Quantification of endocrine disruptors and pesticides in water by gas chromatography-tandem mass spectrometry. Method validation using weighted linear regression schemes.

Science.gov (United States)

Mansilha, C; Melo, A; Rebelo, H; Ferreira, I M P L V O; Pinho, O; Domingues, V; Pinho, C; Gameiro, P

2010-10-22

A multi-residue methodology based on a solid phase extraction followed by gas chromatography-tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC-MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness. Copyright © 2010 Elsevier B.V. All rights reserved.

Development and validation of ultra-performance liquid chromatographic method with tandem mass spectrometry for determination of lenalidomide in rabbit and human plasma

Directory of Open Access Journals (Sweden)

Iqbal Muzaffar

2013-01-01

Full Text Available Abstract Background Lenalidomide (LND is a potent novel thalidomide analog which demonstrated remarkable clinical activity in treatment of multiple myeloma disease via a multiple-pathways mechanism. Validated sensitive method with high throughput is required for the determination of lenalidomide for pharmacokinetics and toxicokinetic studies. Ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS is a preeminent analytical tool for rapid biomedical analysis. Results A simple, highly sensitive UPLC-MS/MS method was developed and validated for the determination of LND in rabbit and human plasma. After a simple protein precipitation using methanol, LND and carbamazepine (IS were separated on Acquity UPLC BEH™ C18 column (50 × 2.1 mm, i.d. 1.7 μm, Waters, USA using a mobile phase consisted of acetonitrile:water:formic acid (65:35:0.1%, v/v/v pumped at a flow rate of 0.2 mL/min. LND and IS were eluted at 0.71 and 1.92 min, respectively. The mass spectrometric determination was carried out using an electrospray interface operated in the positive mode with multiple reaction monitoring (MRM mode. The precursor to product ion transitions of m/z 260.1 > 149.0 and m/z 237.0 > 179.0 were used to quantify LND and IS, respectively. The method was linear in the concentration range of 0.23–1000 ng/mL with a limit of quantitation of 0.23 ng/mL. All the validation parameters were in the ranges acceptable by the guidelines of analytical method validation. Conclusion The proposed UPLC-MS/MS method is simple, rapid and highly sensitive, and hence it could be reliable for pharmacokinetic and toxicokinetic study in both animals and humans.

Quantitative Analysis of Tetramethylenedisulfotetramine ("Tetramine") Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Owens, J; Hok, S; Alcaraz, A; Koester, C

2008-11-13

Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD{sub 50} = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limit of quantitation was 0.10 {micro}g/mL by LC/MS/MS versus 0.15 {micro}g/mL for GC/MS. Fortifications of the beverages at 2.5 {micro}g/mL and 0.25 {micro}g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.

Quantitative Analysis of Tetramethylenedisulfotetramine ('Tetramine') Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry

International Nuclear Information System (INIS)

Owens, J.; Hok, S.; Alcaraz, A.; Koester, C.

2008-01-01

Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD 50 = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limit of quantitation was 0.10 (micro)g/mL by LC/MS/MS versus 0.15 (micro)g/mL for GC/MS. Fortifications of the beverages at 2.5 (micro)g/mL and 0.25 (micro)g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.

Development and validation of a method for detection and quantification of ochratoxin A in green coffee using liquid chromatography coupled to mass spectrometry

Directory of Open Access Journals (Sweden)

Raquel Duarte da Costa Cunha Bandeira

2012-12-01

Full Text Available A method using Liquid Chromatography Tanden Mass Spectrometry (LC-MS/MS with matrix-matched calibration curve was developed and validated for determining ochratoxin A (OTA in green coffee. Linearity was found between 3.0 and 23.0 ng.g-1. Mean recoveries ranged between 90.45% and 108.81%; the relative standard deviation under repeatability and intermediate precision conditions ranged from 5.39% to 9.94% and from 2.20% to 14.34%, respectively. The limits of detection and quantification were 1.2 ng.g-1 and 3.0 ng.g-¹, respectively. The method developed was suitable and contributed to the field of mycotoxin analysis, and it will be used for future production of the Certified Reference Material (CRM for OTA in coffee.

Rapid determination of anti-estrogens by gas chromatography/mass spectrometry in urine: Method validation and application to real samples.

Science.gov (United States)

Gerace, E; Salomone, A; Abbadessa, G; Racca, S; Vincenti, M

2012-02-01

A fast screening protocol was developed for the simultaneous determination of nine anti-estrogenic agents (aminoglutethimide, anastrozole, clomiphene, drostanolone, formestane, letrozole, mesterolone, tamoxifen, testolactone) plus five of their metabolites in human urine. After an enzymatic hydrolysis, these compounds can be extracted simultaneously from urine with a simple liquid-liquid extraction at alkaline conditions. The analytes were subsequently analyzed by fast-gas chromatography/mass spectrometry (fast-GC/MS) after derivatization. The use of a short column, high-flow carrier gas velocity and fast temperature ramping produced an efficient separation of all analytes in about 4 min, allowing a processing rate of 10 samples/h. The present analytical method was validated according to UNI EN ISO/IEC 17025 guidelines for qualitative methods. The range of investigated parameters included the limit of detection, selectivity, linearity, repeatability, robustness and extraction efficiency. High MS-sampling rate, using a benchtop quadrupole mass analyzer, resulted in accurate peak shape definition under both scan and selected ion monitoring modes, and high sensitivity in the latter mode. Therefore, the performances of the method are comparable to the ones obtainable from traditional GC/MS analysis. The method was successfully tested on real samples arising from clinical treatments of hospitalized patients and could profitably be used for clinical studies on anti-estrogenic drug administration.

