broad-based analog field site work linked to the Mars environments where such analysis will occur.

Helium-3 mass spectrometry for low-level tritium analysis of environmental samples

International Nuclear Information System (INIS)

Surano, K.A.; Hudson, G.B.; Failor, R.A.; Sims, J.M.; Holland, R.C.; MacLean, S.C.; Garrison, J.C.

1991-04-01

Helium-3 ( 3 He) mass spectrometry for the analysis of low-level tritium ( 3 H) concentrations in environmental sample matrices was compared with conventional low-level β-decay counting methods. The mass-spectrometry method compared favorably, equaling or surpassing conventional decay-counting methods with respect to most criteria. Additional research and method refinements may make 3 He mass spectrometry the method of choice for routine, low-level to very-low-level 3 H measurements in a wide variety of environmental samples in the future

Continuous flow isotope ratio mass spectrometer (CF-IRMS) and its applications in hydrocarbon research and exploration

International Nuclear Information System (INIS)

Kalpana, G.; Patil, D.J.; Kumar, B.

2004-01-01

Stable isotope ratio mass spectrometers have been widely used to determine the isotopic ratios of light elements such as hydrogen, carbon, nitrogen, oxygen and sulphur. Continuous Flow Isotope Ratio Mass Spectrometry (CFIRMS) provides reliable data on nanomole amount of sample gas without the need for cryogenic trapping using cold fingers as in dual inlet isotope ratio mass spectrometer. High sample throughput is achieved as the system is configured with automated sample preparation devices and auto samplers. This paper presents a brief description of CFIRMS exploration

Determination of 5-fluorouracil in plasma with HPLC-tandem mass spectrometry

NARCIS (Netherlands)

van Kuilenburg, A. B. P.; van Lenthe, H.; Maring, J. G.; van Gennip, A. H.

2006-01-01

In this article, we describe a fast and specific method to measure 5FU with HPLC tandem-mass spectrometry. Reversed-phase HPLC was combined with electrospray ionization tandem mass spectrometry and detection was performed by multiple-reaction monitoring. Stable-isotope-labeled 5FU (1,3-15N2-5FU) was

Proceedings of twelfth ISMAS symposium cum workshop on mass spectrometry

International Nuclear Information System (INIS)

Alamelu, D.; Jaison, P.G.; Aggarwal, S.K.

2007-03-01

Mass Spectrometry is an important analytical tool and has encompassed almost all branches of science and technology including Agricultural, biology, Chemistry, Earth sciences, environment, Forensic Science, Medical Sciences, Hydrology, Nuclear Technology, Oceanography, Physics etc. Recent advancements in the instrumentation of Mass Spectrometry have further strengthened its role for various applications. It is indeed a matter of great pleasure to present this special Issue of ISMAS Bulletin which is brought out on the occasion of the 12th ISMAS Symposium cum Workshop on Mass spectrometry (12th ISMAS-WS 2007) being held at Cidade-de-Goa, Dona Paula, Goa from March 25 to 30, 2007 in association with National Institute of Oceanography, Goa. This Symposium cum Workshop is co-sponsored by Scientific Departments of Government of India. Papers relevant to INIS are indexed separately

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.

Native Mass Spectrometry in Fragment-Based Drug Discovery

Directory of Open Access Journals (Sweden)

Liliana Pedro

2016-07-01

Full Text Available The advent of native mass spectrometry (MS in 1990 led to the development of new mass spectrometry instrumentation and methodologies for the analysis of noncovalent protein–ligand complexes. Native MS has matured to become a fast, simple, highly sensitive and automatable technique with well-established utility for fragment-based drug discovery (FBDD. Native MS has the capability to directly detect weak ligand binding to proteins, to determine stoichiometry, relative or absolute binding affinities and specificities. Native MS can be used to delineate ligand-binding sites, to elucidate mechanisms of cooperativity and to study the thermodynamics of binding. This review highlights key attributes of native MS for FBDD campaigns.

Native Mass Spectrometry in Fragment-Based Drug Discovery.

Science.gov (United States)

Pedro, Liliana; Quinn, Ronald J

2016-07-28

The advent of native mass spectrometry (MS) in 1990 led to the development of new mass spectrometry instrumentation and methodologies for the analysis of noncovalent protein-ligand complexes. Native MS has matured to become a fast, simple, highly sensitive and automatable technique with well-established utility for fragment-based drug discovery (FBDD). Native MS has the capability to directly detect weak ligand binding to proteins, to determine stoichiometry, relative or absolute binding affinities and specificities. Native MS can be used to delineate ligand-binding sites, to elucidate mechanisms of cooperativity and to study the thermodynamics of binding. This review highlights key attributes of native MS for FBDD campaigns.

A MASSive Laboratory Tour. An Interactive Mass Spectrometry Outreach Activity for Children

Science.gov (United States)

Jungmann, Julia H.; Mascini, Nadine E.; Kiss, Andras; Smith, Donald F.; Klinkert, Ivo; Eijkel, Gert B.; Duursma, Marc C.; Cillero Pastor, Berta; Chughtai, Kamila; Chughtai, Sanaullah; Heeren, Ron M. A.

2013-07-01

It is imperative to fascinate young children at an early stage in their education for the analytical sciences. The exposure of the public to mass spectrometry presently increases rapidly through the common media. Outreach activities can take advantage of this exposure and employ mass spectrometry as an exquisite example of an analytical science in which children can be fascinated. The presented teaching modules introduce children to mass spectrometry and give them the opportunity to experience a modern research laboratory. The modules are highly adaptable and can be applied to young children from the age of 6 to 14 y. In an interactive tour, the students explore three major scientific concepts related to mass spectrometry; the building blocks of matter, charged particle manipulation by electrostatic fields, and analyte identification by mass analysis. Also, the students carry out a mass spectrometry experiment and learn to interpret the resulting mass spectra. The multistage, inquiry-based tour contains flexible methods, which teach the students current-day research techniques and possible applications to real research topics. Besides the scientific concepts, laboratory safety and hygiene are stressed and the students are enthused for the analytical sciences by participating in "hands-on" work. The presented modules have repeatedly been successfully employed during laboratory open days. They are also found to be extremely suitable for (early) high school science classes during laboratory visit-focused field trips.

Stable isotope mass spectrometry in petroleum exploration

International Nuclear Information System (INIS)

Mathur, Manju

1997-01-01

The stable isotope mass spectrometry plays an important role to evaluate the stable isotopic composition of hydrocarbons. The isotopic ratios of certain elements in petroleum samples reflect certain characteristics which are useful for petroleum exploration

Fast DNA analysis by laser mass spectrometry for human genome analysis

International Nuclear Information System (INIS)

Tang, K.; Taranenko, N. I.; Allman, S. L.; Chang, L. Y.; Chen, C. H.

1995-01-01

Fast DNA sequencing by laser mass spectrometry is possible if the following 3 criteria are met: (1) Size of DNA fragment should be greater than 300 nucleotides. (2) Enough sensitivity to detect DNA produce from polymerases chain reactins (PCR). (3) Higher resolution of mass spectr. So far, the firt 2 criteria are met: If the resolution can be significantly improve, fast DNA sequencing by laser mass spectrometry weil be a reality in the near feature

IRMS detection of testosterone manipulated with 13C labeled standards in human urine by removing the labeled 13C

International Nuclear Information System (INIS)

Wang, Jingzhu; Yang, Rui; Yang, Wenning; Liu, Xin; Xing, Yanyi; Xu, Youxuan

2014-01-01

Highlights: • 13 C labeled testosterone can be used to adjust the isotope ratio of testosterone. • The novel testosterone cannot be detected by the regular IRMS method in doping test. • A method was explored to remove the labeled 13 C. • The established method can be used to detect the manipulated testosterone. - Abstract: Isotope ratio mass spectrometry (IRMS) is applied to confirm testosterone (T) abuse by determining the carbon isotope ratios (δ 13 C value). However, 13 C labeled standards can be used to control the δ 13 C value and produce manipulated T which cannot be detected by the current method. A method was explored to remove the 13 C labeled atom at C-3 from the molecule of androsterone (Andro), the metabolite of T in urine, to produce the resultant (A-nor-5α-androstane-2,17-dione, ANAD). The difference in δ 13 C values between Andro and ANAD (Δδ 13 C Andro–ANAD , ‰) would change significantly in case manipulated T is abused. Twenty-one volunteers administered T manipulated with different 13 C labeled standards. The collected urine samples were analyzed with the established method, and the maximum value of Δδ 13 C Andro–ANAD post ingestion ranged from 3.0‰ to 8.8‰. Based on the population reference, the cut-off value of Δδ 13 C Andro–ANAD for positive result was suggested as 1.2‰. The developed method could be used to detect T manipulated with 3- 13 C labeled standards

Pyrolysis - gas chromatography - mass spectrometry of lignins

Energy Technology Data Exchange (ETDEWEB)

Martin, F; Saiz-Jimenez, C; Gonzalez-Vila, F J

1979-01-01

Milled wood lignins from spruce, beech and bamboo were pyrolysed. The high-boiling products of pyrolysis were studied by GLC and mass spectrometry. The forty-three products identified provide information on the structural units of lignin.

Mass spectrometry. [review of techniques

Science.gov (United States)

Burlingame, A. L.; Kimble, B. J.; Derrick, P. J.

1976-01-01

Advances in mass spectrometry (MS) and its applications over the past decade are reviewed in depth, with annotated literature references. New instrumentation and techniques surveyed include: modulated-beam MS, chromatographic MS on-line computer techniques, digital computer-compatible quadrupole MS, selected ion monitoring (mass fragmentography), and computer-aided management of MS data and interpretation. Areas of application surveyed include: organic MS and electron impact MS, field ionization kinetics, appearance potentials, translational energy release, studies of metastable species, photoionization, calculations of molecular orbitals, chemical kinetics, field desorption MS, high pressure MS, ion cyclotron resonance, biochemistry, medical/clinical chemistry, pharmacology, and environmental chemistry and pollution studies.

LILBID-mass spectrometry of the mitochondrial preprotein translocase TOM

International Nuclear Information System (INIS)

Mager, Frauke; Lintzel, Julia; Nussberger, Stephan; Sokolova, Lucie; Brutschy, Bernhard

2010-01-01

In the present work we applied a novel mass spectrometry method termed laser-induced liquid bead ion desorption mass spectrometry (LILBID-MS) to the outer mitochondrial membrane protein translocon TOM to analyze its subunit composition and stoichiometry. With TOM core complex, purified at high pH, we demonstrate that a TOM core complex of Neurospora crassa is composed of at least two Tom40 and Tom22 molecules, respectively, and more than five small Tom subunits between 5.5 and 6.4 kDa. We show that the multiprotein complex has a total molecular mass higher than 170 depending on the number of Tom5, Tom6 and Tom7 molecules bound.

LILBID-mass spectrometry of the mitochondrial preprotein translocase TOM

Science.gov (United States)

Mager, Frauke; Sokolova, Lucie; Lintzel, Julia; Brutschy, Bernhard; Nussberger, Stephan

2010-11-01

In the present work we applied a novel mass spectrometry method termed laser-induced liquid bead ion desorption mass spectrometry (LILBID-MS) to the outer mitochondrial membrane protein translocon TOM to analyze its subunit composition and stoichiometry. With TOM core complex, purified at high pH, we demonstrate that a TOM core complex of Neurospora crassa is composed of at least two Tom40 and Tom22 molecules, respectively, and more than five small Tom subunits between 5.5 and 6.4 kDa. We show that the multiprotein complex has a total molecular mass higher than 170 depending on the number of Tom5, Tom6 and Tom7 molecules bound.

Laser desorption mass spectrometry for biomolecule detection and its applications

Science.gov (United States)

Winston Chen, C. H.; Sammartano, L. J.; Isola, N. R.; Allman, S. L.

2001-08-01

During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications.

Laser desorption mass spectrometry for biomolecule detection and its applications

International Nuclear Information System (INIS)

Winston Chen, C.H.; Allman, S.L.; Sammartano, L.J.; Isola, N.R.

2001-01-01

During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications

Clinical review: improving the measurement of serum thyroglobulin with mass spectrometry.

Science.gov (United States)

Hoofnagle, Andrew N; Roth, Mara Y

2013-04-01

Serum thyroglobulin (Tg) measurements are central to the management of patients treated for differentiated thyroid carcinoma. For decades, Tg measurements have relied on methods that are subject to interference by commonly found substances in human serum and plasma, such as Tg autoantibodies. As a result, many patients need additional imaging studies to rule out cancer persistence or recurrence that could be avoided with more sensitive and specific testing methods. The aims of this review are to: 1) briefly review the interferences common to Tg immunoassays; 2) introduce readers to liquid chromatography-tandem mass spectrometry as a method for quantifying proteins in human serum/plasma; and 3) discuss the potential benefits and limitations of the method in the quantification of serum Tg. Mass spectrometric methods have traditionally lacked the sensitivity, robustness, and throughput to be useful clinical assays. These methods failed to meet the necessary clinical benchmarks due to the nature of the mass spectrometry workflow and instrumentation. Over the past few years, there have been major advances in reagents, automation, and instrumentation for the quantification of proteins using mass spectrometry. More recently, methods using mass spectrometry to detect and quantify Tg have been developed and are of sufficient quality to be used in the management of patients. Novel serum Tg assays that use mass spectrometry may avoid the issue of autoantibody interference and other problems with currently available immunoassays for Tg. Prospective studies are needed to fully understand the potential benefits of novel Tg assays to patients and care providers.

Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

Science.gov (United States)

Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

2013-11-01

In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

Elucidating rhizosphere processes by mass spectrometry - A review.

Science.gov (United States)

Rugova, Ariana; Puschenreiter, Markus; Koellensperger, Gunda; Hann, Stephan

2017-03-01

The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. Copyright © 2017 Elsevier B.V. All rights reserved.

The future of the accelerator mass spectrometry of rare long-lived radioactive isotopes

International Nuclear Information System (INIS)

Litherland, A.E.

1990-01-01

Accelerators, originally designed for nuclear physics, can be added to mass spectrometric apparatus to increase the sensitivity so that isotope ratios in the range 10 -12 to 10 -15 can be measured routinely. This significant improvement of high-sensitivity mass spectrometry has been called Accelerator Mass Spectrometry. The present article addresses the basic principles of accelerator mass spectrometry and some recent applications which show its versatility. In particular, it is noted that accelerator mass spectrometry could play an increasing role in the measurement of the levels of long lived radioactivities in the environment, including the actinides, which result from human activities such as the use of nuclear power. To fulfill this promise, continued research and development is necessary to provide ion sources, various types of heavy ion accelerators and peripheral magnetic and electric analysers. (N.K.)

Analytical capabilities of laser-probe mass spectrometry

International Nuclear Information System (INIS)

Kovalev, I.D.; Madsimov, G.A.; Suchkov, A.I.; Larin, N.V.

1978-01-01

The physical bases and quantitative analytical procedures of laser-probe mass spectrometry are considered in this review. A comparison is made of the capabilities of static and dynamic mass spectrometers. Techniques are studied for improving the analytical characteristics of laser-probe mass spectrometers. The advantages, for quantitative analysis, of the Q-switched mode over the normal pulse mode for lasers are: (a) the possibility of analysing metals, semiconductors and insulators without the use of standards; and (b) the possibility of layer-by-layer and local analysis. (Auth.)

Practical aspects and trends in analytical organic mass spectrometry

International Nuclear Information System (INIS)

Schlunegger, U.P.