Development of a methodology for the detection of Ra226 in large volumes of water by gamma spectrometry; modification and validation of the method for detection and quantification of Ra226 in small volumes of water by alpha spectrometry, used by the Centro de Investigacion en Ciencias Atomicas, Nucleares y Moleculares (CICANUM, UCR)

International Nuclear Information System (INIS)

Molina Porras, Arnold

2011-01-01

The test method has been validated for quantifying the specific activity of Ra 226 in water alpha spectrometry. The CICANUM has used this method as part of the proposed harmonization of methods ARCAL (IAEA). The method is based on a first separation and preconcentration of Ra 226 by coprecipitation and subsequent MnO 2 micro precipitation as Ba (Ra) SO 4 . Samples were prepared and then was performed the counting by alpha spectrometry. A methodology of radio sampling for large volumes of water was tested in parallel, using acrylic fibers impregnated with manganese oxide (IV) to determine the amount of Ra 226 present by gamma spectrometry. Small-scale tests, have determined that the best way to prepare the fiber is the reference method found in the literature and using the oven at 60 degrees Celsius. (author) [es

Clinical validation of cutoff target ranges in newborn screening of metabolic disorders by tandem mass spectrometry : A worldwide collaborative project

NARCIS (Netherlands)

McHugh, David M. S.; Cameron, Cynthia A.; Abdenur, Jose E.; Abdulrahman, Mahera; Adair, Ona; Al Nuaimi, Shahira Ahmed; Ahlman, Henrik; Allen, Jennifer J.; Antonozzi, Italo; Archer, Shaina; Au, Sylvia; Auray-Blais, Christiane; Baker, Mei; Bamforth, Fiona; Beckmann, Kinga; Pino, Gessi Bentz; Berberich, Stanton L.; Binard, Robert; Boemer, Francois; Bonham, Jim; Breen, Nancy N.; Bryant, Sandra C.; Caggana, Michele; Caldwell, S. Graham; Camilot, Marta; Campbell, Carlene; Carducci, Claudia; Cariappa, Rohit; Carlisle, Clover; Caruso, Ubaldo; Cassanello, Michela; Miren Castilla, Ane; Castineiras Ramos, Daisy E.; Chakraborty, Pranesh; Chandrasekar, Ram; Ramos, Alfredo Chardon; Cheillan, David; Chien, Yin-Hsiu; Childs, Thomas A.; Chrastina, Petr; Sica, Yuri Cleverthon; Cocho de Juan, Jose Angel; Elena Colandre, Maria; Cornejo Espinoza, Veronica; Corso, Gaetano; Currier, Robert; Cyr, Denis; Czuczy, Noemi; D'Apolito, Oceania; Davis, Tim; de Sain-Van der Velden, Monique G.; Delgado Pecellin, Carmen; Di Gangi, Iole Maria; Di Stefano, Cristina Maria; Dotsikas, Yannis; Downing, Melanie; Downs, Stephen M.; Dy, Bonifacio; Dymerski, Mark; Rueda, Inmaculada; Elvers, Bert; Eaton, Roger; Eckerd, Barbara M.; El Mougy, Fatma; Eroh, Sarah; Espada, Mercedes; Evans, Catherine; Fawbush, Sandy; Fijolek, Kristel F.; Fisher, Lawrence; Franzson, Leifur; Frazier, Dianne M.; Garcia, Luciana R. C.; Garcia-Valdecasas Bermejo, Maria Sierra; Gavrilov, Dimitar; Gerace, Rosemarie; Giordano, Giuseppe; Irazabal, Yolanda Gonzalez; Greed, Lawrence C.; Grier, Robert; Grycki, Elyse; Gu, Xuefan; Gulamali-Majid, Fizza; Hagar, Arthur F.; Han, Lianshu; Hannon, W. Harry; Haslip, Christa; Hassan, Fayza Abdelhamid; He, Miao; Hietala, Amy; Himstedt, Leslie; Hoffman, Gary L.; Hoffman, William; Hoggatt, Philis; Hopkins, Patrick V.; Hougaard, David M.; Hughes, Kerie; Hunt, Patricia R.; Hwu, Wuh-Liang; Hynes, June; Ibarra-Gonzalez, Isabel; Ingham, Cindy A.; Ivanova, Maria; Jacox, Ward B.; John, Catharine; Johnson, John P.; Jonsson, Jon J.; Karg, Eszter; Kasper, David; Klopper, Brenda; Katakouzinos, Dimitris; Khneisser, Issam; Knoll, Detlef; Kobayashi, Hirinori; Koneski, Ronald; Kozich, Viktor; Kouapei, Rasoul; Kohlmueller, Dirk; Kremensky, Ivo; la Marca, Giancarlo; Lavochkin, Marcia; Lee, Soo-Youn; Lehotay, Denis C.; Lemes, Aida; Lepage, Joyce; Lesko, Barbara; Lewis, Barry; Lim, Carol; Linard, Sharon; Lindner, Martin; Lloyd-Puryear, Michele A.; Lorey, Fred; Loukas, Yannis L.; Luedtke, Julie; Maffitt, Neil; Magee, J. Fergall; Manning, Adrienne; Manos, Shawn; Marie, Sandrine; Hadachi, Sonia Marchezi; Marquardt, Gregg; Martin, Stephen J.; Matern, Dietrich; Gibson, Stephanie K. Mayfield; Mayne, Philip; McCallister, Tonya D.; McCann, Mark; McClure, Julie; McGill, James J.; McKeever, Christine D.; McNeilly, Barbara; Morrissey, Mark A.; Moutsatsou, Paraskevi; Mulcahy, Eleanor A.; Nikoloudis, Dimitris; Norgaard-Pedersen, Bent; Oglesbee, Devin; Oltarzewski, Mariusz; Ombrone, Daniela; Ojodu, Jelili; Papakonstantinou, Vagelis; Reoyo, Sherly Pardo; Park, Hyung-Doo; Pasquali, Marzia; Pasquini, Elisabetta; Patel, Pallavi; Pass, Kenneth A.; Peterson, Colleen; Pettersen, Rolf D.; Pitt, James J.; Poh, Sherry; Pollak, Arnold; Porter, Cory; Poston, Philip A.; Price, Ricky W.; Queijo, Cecilia; Quesada, Jonessy; Randell, Edward; Ranieri, Enzo; Raymond, Kimiyo; Reddic, John E.; Reuben, Alejandra; Ricciardi, Charla; Rinaldo, Piero; Rivera, Jeff D.; Roberts, Alicia; Rocha, Hugo; Roche, Geraldine; Greenberg, Cheryl Rochman; Egea Mellado, Jose Maria; Jess Juan-Fita, Maria; Ruiz, Consuelo; Ruoppolo, Margherita; Rutledge, S. Lane; Ryu, Euijung; Saban, Christine; Sahai, Inderneel; Salazar Garcia-Blanco, Maria Isabel; Santiago-Borrero, Pedro; Schenone, Andrea; Schoos, Roland; Schweitzer, Barb; Scott, Patricia; Seashore, Margretta R.; Seeterlin, Mary A.; Sesser, David E.; Sevier, Darrin W.; Shone, Scott M.; Sinclair, Graham; Skrinska, Victor A.; Stanley, Eleanor L.; Strovel, Erin T.; Jones, April L. Studinski; Sunny, Sherlykutty; Takats, Zoltan; Tanyalcin, Tijen; Teofoli, Francesca; Thompson, J. Robert; Tomashitis, Kathy; Domingos, Mouseline Torquado; Torres, Jasmin; Torres, Rosario; Tortorelli, Silvia; Turi, Sandor; Turner, Kimberley; Tzanakos, Nick; Valiente, Alf G.; Vallance, Hillary; Vela-Amieva, Marcela; Vilarinho, Laura; von Doebeln, Ulrika; Vincent, Marie-Francoise; Vorster, B. Chris; Watson, Michael S.; Webster, Dianne; Weiss, Sheila; Wilcken, Bridget; Wiley, Veronica; Williams, Sharon K.; Willis, Sharon A.; Woontner, Michael; Wright, Katherine; Yahyaoui, Raquel; Yamaguchi, Seiji; Yssel, Melissa; Zakowicz, Wendy M.

Purpose: To achieve clinical validation of cutoff values for newborn screening by tandem mass spectrometry through a worldwide collaborative effort. Methods: Cumulative percentiles of amino acids and acylcarnitines in dried blood spots of approximately 25-30 million normal newborns and 10,742

Simultaneous determination of seven flavonoids in Epimedium by liquid chromatography-tandem mass spectrometry method

Institute of Scientific and Technical Information of China (English)

Cai Sheng Wu; Bao Lin Guo; Yu Xin Sheng; Jin Lan Zhang

2008-01-01

In this paper, a sensitive and specific liquid chromatography-electrospray ionisation-mass spectrometry (LC-ESI-MS) method has been developed and validated for the identification and determination of seven flavonoids, namely epimedin A, epimedin B, epimedin C, icariin, sagittatoside B, 2"-0-rhamnosyl icariside II, and baohuoside I in Epimedium from different sources.

Investigation of the presence of β-hydroxy-β-methylbutyric acid and α-hydroxyisocaproic acid in bovine whole milk and fermented dairy products by a validated liquid chromatography-mass spectrometry method.

Science.gov (United States)

Ehling, Stefan; Reddy, Todime M

2014-02-19

A simple, rugged, quantitative, and confirmatory method based on liquid chromatography-mass spectrometry was developed and comprehensively validated for the analysis of the leucine metabolites β-hydroxy-β-methylbutyric acid (HMB) and α-hydroxyisocaproic acid (HICA) in bovine whole milk and yogurt. Mean accuracy (90-110% for HMB and 85-115% for HICA) and total precision (dairy products with HMB and/or HICA appears to be justified.

Validation of a method to quantify chromium, cadmium, manganese, nickel and lead in human whole blood, urine, saliva and hair samples by electrothermal atomic absorption spectrometry

Energy Technology Data Exchange (ETDEWEB)

Olmedo, P.; Pla, A.; Hernandez, A.F.; Lopez-Guarnido, O.; Rodrigo, L. [Department of Legal Medicine and Toxicology, University of Granada, School of Medicine (Spain); Gil, F., E-mail: fgil@ugr.es [Department of Legal Medicine and Toxicology, University of Granada, School of Medicine (Spain)

2010-02-05

For biological monitoring of heavy metal exposure in occupational toxicology, usually whole blood and urine samples are the most widely used and accepted matrix to assess internal xenobiotic exposure. Hair samples and saliva are also of interest in occupational and environmental health surveys but procedures for the determination of metals in saliva and hair are very scarce and to our knowledge there is no validation of a method to quantify Cr, Cd, Mn, Ni and Pb in four different human biological materials (whole blood, urine, saliva and axilary hair) by electrothermal atomization atomic absorption spectrometry (ETAAS). In the present study, quantification methods for the determination of Cr, Cd, Mn, Ni and Pb in whole blood, urine, saliva and axilary hair were validated according to the EU common standards. Pyrolisis and atomization temperatures have been determined. The main parameters evaluated were: detection and quantification limits, linearity range, repeatability, reproducibility, recovery and uncertainty. Accuracy of the methods was tested with the whole blood, urine and hair certified reference materials and recoveries of the spiked samples were acceptable ranged from 96.3 to 107.8%.