1981-01-01

Proceeding from the fundamentals of mass spectrometry (MS), some more recent developments of analytical organic MS are shown in comparison with conventional MS. Sections are headed: the vacuum, production of ions in the mass spectrometer, ions in the analyzer of a mass spectrometer, general considerations, practice of modern MS: selected examples

SU-8 as a material for lab-on-a-chip-based mass spectrometry.

Science.gov (United States)

Arscott, Steve

2014-10-07

This short review focuses on the application of SU-8 for the microchip-based approach to the miniaturization of mass spectrometry. Chip-based mass spectrometry will make the technology commonplace and bring benefits such as lower costs and autonomy. The chip-based miniaturization of mass spectrometry necessitates the use of new materials which are compatible with top-down fabrication involving both planar and non-planar processes. In this context, SU-8 is a very versatile epoxy-based, negative tone resist which is sensitive to ultraviolet radiation, X-rays and electron beam exposure. It has a very wide thickness range, from nanometres to millimetres, enabling the formation of mechanically rigid, very high aspect ratio, vertical, narrow width structures required to form microfluidic slots and channels for laboratory-on-a-chip design. It is also relatively chemically resistant and biologically compatible in terms of the liquid solutions used for mass spectrometry. This review looks at the impact and potential of SU-8 on the different parts of chip-based mass spectrometry - pre-treatment, ionization processes, and ion sorting and detection.

Ammonia IRMS-TPD measurements and DFT calculation on acidic hydroxyl groups in CHA-type zeolites.

Science.gov (United States)

Suzuki, Katsuki; Sastre, German; Katada, Naonobu; Niwa, Miki

2007-12-07

Brønsted acidity of H-chabazite (CHA) zeolites (Si : Al(2) = 4.2) was investigated by means of ammonia infrared-mass spectrometry/temperature-programmed desorption (IRMS-TPD) methods and density functional calculations. Four IR bands were observed at 3644, 3616, 3575 and 3538 cm(-1), and they were ascribable to the acidic OH groups on four nonequivalent oxygen sites in the CHA structure. The absorption band at 3538 cm(-1) was attributed to the O(4)H in the 6-membered ring (MR), and ammonia adsorption energy (DeltaU) of this OH group was the lowest among the 4 kinds of OH groups. The other 3 bands were assigned to the acidic OH groups in 8MR. It was observed that the DeltaU in 8 and 6MR were 131 (+/-3) and 101 kJ mol(-1), respectively. On the other hand, the density functional theory (DFT) calculations within periodic boundary conditions yielded the adsorption energies on these OH groups in 8 and 6MR to be ca. 130 and 110 kJ mol(-1), respectively, in good agreement with the experimentally-observed values.

Laser sputter neutral mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

King, B.V.; Clarke, M.; Hu, H.; Betz [Newcastle Univ., NSW (Australia). Dept. of Physics

1993-12-31

Laser sputter neutral mass spectrometry (LSNMS) is an emerging technique for highly sensitive surface analysis. In this technique a target is bombarded with a pulsed beam of keV ions. The sputtered particles are intercepted by a high intensity pulsed laser beam above the surface and ionised with almost 100% efficiency. The photions may then be mass analysed using a quadrupole or, more commonly, using time of flight (TOF) techniques. In this method photoions are extracted from the ionisation region, accelerated to a known energy E{sub o} and strike a channelplate detector a distance `d` away. The flight time `t` of the photoions is then related to their mass by `d` {radical}m / {radical} 2E{sub o} so measurement of `t` allows mass spectra to be obtained. It is found that LSNMS is an emerging technique of great sensitivity and flexibility, useful for both applied analysis and to investigate basic sputtering processes. 4 refs., 3 figs.

Laser sputter neutral mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

King, B V; Clarke, M; Hu, H; Betz, [Newcastle Univ., NSW (Australia). Dept. of Physics

1994-12-31

Laser sputter neutral mass spectrometry (LSNMS) is an emerging technique for highly sensitive surface analysis. In this technique a target is bombarded with a pulsed beam of keV ions. The sputtered particles are intercepted by a high intensity pulsed laser beam above the surface and ionised with almost 100% efficiency. The photions may then be mass analysed using a quadrupole or, more commonly, using time of flight (TOF) techniques. In this method photoions are extracted from the ionisation region, accelerated to a known energy E{sub o} and strike a channelplate detector a distance `d` away. The flight time `t` of the photoions is then related to their mass by `d` {radical}m / {radical} 2E{sub o} so measurement of `t` allows mass spectra to be obtained. It is found that LSNMS is an emerging technique of great sensitivity and flexibility, useful for both applied analysis and to investigate basic sputtering processes. 4 refs., 3 figs.

[Simultaneous determination of delta13C values of glycerol and ethanol in wine by liquid chromatography coupled with isotope ratio mass spectrometry].

Science.gov (United States)

Li, Xuemin; Jia, Guangqun; Cao, Yanzhong; Zhang, Jinjie; Wang, Lei; Sun, Huiyuan

2013-12-01

A novel procedure was established for the characterization of delta13C values of glycerol and ethanol in wine by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing the separation of glycerol and ethanol from wine matrix were optimized. The precision and accuracy of the proposed method were 0.15 per thousand to 0.26 per thousand and 0.11 per thousand to 0.28 per thousand, respectively. The results obtained for 40 wine samples displayed that the delta13C value of glycerol ranged from--26.87 per thousand to--32.96 per thousand and that of ethanol ranged from--24.06 per thousand to--28.29 per thousand. Close correlations (R = 0.82) were obtained between the delta13C values of glycerol and ethanol. The proposed method didn't need complex sample treatment, and the delta13C values of glycerol and ethanol in wine can be simultaneously determined, thus improving the method in terms of simplicity and speed compared with traditional methods.

Radiocarbon accelerator mass spectrometry: background and contamination

International Nuclear Information System (INIS)

Beukens, R.P.

1993-01-01

Since the advent of radiocarbon accelerator mass spectrometry (AMS) many studies have been conducted to understand the background from mass spectrometric processes and the origins of contamination associated with the ion source and sample preparation. By studying the individual contributions a better understanding of these processes has been obtained and it has been demonstrated that it is possible to date samples reliably up to 60 000 BP. (orig.)

Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by 13C nuclear magnetic resonance spectrometry

International Nuclear Information System (INIS)

Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J.; Remaud, Gérald S.

2015-01-01

Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by 13 C NMR (irm- 13 C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. - Highlights: • Position-Specific Isotope Analysis (PSIA) by 13 C NMR spectrometry. • PSIA on isotope fractionation during several vaporization processes. • PSIA for isotope profiling in environment pollutants. • Intramolecular 13 C reveal normal and inverse effects, bulk values being unchanged. - PSIA in pollutants during evaporation processes shows more detailed information for discerning the nature of the process involved than does bulk isotope measurements

Surface analysis of lipids by mass spectrometry: more than just imaging.

Science.gov (United States)

Ellis, Shane R; Brown, Simon H; In Het Panhuis, Marc; Blanksby, Stephen J; Mitchell, Todd W

2013-10-01

Mass spectrometry is now an indispensable tool for lipid analysis and is arguably the driving force in the renaissance of lipid research. In its various forms, mass spectrometry is uniquely capable of resolving the extensive compositional and structural diversity of lipids in biological systems. Furthermore, it provides the ability to accurately quantify molecular-level changes in lipid populations associated with changes in metabolism and environment; bringing lipid science to the "omics" age. The recent explosion of mass spectrometry-based surface analysis techniques is fuelling further expansion of the lipidomics field. This is evidenced by the numerous papers published on the subject of mass spectrometric imaging of lipids in recent years. While imaging mass spectrometry provides new and exciting possibilities, it is but one of the many opportunities direct surface analysis offers the lipid researcher. In this review we describe the current state-of-the-art in the direct surface analysis of lipids with a focus on tissue sections, intact cells and thin-layer chromatography substrates. The suitability of these different approaches towards analysis of the major lipid classes along with their current and potential applications in the field of lipid analysis are evaluated. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Analytical strategies in mass spectrometry-based phosphoproteomics

DEFF Research Database (Denmark)

Rosenqvist, Heidi; Ye, Juanying; Jensen, Ole N

2011-01-01

then discuss various tandem mass spectrometry approaches for phosphopeptide sequencing and quantification, and we consider aspects of phosphoproteome data analysis and interpretation. Efficient integration of these stages of phosphoproteome analysis is highly important to ensure a successful outcome of large...