Validation of a method to quantify chromium, cadmium, manganese, nickel and lead in human whole blood, urine, saliva and hair samples by electrothermal atomic absorption spectrometry

International Nuclear Information System (INIS)

Olmedo, P.; Pla, A.; Hernandez, A.F.; Lopez-Guarnido, O.; Rodrigo, L.; Gil, F.

2010-01-01

For biological monitoring of heavy metal exposure in occupational toxicology, usually whole blood and urine samples are the most widely used and accepted matrix to assess internal xenobiotic exposure. Hair samples and saliva are also of interest in occupational and environmental health surveys but procedures for the determination of metals in saliva and hair are very scarce and to our knowledge there is no validation of a method to quantify Cr, Cd, Mn, Ni and Pb in four different human biological materials (whole blood, urine, saliva and axilary hair) by electrothermal atomization atomic absorption spectrometry (ETAAS). In the present study, quantification methods for the determination of Cr, Cd, Mn, Ni and Pb in whole blood, urine, saliva and axilary hair were validated according to the EU common standards. Pyrolisis and atomization temperatures have been determined. The main parameters evaluated were: detection and quantification limits, linearity range, repeatability, reproducibility, recovery and uncertainty. Accuracy of the methods was tested with the whole blood, urine and hair certified reference materials and recoveries of the spiked samples were acceptable ranged from 96.3 to 107.8%.

Development and validation of automatic HS-SPME with a gas chromatography-ion trap/mass spectrometry method for analysis of volatiles in wines.

Science.gov (United States)

Paula Barros, Elisabete; Moreira, Nathalie; Elias Pereira, Giuliano; Leite, Selma Gomes Ferreira; Moraes Rezende, Claudia; Guedes de Pinho, Paula

2012-11-15

An automated headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-ion trap/mass spectrometry (GC-IT/MS) was developed in order to quantify a large number of volatile compounds in wines such as alcohols, ester, norisoprenoids and terpenes. The procedures were optimized for SPME fiber selection, pre-incubation temperature and time, extraction temperature and time, and salt addition. A central composite experimental design was used in the optimization of the extraction conditions. The volatile compounds showed optimal extraction using a DVB/CAR/PDMS fiber, incubation of 5 ml of wine with 2g NaCl at 45 °C during 5 min, and subsequent extraction of 30 min at the same temperature. The method allowed the identification of 64 volatile compounds. Afterwards, the method was validated successfully for the most significant compounds and was applied to study the volatile composition of different white wines. Copyright © 2012 Elsevier B.V. All rights reserved.

Development and validation of an ultra-high performance liquid chromatography-tandem mass spectrometry method to measure creatinine in human urine.

Science.gov (United States)

Fraselle, S; De Cremer, K; Coucke, W; Glorieux, G; Vanmassenhove, J; Schepers, E; Neirynck, N; Van Overmeire, I; Van Loco, J; Van Biesen, W; Vanholder, R

2015-04-15

Despite decades of creatinine measurement in biological fluids using a large variety of analytical methods, an accurate determination of this compound remains challenging. Especially with the novel trend to assess biomarkers on large sample sets preserved in biobanks, a simple and fast method that could cope with both a high sample throughput and a low volume of sample is still of interest. In answer to these challenges, a fast and accurate ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to measure creatinine in small volumes of human urine. In this method, urine samples are simply diluted with a basic mobile phase and injected directly under positive electrospray ionization (ESI) conditions, without further purification steps. The combination of an important diluting factor (10(4) times) due to the use of a very sensitive triple quadrupole mass spectrometer (XEVO TQ) and the addition of creatinine-d3 as internal standard completely eliminates matrix effects coming from the urine. The method was validated in-house in 2012 according to the EMA guideline on bioanalytical method validation using Certified Reference samples from the German External Quality Assessment Scheme (G-Equas) proficiency test. All obtained results for accuracy and recovery are within the authorized tolerance ranges defined by G-Equas. The method is linear between 0 and 5 g/L, with LOD and LOQ of 5 × 10(-3) g/L and 10(-2) g/L, respectively. The repeatability (CV(r) = 1.03-2.07%) and intra-laboratory reproducibility (CV(RW) = 1.97-2.40%) satisfy the EMA 2012 guideline. The validated method was firstly applied to perform the German G-Equas proficiency test rounds 51 and 53, in 2013 and 2014, respectively. The obtained results were again all within the accepted tolerance ranges and very close to the reference values defined by the organizers of the proficiency test scheme, demonstrating an excellent accuracy of the developed method. The

Nickel quantification in serum by a validated sector-field inductively coupled plasma mass spectrometry method: Assessment of tentative reference values for an Italian population.

Science.gov (United States)

Bocca, Beatrice; Forte, Giovanni; Ronchi, Anna; Gaggeri, Raffaella; Alimonti, Alessandro; Minoia, Claudio

2006-01-01

The daily exposure to Ni from food, industrial processes, jewellery and coins makes the determination of Ni in human serum an important way to monitor the health status in non-occupationally exposed subjects. To this end, a method based on sector-field inductively coupled plasma mass spectrometry was developed and validated. The limits of detection (LoD) and quantification (LoQ), sensitivity, linearity range, trueness, repeatability, within-laboratory reproducibility and robustness were the considered issues of the validation process. The uncertainty associated with the measurements was also calculated, according to the Eurachem/Citac Guide. The method LoD and LoQ were 0.03 and 0.09 ng mL(-1), linearity was over two order of magnitude, trueness was -3.57%, and the repeatability and reproducibility showed relative standard deviations equal to 4.56% and 6.52%, respectively. The relative expanded uncertainty was 21.8% at the Ni levels found in the general population. The tentative reference value for serum Ni was 0.466 +/- 0.160 ng mL(-1) with a related interval between 0.226 and 1.026 ng mL(-1). Copyright 2006 John Wiley & Sons, Ltd.

Novel Selectivity-Based Forensic Toxicological Validation of a Paper Spray Mass Spectrometry Method for the Quantitative Determination of Eight Amphetamines in Whole Blood

Science.gov (United States)

Teunissen, Sebastiaan F.; Fedick, Patrick W.; Berendsen, Bjorn J. A.; Nielen, Michel W. F.; Eberlin, Marcos N.; Graham Cooks, R.; van Asten, Arian C.

2017-12-01

Paper spray tandem mass spectrometry is used to identify and quantify eight individual amphetamines in whole blood in 1.3 min. The method has been optimized and fully validated according to forensic toxicology guidelines, for the quantification of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy- N-methylamphetamine (MDMA), 3,4-methylenedioxy- N-ethylamphetamine (MDEA), para-methoxyamphetamine (PMA), para-methoxymethamphetamine (PMMA), and 4-fluoroamphetamine (4-FA). Additionally, a new concept of intrinsic and application-based selectivity is discussed, featuring increased confidence in the power to discriminate the amphetamines from other chemically similar compounds when applying an ambient mass spectrometric method without chromatographic separation. Accuracy was within ±15% and average precision was better than 15%, and better than 20% at the LLOQ. Detection limits between 15 and 50 ng/mL were obtained using only 12 μL of whole blood. [Figure not available: see fulltext.

COPD Exacerbation Biomarkers Validated Using Multiple Reaction Monitoring Mass Spectrometry.

Directory of Open Access Journals (Sweden)

Janice M Leung

Full Text Available Acute exacerbations of chronic obstructive pulmonary disease (AECOPD result in considerable morbidity and mortality. However, there are no objective biomarkers to diagnose AECOPD.We used multiple reaction monitoring mass spectrometry to quantify 129 distinct proteins in plasma samples from patients with COPD. This analytical approach was first performed in a biomarker cohort of patients hospitalized with AECOPD (Cohort A, n = 72. Proteins differentially expressed between AECOPD and convalescent states were chosen using a false discovery rate 1.2. Protein selection and classifier building were performed using an elastic net logistic regression model. The performance of the biomarker panel was then tested in two independent AECOPD cohorts (Cohort B, n = 37, and Cohort C, n = 109 using leave-pair-out cross-validation methods.Five proteins were identified distinguishing AECOPD and convalescent states in Cohort A. Biomarker scores derived from this model were significantly higher during AECOPD than in the convalescent state in the discovery cohort (p<0.001. The receiver operating characteristic cross-validation area under the curve (CV-AUC statistic was 0.73 in Cohort A, while in the replication cohorts the CV-AUC was 0.77 for Cohort B and 0.79 for Cohort C.A panel of five biomarkers shows promise in distinguishing AECOPD from convalescence and may provide the basis for a clinical blood test to diagnose AECOPD. Further validation in larger cohorts is necessary for future clinical translation.

Validation of an analytical method for nitrous oxide (N2O) laughing gas by headspace gas chromatography coupled to mass spectrometry (HS-GC-MS): forensic application to a lethal intoxication.

Science.gov (United States)

Giuliani, N; Beyer, J; Augsburger, M; Varlet, V

2015-03-01

Drug abuse is a widespread problem affecting both teenagers and adults. Nitrous oxide is becoming increasingly popular as an inhalation drug, causing harmful neurological and hematological effects. Some gas chromatography-mass spectrometry (GC-MS) methods for nitrous oxide measurement have been previously described. The main drawbacks of these methods include a lack of sensitivity for forensic applications; including an inability to quantitatively determine the concentration of gas present. The following study provides a validated method using HS-GC-MS which incorporates hydrogen sulfide as a suitable internal standard allowing the quantification of nitrous oxide. Upon analysis, sample and internal standard have similar retention times and are eluted quickly from the molecular sieve 5Å PLOT capillary column and the Porabond Q column therefore providing rapid data collection whilst preserving well defined peaks. After validation, the method has been applied to a real case of N2O intoxication indicating concentrations in a mono-intoxication. Copyright © 2015 Elsevier B.V. All rights reserved.

A high-throughput method for liquid chromatography-tandem mass spectrometry determination of plasma alkylresorcinols, biomarkers of whole grain wheat and rye intake

DEFF Research Database (Denmark)

Ross, Alastair B; Svelander, Cecilia; Savolainen, Otto I

2016-01-01

supported extraction methods for extracting alkylresorcinols from plasma and improved a normal-phase liquid chromatography coupled to a tandem mass spectrometer method to reduce sample analysis time. The method was validated and compared with gas chromatography-mass spectrometry analysis. Sample preparation...

Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry.

Science.gov (United States)

Torres, Daiane Placido; Martins-Teixeira, Maristela Braga; Cadore, Solange; Queiroz, Helena Müller

2015-01-01

A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg(-1) (square regression) and 250.0 and 2000.0 μg kg(-1) (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg(-1), respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025.

Development and Validation of a Sensitive Method for Trace Nickel Determination by Slotted Quartz Tube Flame Atomic Absorption Spectrometry After Dispersive Liquid-Liquid Microextraction.