Multi-Reflection Time-of-Flight Mass Separation and Spectrometry

CERN Document Server

Kreim, Susanne; Wolf, R N

2014-01-01

The mass of a nucleus is one of its most fundamental ground-state properties and reveals the strength of nuclear binding. Investigating the binding energy of nuclei with respect to the number of protons and neutrons in a nucleus is important for advancing nuclear theory and increases our understanding of nucleosynthesis in supernovae and neutron stars. Precision mass measurements on radioactive nuclides belong to the state-of-the-art techniques [1, 2]. Presently, four complementary techniques are applied: isochronous and Schottky mass spectrometry in storage rings (IMS and SMS, respectively), magnetic-rigidity time-of-flight (TOF-ρ) measurements, and Penning-trap mass spectrometry (PTMS). With measurement cycles in the sub-ms range, IMS and TOF-Bρ MS are well suited for very short-lived species while offering moderate relative precision on the level of 10−6. A higher precision is achieved by SMS but with the need for measurement times on the order of several seconds. As soon as masses with a relative prec...

High efficiency nebulization for helium inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Jorabchi, Kaveh; McCormick, Ryan; Levine, Jonathan A.; Liu Huiying; Nam, S.-H.; Montaser, Akbar

2006-01-01

A pneumatically-driven, high efficiency nebulizer is explored for helium inductively coupled plasma mass spectrometry. The aerosol characteristics and analyte transport efficiencies of the high efficiency nebulizer for nebulization with helium are measured and compared to the results obtained with argon. Analytical performance indices of the helium inductively coupled plasma mass spectrometry are evaluated in terms of detection limits and precision. The helium inductively coupled plasma mass spectrometry detection limits obtained with the high efficiency nebulizer at 200 μL/min are higher than those achieved with the ultrasonic nebulizer consuming 2 mL/min solution, however, precision is generally better with high efficiency nebulizer (1-4% vs. 3-8% with ultrasonic nebulizer). Detection limits with the high efficiency nebulizer at 200 μL/min solution uptake rate approach those using ultrasonic nebulizer upon efficient desolvation with a heated spray chamber followed by a Peltier-cooled multipass condenser

Multi photon ionization mass spectrometry of carbamate pesticides, herbicides and fungicides

International Nuclear Information System (INIS)

Grun, Carsten; Koenig, Marcelle; Grotemeyer, Juergen

2001-01-01

Pesticides and herbicides are useful for a wide range of applications today. The determination of these substances either in the pure form or in complex matrices is of high analytical interest. Especially since these substances can by found in every day products. The combination of multi photon ionization (MUPI) and time of flight laser mass spectrometry may be a powerful tool for achieving fast well interpretable mass spectra for analytical purposes. In this paper we will discuss the mass spectra of several pesticides and herbicides accessed by MUPI-time-of-flight mass spectrometry. The influence of the laser pulse duration on the mass spectra are discussed

Current medical research with the application of coupled techniques with mass spectrometry

OpenAIRE

Ka?u?na-Czapli?ska, Joanna

2011-01-01

Summary The most effective methods of analysis of organic compounds in biological fluids are coupled chromatographic techniques. Capillary gas chromatography/mass spectrometry (GC-MS) allows the most efficient separation, identification and quantification of volatile metabolites in biological fluids. Liquid chromatography-mass spectrometry (LC-MS) is especially suitable for the analysis of non-volatile and/or thermally unstable compounds. A major drawback of liquid chromatography-mass spectro...

Mass Spectrometry Applications for Toxicology

OpenAIRE

Mbughuni, Michael M.; Jannetto, Paul J.; Langman, Loralie J.

2016-01-01

Toxicology is a multidisciplinary study of poisons, aimed to correlate the quantitative and qualitative relationships between poisons and their physiological and behavioural effects in living systems. Other key aspects of toxicology focus on elucidation of the mechanisms of action of poisons and development of remedies and treatment plans for associated toxic effects. In these endeavours, Mass spectrometry (MS) has become a powerful analytical technique with a wide range of application used i...

Space Applications of Mass Spectrometry. Chapter 31

Science.gov (United States)

Hoffman, John H.; Griffin, Timothy P.; Limero, Thomas; Arkin, C. Richard

2010-01-01

Mass spectrometers have been involved in essentially all aspects of space exploration. This chapter outlines some of these many uses. Mass spectrometers have not only helped to expand our knowledge and understanding of the world and solar system around us, they have helped to put man safely in space and expand our frontier. Mass spectrometry continues to prove to be a very reliable, robust, and flexible analytical instrument, ensuring that its use will continue to help aid our investigation of the universe and this small planet that we call home.

Identification of bacteria using mass spectrometry techniques

Czech Academy of Sciences Publication Activity Database

Krásný, Lukáš; Hynek, R.; Hochel, I.

2013-01-01

Roč. 353, NOV 2013 (2013), s. 67-79 ISSN 1387-3806 R&D Projects: GA ČR GAP503/10/0664 Institutional support: RVO:61388971 Keywords : Mass spectrometry * Bacteria * Identification Subject RIV: EE - Microbiology, Virology Impact factor: 2.227, year: 2013

Mass spectrometry in structural biology and biophysics architecture, dynamics, and interaction of biomolecules

CERN Document Server

Kaltashov, Igor A; Desiderio, Dominic M; Nibbering, Nico M

2012-01-01

The definitive guide to mass spectrometry techniques in biology and biophysics The use of mass spectrometry (MS) to study the architecture and dynamics of proteins is increasingly common within the biophysical community, and Mass Spectrometry in Structural Biology and Biophysics: Architecture, Dynamics, and Interaction of Biomolecules, Second Edition provides readers with detailed, systematic coverage of the current state of the art. Offering an unrivalled overview of modern MS-based armamentarium that can be used to solve the most challenging problems in biophysics, structural biol

imzML: Imaging Mass Spectrometry Markup Language: A common data format for mass spectrometry imaging.

Science.gov (United States)

Römpp, Andreas; Schramm, Thorsten; Hester, Alfons; Klinkert, Ivo; Both, Jean-Pierre; Heeren, Ron M A; Stöckli, Markus; Spengler, Bernhard

2011-01-01

Imaging mass spectrometry is the method of scanning a sample of interest and generating an "image" of the intensity distribution of a specific analyte. The data sets consist of a large number of mass spectra which are usually acquired with identical settings. Existing data formats are not sufficient to describe an MS imaging experiment completely. The data format imzML was developed to allow the flexible and efficient exchange of MS imaging data between different instruments and data analysis software.For this purpose, the MS imaging data is divided in two separate files. The mass spectral data is stored in a binary file to ensure efficient storage. All metadata (e.g., instrumental parameters, sample details) are stored in an XML file which is based on the standard data format mzML developed by HUPO-PSI. The original mzML controlled vocabulary was extended to include specific parameters of imaging mass spectrometry (such as x/y position and spatial resolution). The two files (XML and binary) are connected by offset values in the XML file and are unambiguously linked by a universally unique identifier. The resulting datasets are comparable in size to the raw data and the separate metadata file allows flexible handling of large datasets.Several imaging MS software tools already support imzML. This allows choosing from a (growing) number of processing tools. One is no longer limited to proprietary software, but is able to use the processing software which is best suited for a specific question or application. On the other hand, measurements from different instruments can be compared within one software application using identical settings for data processing. All necessary information for evaluating and implementing imzML can be found at http://www.imzML.org .

Mass Determination of Entire Amyloid Fibrils by Using Mass Spectrometry.

Science.gov (United States)

Doussineau, Tristan; Mathevon, Carole; Altamura, Lucie; Vendrely, Charlotte; Dugourd, Philippe; Forge, Vincent; Antoine, Rodolphe

2016-02-12

Amyloid fibrils are self-assembled protein structures with important roles in biology (either pathogenic or physiological), and are attracting increasing interest in nanotechnology. However, because of their high aspect ratio and the presence of some polymorphism, that is, the possibility to adopt various structures, their characterization is challenging and basic information such as their mass is unknown. Here we show that charge-detection mass spectrometry, recently developed for large self-assembled systems such as viruses, provides such information in a straightforward manner. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Sample preparation and bioanalysis in mass spectrometry].

Science.gov (United States)

Bourgogne, Emmanuel; Wagner, Michel

2015-01-01

The quantitative analysis of compounds of clinical interest of low molecular weight (sample preparation. Sample preparation is a crucial part of chemical/biological analysis and in a sense is considered the bottleneck of the whole analytical process. The main objectives of sample preparation are the removal of potential interferences, analyte preconcentration, and converting (if needed) the analyte into a more suitable form for detection or separation. Without chromatographic separation, endogenous compounds, co-eluted products may affect a quantitative method in mass spectrometry performance. This work focuses on three distinct parts. First, quantitative bioanalysis will be defined, different matrices and sample preparation techniques currently used in bioanalysis by mass spectrometry of/for small molecules of clinical interest in biological fluids. In a second step the goals of sample preparation will be described. Finally, in a third step, sample preparation strategies will be made either directly ("dilute and shoot") or after precipitation.

Direct analysis of δ13C and concentration of dissolved organic carbon (DOC) in environmental samples by TOC-IRMS

Science.gov (United States)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2014-05-01

Dissolved organic carbon (DOC) plays an important role in carbon cycling in terrestrial and aquatic systems. Stable isotope analysis (delta 13C) of DOC could provide valuable insights in its origin, fluxes and environmental fate. Precise and routine analysis of delta 13C and DOC concentration are therefore highly desirable. A promising, new system has been developed for this purpose, linking a high-temperature combustion TOC analyzer trough an interface with a continuous flow isotope ratio mass spectrometer (Elementar group, Hanau, Germany). This TOC-IRMS system enables simultaneous stable isotope (bulk delta 13C) and concentration analysis of DOC, with high oxidation efficiency by high-temperature combustion for complex mixtures as natural DOC. To give delta 13C analysis by TOC-IRMS the necessary impulse for broad-scale application, we present a detailed evaluation of its analytical performance for realistic and challenging conditions inclusive low DOC concentrations and environmental samples. High precision (standard deviation, SD predominantly TOC-IRMS and conventional EA-IRMS) were achieved by TOC-IRMS for a broad diversity of DOC solutions. This precision is comparable or even slightly better than that typically reported for EA-IRMS systems, and improves previous techniques for δ13C analysis of DOC. Simultaneously, very good precision was obtained for DOC concentration measurements. Assessment of natural abundance and slightly 13C enriched DOC, a wide range of concentrations (0.2-150 mgC/L) and injection volumes (0.05-3 ml), demonstrated good analytical performance with negligible memory effects, no concentration/volume effects and a wide linearity. Low DOC concentrations (TOC-IRMS was successfully applied to analyze DOC from diverse terrestrial, freshwater and marine environments (SD TOC-IRMS performs fast and reliable analysis of DOC concentration and δ13C in aqueous samples, without any pre-concentration/freeze-drying. Flexible usage is highlighted by

Simulation of Two Dimensional Electrophoresis and Tandem Mass Spectrometry for Teaching Proteomics

Science.gov (United States)

Fisher, Amanda; Sekera, Emily; Payne, Jill; Craig, Paul

2012-01-01

In proteomics, complex mixtures of proteins are separated (usually by chromatography or electrophoresis) and identified by mass spectrometry. We have created 2DE Tandem MS, a computer program designed for use in the biochemistry, proteomics, or bioinformatics classroom. It contains two simulations--2D electrophoresis and tandem mass spectrometry.…

Mapping posttranscriptional modifications in 5S ribosomal RNA by MALDI mass spectrometry.

OpenAIRE

Kirpekar, F; Douthwaite, S; Roepstorff, P

2000-01-01

We present a method to screen RNA for posttranscriptional modifications based on Matrix Assisted Laser Desorption/Ionization mass spectrometry (MALDI-MS). After the RNA is digested to completion with a nucleotide-specific RNase, the fragments are analyzed by mass spectrometry. A comparison of the observed mass data with the data predicted from the gene sequence identifies fragments harboring modified nucleotides. Fragments larger than dinucleotides were valuable for the identification of post...

Direct Analysis of Large Living Organism by Megavolt Electrostatic Ionization Mass Spectrometry

Science.gov (United States)

Ng, Kwan-Ming; Tang, Ho-Wai; Man, Sin-Heng; Mak, Pui-Yuk; Choi, Yi-Ching; Wong, Melody Yee-Man

2014-09-01

A new ambient ionization method allowing the direct chemical analysis of living human body by mass spectrometry (MS) was developed. This MS method, namely Megavolt Electrostatic Ionization Mass Spectrometry, is based on electrostatic charging of a living individual to megavolt (MV) potential, illicit drugs, and explosives on skin/glove, flammable solvent on cloth/tissue paper, and volatile food substances in breath were readily ionized and detected by a mass spectrometer.

Mass Spectrometry Parameters Optimization for the 46 Multiclass Pesticides Determination in Strawberries with Gas Chromatography Ion-Trap Tandem Mass Spectrometry

Science.gov (United States)

Fernandes, Virgínia C.; Vera, Jose L.; Domingues, Valentina F.; Silva, Luís M. S.; Mateus, Nuno; Delerue-Matos, Cristina

2012-12-01

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET), maximum excitation energy or " q" value (q), and isolation mass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit. Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

The combined measurement of uranium by alpha spectrometry and secondary ion mass spectrometry (SIMS)

International Nuclear Information System (INIS)

Harvan, D.

2009-01-01

The aim of thesis was to found the dependence between radiometric method - alpha spectrometry and surface sensitive method - Secondary Ion Mass Spectrometry (SIMS). Uranium or naturally occurring uranium isotopes were studied. Samples (high polished stainless steel discs) with uranium isotopes were prepared by electrodeposition. Samples were measured by alpha spectrometry after electrodeposition and treatment. It gives surface activities. Weights, as well as surface's weights of uranium isotopes were calculated from their activities, After alpha spectrometry samples were analyzed by TOF-SIMS IV instrument in International Laser Centre in Bratislava. By the SIMS analysis intensities of uranium-238 were obtained. The interpretation of SIMS intensities vs. surface activity, or surface's weights of uranium isotopes indicates the possibility to use SIMS in quantitative analysis of surface contamination by uranium isotopes, especially 238 U. (author)

Water stable isotope measurements of Antarctic samples by means of IRMS and WS-CRDS techniques

Science.gov (United States)

Michelini, Marzia; Bonazza, Mattia; Braida, Martina; Flora, Onelio; Dreossi, Giuliano; Stenni, Barbara

2010-05-01

In the last years in the scientific community there has been an increasing interest for the application of stable isotope techniques to several environmental problems such as drinking water safeguarding, groundwater management, climate change, soils and paleoclimate studies etc. For example, the water stable isotopes, being natural tracers of the hydrological cycle, have been extensively used as tools to characterize regional aquifers and to reconstruct past temperature changes from polar ice cores. Here the need for improvements in analytical techniques: the high request for information calls for technologies that can offer a great quantity of analyses in short times and with low costs. Furthermore, sometimes it is difficult to obtain big amount of samples (as is the case for Antarctic ice cores or interstitial water) preventing the possibility to replicate the analyses. Here, we present oxygen and hydrogen measurements performed on water samples covering a big range of isotopic values (from very negative antarctic precipitation to mid-latitude precipitation values) carried out with both the conventional Isotope Ratio Mass Spectrometry (IRMS) technique and with a new method based on laser absorption techniques, the Wavelenght Scanned Cavity Ringdown Spectroscopy (WS-CRDS). This study is focusing on improving the precision of the measurements carried out with WS-CRDS in order to extensively apply this method to Antarctic ice core paleoclimate studies. The WS-CRDS is a variation of the CRDS developed in 1988 by O'Keef and Deacon. In CRDS a pulse of light goes through a box with high reflective inner surfaces; when there is no sample in the box the light beam doesn't find any obstacle in its path, but the reflectivity of the walls is not perfect so eventually there will be an absorption of the light beam; when the sample is injected in the box there is absorption and the difference between the time of absorption without and with sample is proportional to the quantity

Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry

International Nuclear Information System (INIS)

Laskin, Julia; Futrell, Jean H.