Science.gov (United States)

Yolcu, Şükran Melda; Fırat, Merve; Chormey, Dotse Selali; Büyükpınar, Çağdaş; Turak, Fatma; Bakırdere, Sezgin

2018-05-01

In this study, dispersive liquid-liquid microextraction was systematically optimized for the preconcentration of nickel after forming a complex with diphenylcarbazone. The measurement output of the flame atomic absorption spectrometer was further enhanced by fitting a custom-cut slotted quartz tube to the flame burner head. The extraction method increased the amount of nickel reaching the flame and the slotted quartz tube increased the residence time of nickel atoms in the flame to record higher absorbance. Two methods combined to give about 90 fold enhancement in sensitivity over the conventional flame atomic absorption spectrometry. The optimized method was applicable over a wide linear concentration range, and it gave a detection limit of 2.1 µg L -1 . Low relative standard deviations at the lowest concentration in the linear calibration plot indicated high precision for both extraction process and instrumental measurements. A coal fly ash standard reference material (SRM 1633c) was used to determine the accuracy of the method, and experimented results were compatible with the certified value. Spiked recovery tests were also used to validate the applicability of the method.

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.

Formic acid hydrolysis/liquid chromatography isotope dilution mass spectrometry: An accurate method for large DNA quantification.

Science.gov (United States)

Shibayama, Sachie; Fujii, Shin-Ichiro; Inagaki, Kazumi; Yamazaki, Taichi; Takatsu, Akiko

2016-10-14

Liquid chromatography-isotope dilution mass spectrometry (LC-IDMS) with formic acid hydrolysis was established for the accurate quantification of λDNA. The over-decomposition of nucleobases in formic acid hydrolysis was restricted by optimizing the reaction temperature and the reaction time, and accurately corrected by using deoxynucleotides (dNMPs) and isotope-labeled dNMPs as the calibrator and the internal standard, respectively. The present method could quantify λDNA with an expanded uncertainty of 4.6% using 10fmol of λDNA. The analytical results obtained with the present method were validated by comparing with the results of phosphate-base quantification by inductively coupled plasma-mass spectrometry (ICP-MS). The results showed good agreement with each other. We conclude that the formic acid hydrolysis/LC-IDMS method can quantify λDNA accurately and is promising as the primary method for the certification of DNA as reference material. Copyright © 2016 Elsevier B.V. All rights reserved.

Validation of Am-241 measurement in ion chamber type smoke detector by using gamma spectrometry system

International Nuclear Information System (INIS)

Yii Mei Wo; Khairul Nizam Razali

2005-01-01

Smoke detectors are useful devices in modern days that able to save many lives. Even though, the use of ion chamber type smoke detector (usually contain Americium-241) was exempted in Malaysia, but the trading of this device was controlled by regulation, under the Atomic Energy Licensing Act (Act 304). The activity of the Am-241 can be measured by using the Gamma Spectrometry System since it was much easier, compared to Alpha Spectrometry System. To do so, the system was first need to be calibrated using the standard reference source to find the efficiency of the germanium detector. The method used for the measurement was first validated for several relevant parameters, which include specificity, precision (repeatability), bias (accuracy), linearity, working range, detection limit, robustness and ruggedness to ensure it was fit for the purpose. The measured Am-241 activity inside the smoke detector will be reported together with a reasonable expanded uncertainty arise from the measurement. (Author)

Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio

International Nuclear Information System (INIS)

Keck, B.D.; Ognibene, T.; Vogel, J.S.

2010-01-01

Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of 14 C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of 14 C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the 14 C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with 14 C corresponds to 30 fg equivalents. AMS

Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

Energy Technology Data Exchange (ETDEWEB)

Keck, B D; Ognibene, T; Vogel, J S

2010-02-05

Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

MSX-3D: a tool to validate 3D protein models using mass spectrometry.

Science.gov (United States)

Heymann, Michaël; Paramelle, David; Subra, Gilles; Forest, Eric; Martinez, Jean; Geourjon, Christophe; Deléage, Gilbert

2008-12-01

The technique of chemical cross-linking followed by mass spectrometry has proven to bring valuable information about the protein structure and interactions between proteic subunits. It is an effective and efficient way to experimentally investigate some aspects of a protein structure when NMR and X-ray crystallography data are lacking. We introduce MSX-3D, a tool specifically geared to validate protein models using mass spectrometry. In addition to classical peptides identifications, it allows an interactive 3D visualization of the distance constraints derived from a cross-linking experiment. Freely available at http://proteomics-pbil.ibcp.fr

Development and validation of a multi-residue method for the detection of a wide range of hormonal anabolic compounds in hair using gas chromatography-tandem mass spectrometry

International Nuclear Information System (INIS)

Rambaud, Lauriane; Monteau, Fabrice; Deceuninck, Yoann; Bichon, Emmanuelle; Andre, Francois; Le Bizec, Bruno

2007-01-01

The monitoring of anabolic steroid residues in hair is undoubtedly one of the most efficient strategies to demonstrate the long-term administration of these molecules in meat production animals. A multi-residue sample preparation procedure was developed and validated for 28 steroids. A 100 mg hair sample was grinded into powder and extracted at 50 deg. C with methanol. After acidic hydrolysis and extraction with ethyl acetate, phenolsteroids, such as estrogens, resorcyclic acid lactones and stilbens in one hand, are separated from androgens and progestagens in the other hand. Solid phase extractions were performed before applying a specific derivatisation for each compound sub-group. Detection and identification were achieved using gas chromatography-tandem mass spectrometry with acquisition in the selected reaction monitoring mode after electron ionisation. The method was validated according to the 2002/657/EC guideline. Decision limits (CCα) for main steroids were in the 0.1-10 μg kg -1 range

Development and validation of a multi-residue method for the detection of a wide range of hormonal anabolic compounds in hair using gas chromatography-tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Rambaud, Lauriane [LABERCA, Ecole Nationale Veterinaire de Nantes, Route de Gachet, BP50707, 44307 Nantes Cedex 3 (France); Monteau, Fabrice [LABERCA, Ecole Nationale Veterinaire de Nantes, Route de Gachet, BP50707, 44307 Nantes Cedex 3 (France); Deceuninck, Yoann [LABERCA, Ecole Nationale Veterinaire de Nantes, Route de Gachet, BP50707, 44307 Nantes Cedex 3 (France); Bichon, Emmanuelle [LABERCA, Ecole Nationale Veterinaire de Nantes, Route de Gachet, BP50707, 44307 Nantes Cedex 3 (France); Andre, Francois [LABERCA, Ecole Nationale Veterinaire de Nantes, Route de Gachet, BP50707, 44307 Nantes Cedex 3 (France); Le Bizec, Bruno [LABERCA, Ecole Nationale Veterinaire de Nantes, Route de Gachet, BP50707, 44307 Nantes Cedex 3 (France)]. E-mail: lebizec@vet-nantes.fr

2007-03-14

The monitoring of anabolic steroid residues in hair is undoubtedly one of the most efficient strategies to demonstrate the long-term administration of these molecules in meat production animals. A multi-residue sample preparation procedure was developed and validated for 28 steroids. A 100 mg hair sample was grinded into powder and extracted at 50 deg. C with methanol. After acidic hydrolysis and extraction with ethyl acetate, phenolsteroids, such as estrogens, resorcyclic acid lactones and stilbens in one hand, are separated from androgens and progestagens in the other hand. Solid phase extractions were performed before applying a specific derivatisation for each compound sub-group. Detection and identification were achieved using gas chromatography-tandem mass spectrometry with acquisition in the selected reaction monitoring mode after electron ionisation. The method was validated according to the 2002/657/EC guideline. Decision limits (CC{alpha}) for main steroids were in the 0.1-10 {mu}g kg{sup -1} range.

Validation of methods to measure uranium isotopes using magnetic sector mass spectrometry with inductively coupled plasma source

International Nuclear Information System (INIS)

Hernandez M, H.; Rios L, M. J.; Romero G, E. T.

2017-10-01

The mass spectrometry technique with inductively coupled plasma source (Icp-Ms) has been widely used to measure isotopic ratios of elements toxic to human health. Reason for which, in this work several measurement methods for the analysis of uranium isotopes in different matrices were implemented using magnetic sector mass spectrometry with inductively coupled plasma source (Icp-SFMS). Groundwater, sediment, soil and urine were the matrices analyzed, which were supplied by intercomparison tests conducted by the IAEA and Association for the Promotion of Quality Control of Medical Biology Analysis in Radio-toxicology. The procedures used in the treatment of soil, sediment and water samples were based on US EPA methods. In the case of the urine sample, the preparation was rapid (1:20 dilution). The average of the results obtained in yield of each matrix was 94, 71, 72 and 78% for water, urine, soil and sediment respectively. In addition, the precision in terms of standard relative deviation was less than 5% and the accuracy was less than 4%. In conclusion, the Icp-SFMS is a very sensitive technique for measuring isotopes of U in different matrices. However, careful tuning is necessary, especially in the mass regions of interest 234, 235 and 238 if an external quantification is considered using natural U solutions. (Author)

A validated liquid chromatography-tandem mass spectrometry method for the quantitative determination of 4 beta-hydroxycholesterol in human plasma

NARCIS (Netherlands)

van de Merbel, Nico C.; Bronsema, Kees J.; van Hout, Mischa W. J.; Nilsson, Ralf; Sillen, Henrik

2011-01-01

A novel liquid chromatography-tandem mass spectrometry method is described for the quantitative determination of the endogenous CYP 3A4/5 marker 4 beta-hydroxycholesterol in human K(2)-EDTA plasma. It is based on alkaline hydrolysis to convert esterified to free 4 beta-hydroxycholesterol, followed

Cross validation of gas chromatography-flame photometric detection and gas chromatography-mass spectrometry methods for measuring dialkylphosphate metabolites of organophosphate pesticides in human urine.

Science.gov (United States)

Prapamontol, Tippawan; Sutan, Kunrunya; Laoyang, Sompong; Hongsibsong, Surat; Lee, Grace; Yano, Yukiko; Hunter, Ronald Elton; Ryan, P Barry; Barr, Dana Boyd; Panuwet, Parinya

2014-01-01

We report two analytical methods for the measurement of dialkylphosphate (DAP) metabolites of organophosphate pesticides in human urine. These methods were independently developed/modified and implemented in two separate laboratories and cross validated. The aim was to develop simple, cost effective, and reliable methods that could use available resources and sample matrices in Thailand and the United States. While several methods already exist, we found that direct application of these methods required modification of sample preparation and chromatographic conditions to render accurate, reliable data. The problems encountered with existing methods were attributable to urinary matrix interferences, and differences in the pH of urine samples and reagents used during the extraction and derivatization processes. Thus, we provide information on key parameters that require attention during method modification and execution that affect the ruggedness of the methods. The methods presented here employ gas chromatography (GC) coupled with either flame photometric detection (FPD) or electron impact ionization-mass spectrometry (EI-MS) with isotopic dilution quantification. The limits of detection were reported from 0.10ng/mL urine to 2.5ng/mL urine (for GC-FPD), while the limits of quantification were reported from 0.25ng/mL urine to 2.5ng/mL urine (for GC-MS), for all six common DAP metabolites (i.e., dimethylphosphate, dimethylthiophosphate, dimethyldithiophosphate, diethylphosphate, diethylthiophosphate, and diethyldithiophosphate). Each method showed a relative recovery range of 94-119% (for GC-FPD) and 92-103% (for GC-MS), and relative standard deviations (RSD) of less than 20%. Cross-validation was performed on the same set of urine samples (n=46) collected from pregnant women residing in the agricultural areas of northern Thailand. The results from split sample analysis from both laboratories agreed well for each metabolite, suggesting that each method can produce

Mass Spectrometry-Based Serum Proteomics for Biomarker Discovery and Validation.