2003-01-01

In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

'Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry'

International Nuclear Information System (INIS)

Laskin, Julia; Futrell, Jean H.

2003-01-01

In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

Four decades of joy in mass spectrometry

NARCIS (Netherlands)

Nibbering, N.M.M.

2006-01-01

Tremendous developments in mass spectrometry have taken place in the last 40 years. This holds for both the science and the instrumental revolutions in this field. In chemistry the research was heavily focused on organic molecules that upon electron ionization fragmented via complex mechanistic

Inductively coupled plasma- mass spectrometry. Chapter 13

International Nuclear Information System (INIS)

Mahalingam, T.R.

1997-01-01

Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) is a new technique for elemental and isotopic analysis which is currently attracting a great deal of interest. This relatively new technique has found wide applications in different fields of research viz., nuclear, geological, biological and environmental sciences

Determination of {sup 135}Cs by accelerator mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

MacDonald, C.M.; Charles, C.R.J. [Andre. E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Zhao, X.-L.; Kieser, W.E. [Andre. E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Cornett, R.J. [Andre. E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Litherland, A.E. [IsoTrace Laboratory, University of Toronto, 60 St. George St., Toronto, ON M5S 1A7 (Canada)

2015-10-15

The ratio of anthropogenic {sup 135}Cs and {sup 137}Cs isotopes is characteristic of a uranium fission source. This research evaluates the technique of isotope dilution (yield tracing) for the purpose of quantifying {sup 135}Cs by accelerator mass spectrometry with on-line isobar separation. Interferences from Ba, Zn{sub 2}, and isotopes of equal mass to charge ratios were successfully suppressed. However, some sample crosstalk from source contamination remains. The transmission and di-fluoride ionization efficiencies of Cs isotopes were found to be 8 × 10{sup −3} and 1.7 × 10{sup −7} respectively. This quantification of {sup 135}Cs using yield tracing by accelerator mass spectrometry shows promise for future environmental sample analysis once the issues of sample crosstalk and low efficiency can be resolved.

Laser mass spectrometry of chemical warfare agents using ultrashort laser pulses

International Nuclear Information System (INIS)

Weickhardt, C.; Grun, C.; Grotemeyer, J.

1998-01-01

Fast relaxation processes in excited molecules such as IC, ISC, and fragmentation are observed in many environmentally and technically relevant substances. They cause severe problems to resonance ionization mass spectrometry because they reduce the ionization yield and lead to mass spectra which do not allow the identification of the compound. By the use of ultrashort laser pulses these problems can be overcome and the advantages of REMPI over conventional ionization techniques in mass spectrometry can be regained. This is demonstrated using soil samples contaminated with a chemical warfare agent

Mass spectrometry in nuclear technology - a review of application of thermal ionization mass spectrometry in fuel reprocessing plants. PD-7-1

International Nuclear Information System (INIS)

Dakshinamoorthy, A.

2007-01-01

Mass spectrometry finds the widespread application in nuclear science and technology due to the fact that it can be employed for isotope composition measurements of different elements of interest and also concentration measurements of these elements using isotope dilution techniques. Thermal ionization mass spectrometer (TIMS), Inductively coupled plasma mass spectrometer (ICP-MS) and gas chromatography mass spectrometer (GC-MS) are the different types of mass spectrometers used in nuclear industry for the analyses of isotope composition of special nuclear material, trace impurities in nuclear fuels and components and characterization of various solvents respectively. Among them, TIMS plays a vital role in the nuclear fuel cycle in determining precisely the isotope composition of uranium, plutonium, D/H ratio in heavy water etc. TIMS is an indispensable analytical tool for nuclear material accounting at the input stage of a reprocessing plant by carrying out precise and accurate concentration measurement of plutonium and uranium by isotope dilution mass spectrometry (IDMS). It is the only accepted measurement technique for the purpose because of its high precision, better sensitivity and no quantitative separation is needed. The isotope abundance measurements of uranium and plutonium at this point are also useful for burn-up studies and isotope correlations. Mass spectrometric analysis of uranium and plutonium is also required for nuclear data measurements and calibrating other chemical methods

Polymer and Additive Mass Spectrometry Literature Review

Energy Technology Data Exchange (ETDEWEB)

Shear, Trevor Allan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-06-06

The use of mass spectrometry in fields related to polymers has increased significantly over the past three decades and will be explored in this literature review. The importance of this technique is highlighted when exploring how polymers degrade, verifying purchased materials, and as internal requirements change. The primary focus will be on four ionization techniques and the triple quadrupole and quadrupole / time-of-flight mass spectrometers. The advantages and limitations of each will also be explored.

Recent applications of mass spectrometry in forensic toxicology

Science.gov (United States)

Foltz, Rodger L.

1992-09-01

This review encompasses applications of mass spectrometry reported during the years 1989, 1990 and 1991 for the analysis of cannabinoids, cocaine, opiates, amphetamines, lysergic acid diethylamide (LSD), and their metabolites in physiological specimens.

Radiocarbon positive-ion mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Freeman, Stewart P.H.T.; Shanks, Richard P. [Scottish Universities Environmental Research Centre (SUERC), Scottish Enterprise Technology Park, East Kilbride G75 0QF (United Kingdom); Donzel, Xavier; Gaubert, Gabriel [Pantechnik S.A., 13 Rue de la Résistance, 14400 Bayeux (France)

2015-10-15

Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

Radiocarbon positive-ion mass spectrometry

International Nuclear Information System (INIS)

Freeman, Stewart P.H.T.; Shanks, Richard P.; Donzel, Xavier; Gaubert, Gabriel

2015-01-01

Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

Mass Spectrometry for Large Undergraduate Laboratory Sections

Science.gov (United States)

Illies, A.; Shevlin, P. B.; Childers, G.; Peschke, M.; Tsai, J.

1995-08-01

Mass spectrometry is routinely covered in undergraduate organic chemistry courses and a number of valuable laboratory experiments featuring its use have been discussed (1-7). Although such experiments work well at institutions with limited laboratory enrollments, we typically teach laboratories with enrollments of 160 or more in which it is difficult to allow each student to carry out a meaningful "hands on" mass spectrometry experiment. Since we feel that some practical experience with this technique is important, we have designed a simple gas chromatography-mass spectrometry (gc/ms) exercise that allows each student to analyze the products of a simple synthesis that they have performed. The exercise starts with the microscale SN2 synthesis of 1-bromobutane from 1-butanol as described by Williamson (8). The students complete the synthesis and place one drop of the distilled product in a screw capped vial. The vials are then sealed, labeled with the students name and taken to the mass spectrometry laboratory by a teaching assistant. Students are instructed to sign up for a 20-min block of time over the next few days in order to analyze their sample. When the student arrives at the laboratory, he or she adds 1 ml CH2Cl2 to the sample and injects 0.3 microliters of the solution into the gas chromatograph. The samples typically contain the 1-butanol starting material and the 1-bromobutane product along with traces of dibutyl ether. The figure shows a mass chromatogram along with the mass spectra of the starting material and product from an actual student run. For this analysis to be applicable to large numbers of students, the gc separation must be as rapid as possible. We have been able to analyze each sample in 6 minutes on a 30 m DB-5 capillary column with the following temperature program: 70 oC for 1 min, 70-80 oC at 10 oC/min, 86-140 oC at 67.5 oC/min, 140-210 oC at 70 oC/min, and 210 oC for 1 min. A mass range of 20-200 amu is scanned with a solvent delay of 2

Can laser-ionisation time-of-flight mass spectrometry be a promising alternative to laser ablation/inductively-coupled plasma mass spectrometry and glow discharge mass spectrometry for the elemental analysis of solids?

NARCIS (Netherlands)

Sysoev, AA; Sysoev, AA

2002-01-01

At the beginning of the age of laser-ionisation mass spectrometry (LIMS) increasing numbers of publications were observed. However, later the method began to run into obstacles associated with poor reproducibility of analysis and large variations in elemental sensitivities so that the wide interest

δ15N measurement of organic and inorganic substances by EA-IRMS: a speciation-dependent procedure.

Science.gov (United States)

Gentile, Natacha; Rossi, Michel J; Delémont, Olivier; Siegwolf, Rolf T W

2013-01-01

Little attention has been paid so far to the influence of the chemical nature of the substance when measuring δ(15)N by elemental analysis (EA)-isotope ratio mass spectrometry (IRMS). Although the bulk nitrogen isotope analysis of organic material is not to be questioned, literature from different disciplines using IRMS provides hints that the quantitative conversion of nitrate into nitrogen presents difficulties. We observed abnormal series of δ(15)N values of laboratory standards and nitrates. These unexpected results were shown to be related to the tailing of the nitrogen peak of nitrate-containing compounds. A series of experiments were set up to investigate the cause of this phenomenon, using ammonium nitrate (NH(4)NO(3)) and potassium nitrate (KNO(3)) samples, two organic laboratory standards as well as the international secondary reference materials IAEA-N1, IAEA-N2-two ammonium sulphates [(NH(4))(2)SO(4)]-and IAEA-NO-3, a potassium nitrate. In experiment 1, we used graphite and vanadium pentoxide (V(2)O(5)) as additives to observe if they could enhance the decomposition (combustion) of nitrates. In experiment 2, we tested another elemental analyser configuration including an additional section of reduced copper in order to see whether or not the tailing could originate from an incomplete reduction process. Finally, we modified several parameters of the method and observed their influence on the peak shape, δ(15)N value and nitrogen content in weight percent of nitrogen of the target substances. We found the best results using mere thermal decomposition in helium, under exclusion of any oxygen. We show that the analytical procedure used for organic samples should not be used for nitrates because of their different chemical nature. We present the best performance given one set of sample introduction parameters for the analysis of nitrates, as well as for the ammonium sulphate IAEA-N1 and IAEA-N2 reference materials. We discuss these results considering the

Cortisol production rates measured by liquid chromatography/mass spectrometry

International Nuclear Information System (INIS)

Esteban, N.V.; Yergey, A.L.

1990-01-01

Cortisol production rates (FPRs) in physiologic and pathologic states in humans have been investigated over the past 30 years. However, there has been conflicting evidence concerning the validity of the currently accepted value of FPRs in humans (12 to 15 mg/m2/d) as determined by radiotracer methodology. The present study reviews previous methods proposed for the measurement of FPRs in humans and discusses the applications of the first method for the direct determination of 24-hour plasma FPRs during continuous administration of a stable isotope, using a thermospray high-pressure liquid chromatography-mass spectrometry technique. The technique is fast, sensitive, and, unlike gas chromatography-mass spectrometry methods, does not require derivatization, allowing on-line detection and quantification of plasma cortisol after a simple extraction procedure. The results of determination of plasma FPRs by stable tracer/mass spectrometry are directly in units of mass/time and, unlike radiotracer methods, are independent of any determination of volume of distribution or cortisol concentration. Our methodology offers distinct advantages over radiotracer techniques in simplicity and reliability since only single measurements of isotope ratios are required. The technique was validated in adrenalectomized patients. Circadian variations in daily FRPs were observed in normal volunteers, and, to date, results suggest a lower FRP in normal children and adults than previously believed. 88 references

Measurement of organic carbon stable isotope composition of different soil types by EA-IRMS system

International Nuclear Information System (INIS)

Qi Biao; Ding Lingling; Cui Jiehua; Wang Yanhong

2009-01-01

Element analyzer-isotope ratio mass spectrometers (EA-IRMS) is a rapid and precise method for measuring stable carbon isotope. Pure CO 2 reference gas was calibrated via international standard-Urea, and the δ 13 C us PDB value of pure CO 2 is (-29.523 ± 0.0181)%. Stability and linearity of the EA-IRMS system, precision of δ 13 C measurement for samples were tested through experimental comparison. Moreover, determination method of organic carbon stable isotope in soil was based on the system. The EA-IRMS system had well linearity when ion intensity ranged from 1.0 to 7.0V, and it excelled the total linearity when the ion intensity was from 1.5 to 5.0V, and the accurate result of δ 13 C for sample analysis could be obtained with precision of 0.015%. If carbon content in sample is more than 5μg, the requirement for analyzing accurate result of δ 13 C could be achieved. The organic carbon stable isotope was measured in 18 different types soil samples, the average natural abundance of 13 C was 1.082%, and the organic carbon stable isotope composition was significantly different among different type soils. (authors)

A theory of stable-isotope dilution mass spectrometry

International Nuclear Information System (INIS)

Pickup, J.F.; McPherson, C.K.

1977-01-01

In order to perform quantitative analysis using stable isotope dilution with mass spectrometry, an equation is derived which describes the relationship between the relative proportions of natural and labelled material and measured isotope ratios

Analysis of hydroxamate siderophores in soil solution using liquid chromatography with mass spectrometry and tandem mass spectrometry with on-line sample preconcentration.

Science.gov (United States)

Olofsson, Madelen A; Bylund, Dan

2015-10-01

A liquid chromatography with electrospray ionization mass spectrometry method was developed to quantitatively and qualitatively analyze 13 hydroxamate siderophores (ferrichrome, ferrirubin, ferrirhodin, ferrichrysin, ferricrocin, ferrioxamine B, D1 , E and G, neocoprogen I and II, coprogen and triacetylfusarinine C). Samples were preconcentrated on-line by a switch-valve setup prior to analyte separation on a Kinetex C18 column. Gradient elution was performed using a mixture of an ammonium formate buffer and acetonitrile. Total analysis time including column conditioning was 20.5 min. Analytes were fragmented by applying collision-induced dissociation, enabling structural identification by tandem mass spectrometry. Limit of detection values for the selected ion monitoring method ranged from 71 pM to 1.5 nM with corresponding values of two to nine times higher for the multiple reaction monitoring method. The liquid chromatography with mass spectrometry method resulted in a robust and sensitive quantification of hydroxamate siderophores as indicated by retention time stability, linearity, sensitivity, precision and recovery. The analytical error of the methods, assessed through random-order, duplicate analysis of soil samples extracted with a mixture of 10 mM phosphate buffer and methanol, appears negligible in relation to between-sample variations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

Science.gov (United States)

Thomas, Freddy; Jamin, Eric

2009-09-01

An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and

2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: International collaborative study report

International Nuclear Information System (INIS)

Thomas, Freddy; Jamin, Eric

2009-01-01

An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2 H/ 1 H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13 C/ 12 C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18 O/ 16 O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring δ 13 C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per mille , and the average reproducibility (R) was 0.91 per mille . As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2 H/ 1 H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (δ 13 C and δ 18 O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring δ 18 O were found to be similar to the values previously obtained for other methods applied to wine and

Resonance ionization mass spectrometry system for measurement of environmental samples

International Nuclear Information System (INIS)

Pibida, L.; McMahon, C.A.; Noertershaeuser, W.; Bushaw, B.A.

2002-01-01

A resonance ionization mass spectrometry (RIMS) system has been developed at the National Institute of Standards and Technology (NIST) for sensitive and selective determination of radio-cesium in the environment. The overall efficiency was determined to be 4x10-7 with a combined (laser and mass spectrometer) selectivity of 108 for both 135Cs and 137Cs with respect to 133Cs. RIMS isotopic ratio measurements of 135Cs/ 137Cs were performed on a nuclear fuel burn-up sample and compared to measurements on a similar system at Pacific Northwest National Laboratory (PNNL) and to conventional thermal ionization mass spectrometry (TIMS). Results of preliminary RIMS investigations on a freshwater lake sediment sample are also discussed

Structural characterization of suppressor lipids by high-resolution mass spectrometry

DEFF Research Database (Denmark)

Rovillos, Mary Joy; Pauling, Josch Konstantin; Hannibal-Bach, Hans Kristian

2016-01-01

RATIONALE: Suppressor lipids were originally identified in 1993 and reported to encompass six lipid classes that enable Saccharomyces cerevisiae to live without sphingolipids. Structural characterization, using non-mass spectrometric approaches, revealed that these suppressor lipids are very long...... chain fatty acid (VLCFA)-containing glycerophospholipids with polar head groups that are typically incorporated into sphingolipids. Here we report, for the first time, the structural characterization of the yeast suppressor lipids using high-resolution mass spectrometry. METHODS: Suppressor lipids were...... isolated by preparative chromatography and subjected to structural characterization using hybrid quadrupole time-of-flight and ion trap-orbitrap mass spectrometry. RESULTS: Our investigation recapitulates the overall structural features of the suppressor lipids and provides an in-depth characterization...

Negative ion electrospray ionization mass spectrometry of nucleoside phosphoramidate monoesters: elucidation of novel rearrangement mechanisms by multistage mass spectrometry incorporating in-source deuterium labelling.

Science.gov (United States)

Xu, Peng-Xiang; Hu, An-Fu; Hu, Dan; Gao, Xiang; Zhao, Yu-Fen

2008-10-01

Several O-2',3'-isopropylideneuridine-O-5'-phosphoramidate monoesters were synthesized and analyzed by negative ion electrospray ionization tandem mass spectrometry (ESI-MS(n)). Two kinds of novel rearrangement reactions were observed due to the difference in the amino acid in the nucleoside phosphoramidate monoesters, and possible mechanisms were proposed. One involves a five-membered cyclic transition state. The other is formation of a stable five-membered ring intermediate by Michael addition. Results were confirmed by tandem mass spectrometry and isotopically labeled hydrogen atoms. Furthermore, the internal hydrogen exchange between active hydrogen and methyl acrylate in the heated capillary of the mass spectrometer was found. The characteristic fragmentation behavior in ESI-MS may be used to monitor this kind of compounds in the biological metabolism.

Advancements in mass spectrometry for biological samples: Protein chemical cross-linking and metabolite analysis of plant tissues

Energy Technology Data Exchange (ETDEWEB)

Klein, Adam [Iowa State Univ., Ames, IA (United States)

2015-01-01

This thesis presents work on advancements and applications of methodology for the analysis of biological samples using mass spectrometry. Included in this work are improvements to chemical cross-linking mass spectrometry (CXMS) for the study of protein structures and mass spectrometry imaging and quantitative analysis to study plant metabolites. Applications include using matrix-assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) to further explore metabolic heterogeneity in plant tissues and chemical interactions at the interface between plants and pests. Additional work was focused on developing liquid chromatography-mass spectrometry (LC-MS) methods to investigate metabolites associated with plant-pest interactions.

Issues and opportunities in accelerator mass spectrometry for stable isotopes.

Science.gov (United States)

Matteson, Sam

2008-01-01

Accelerator mass spectrometry (AMS) has developed in the last 30 years many notable applications to the spectrometry of radioisotopes, particularly in radiocarbon dating. The instrumentation science of trace element AMS (TEAMS) that analyzes stable isotopes, also called Accelerator SIMS or MegaSIMS, while unique in many features, has also shared in many of these significant advances and has pushed TEAMS sensitivity to concentration levels surpassing many competing mass spectroscopic technologies. This review examines recent instrumentation developments, the capabilities of the new instrumentation and discernable trends for future development. Copyright 2008 Wiley Periodicals, Inc.

Major roles for minor bacterial lipids identified by mass spectrometry.

Science.gov (United States)

Garrett, Teresa A

2017-11-01

Mass spectrometry of lipids, especially those isolated from bacteria, has ballooned over the past two decades, affirming in the process the complexity of the lipidome. With this has come the identification of new and interesting lipid structures. Here is an overview of several novel lipids, from both Gram-negative and Gram-positive bacteria with roles in health and disease, whose structural identification was facilitated using mass spectrometry. This article is part of a Special Issue entitled: Bacterial Lipids edited by Russell E. Bishop. Copyright © 2016 Elsevier B.V. All rights reserved.

Improving mass measurement accuracy in mass spectrometry based proteomics by combining open source tools for chromatographic alignment and internal calibration.

Science.gov (United States)

Palmblad, Magnus; van der Burgt, Yuri E M; Dalebout, Hans; Derks, Rico J E; Schoenmaker, Bart; Deelder, André M

2009-05-02

Accurate mass determination enhances peptide identification in mass spectrometry based proteomics. We here describe the combination of two previously published open source software tools to improve mass measurement accuracy in Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). The first program, msalign, aligns one MS/MS dataset with one FTICRMS dataset. The second software, recal2, uses peptides identified from the MS/MS data for automated internal calibration of the FTICR spectra, resulting in sub-ppm mass measurement errors.

Mass spectrometry-based metabolomics: Targeting the crosstalk between gut microbiota and brain in neurodegenerative disorders.

Science.gov (United States)

Luan, Hemi; Wang, Xian; Cai, Zongwei

2017-11-12

Metabolomics seeks to take a "snapshot" in a time of the levels, activities, regulation and interactions of all small molecule metabolites in response to a biological system with genetic or environmental changes. The emerging development in mass spectrometry technologies has shown promise in the discovery and quantitation of neuroactive small molecule metabolites associated with gut microbiota and brain. Significant progress has been made recently in the characterization of intermediate role of small molecule metabolites linked to neural development and neurodegenerative disorder, showing its potential in understanding the crosstalk between gut microbiota and the host brain. More evidence reveals that small molecule metabolites may play a critical role in mediating microbial effects on neurotransmission and disease development. Mass spectrometry-based metabolomics is uniquely suitable for obtaining the metabolic signals in bidirectional communication between gut microbiota and brain. In this review, we summarized major mass spectrometry technologies including liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry, and imaging mass spectrometry for metabolomics studies of neurodegenerative disorders. We also reviewed the recent advances in the identification of new metabolites by mass spectrometry and metabolic pathways involved in the connection of intestinal microbiota and brain. These metabolic pathways allowed the microbiota to impact the regular function of the brain, which can in turn affect the composition of microbiota via the neurotransmitter substances. The dysfunctional interaction of this crosstalk connects neurodegenerative diseases, including Parkinson's disease, Alzheimer's disease and Huntington's disease. The mass spectrometry-based metabolomics analysis provides information for targeting dysfunctional pathways of small molecule metabolites in the development of the neurodegenerative diseases, which may be valuable for the

Quantitation of mycotoxins using direct analysis in real time (DART)-mass spectrometry (MS)

Science.gov (United States)

Ambient ionization represents a new generation of mass spectrometry ion sources which is used for rapid ionization of small molecules under ambient conditions. The combination of ambient ionization and mass spectrometry allows analyzing multiple food samples with simple or no sample treatment, or in...