Science.gov (United States)

Bhosale, Santosh D; Moulder, Robert; Kouvonen, Petri; Lahesmaa, Riitta; Goodlett, David R

2017-01-01

Blood protein measurements are used frequently in the clinic in the assessment of patient health. Nevertheless, there remains the need for new biomarkers with better diagnostic specificities. With the advent of improved technology for bioanalysis and the growth of biobanks including collections from specific disease risk cohorts, the plasma proteome has remained a target of proteomics research toward the characterization of disease-related biomarkers. The following protocol presents a workflow for serum/plasma proteomics including details of sample preparation both with and without immunoaffinity depletion of the most abundant plasma proteins and methodology for selected reaction monitoring mass spectrometry validation.

Determination of plutonium isotopes in bilberry using liquid scintillation spectrometry and alpha-particle spectrometry

International Nuclear Information System (INIS)

Seferinoğlu, Meryem; Aslan, Nazife; Kurt, Aylin; Erden, Pınar Esra; Mert, Hülya

2014-01-01

This paper presents α-particle spectrometry and liquid scintillation spectrometry methods to determine plutonium isotopes in bilberry. The analytical procedure involves sample preparation steps for ashing, digestion of bilberry samples, radiochemical separation of plutonium radioisotopes and their measurement. The validity of the method was checked for coherence using the ζ test, z-test, relative bias and relative uncertainty outlier tests. The results indicated that the recommended procedures for both measurement systems could be successfully applied for the accurate determination of plutonium activities in bilberry samples. - Highlights: • Sample preparation methods for Pu using LSS and alpha spectrometry developed. • Complete separation of plutonium from interfering radionuclides. • Commercial bilberry was spiked with NPL 2011 (AH-B11144) proficiency test sample. • Results were checked using ζ test, z-test, rel. bias and rel. uncert. outlier tests. • Recommended procedures successfully applied to bilberry samples

Prediction, Detection, and Validation of Isotope Clusters in Mass Spectrometry Data

Directory of Open Access Journals (Sweden)

Hendrik Treutler

2016-10-01

Full Text Available Mass spectrometry is a key analytical platform for metabolomics. The precise quantification and identification of small molecules is a prerequisite for elucidating the metabolism and the detection, validation, and evaluation of isotope clusters in LC-MS data is important for this task. Here, we present an approach for the improved detection of isotope clusters using chemical prior knowledge and the validation of detected isotope clusters depending on the substance mass using database statistics. We find remarkable improvements regarding the number of detected isotope clusters and are able to predict the correct molecular formula in the top three ranks in 92 % of the cases. We make our methodology freely available as part of the Bioconductor packages xcms version 1.50.0 and CAMERA version 1.30.0.

Dereplication of plant phenolics using a mass-spectrometry database independent method.

Science.gov (United States)

Borges, Ricardo M; Taujale, Rahil; de Souza, Juliana Santana; de Andrade Bezerra, Thaís; Silva, Eder Lana E; Herzog, Ronny; Ponce, Francesca V; Wolfender, Jean-Luc; Edison, Arthur S

2018-05-29

Dereplication, an approach to sidestep the efforts involved in the isolation of known compounds, is generally accepted as being the first stage of novel discoveries in natural product research. It is based on metabolite profiling analysis of complex natural extracts. To present the application of LipidXplorer for automatic targeted dereplication of phenolics in plant crude extracts based on direct infusion high-resolution tandem mass spectrometry data. LipidXplorer uses a user-defined molecular fragmentation query language (MFQL) to search for specific characteristic fragmentation patterns in large data sets and highlight the corresponding metabolites. To this end, MFQL files were written to dereplicate common phenolics occurring in plant extracts. Complementary MFQL files were used for validation purposes. New MFQL files with molecular formula restrictions for common classes of phenolic natural products were generated for the metabolite profiling of different representative crude plant extracts. This method was evaluated against an open-source software for mass-spectrometry data processing (MZMine®) and against manual annotation based on published data. The targeted LipidXplorer method implemented using common phenolic fragmentation patterns, was found to be able to annotate more phenolics than MZMine® that is based on automated queries on the available databases. Additionally, screening for ascarosides, natural products with unrelated structures to plant phenolics collected from the nematode Caenorhabditis elegans, demonstrated the specificity of this method by cross-testing both groups of chemicals in both plants and nematodes. Copyright © 2018 John Wiley & Sons, Ltd.

Liquid chromatography tandem mass spectrometry method for the estimation of lamotrigine in human plasma: Application to a pharmacokinetic study

Directory of Open Access Journals (Sweden)

Santosh Ghatol

2013-04-01

Full Text Available A reliable, selective and sensitive liquid chromatography tandem mass spectrometry method was developed and validated for the quantification of lamotrigine in human plasma using lamotrigine-13C3, d3 as an internal standard. Analyte and internal standard were extracted from human plasma by solid-phase extraction and detected in positive ion mode by tandem mass spectrometry with electrospray ionization (ESI interface. Chromatographic separation was performed on a Chromolith® SpeedROD; RP-18e column (50−4.6 mm i.d. using acetonitrile: 5±0.1 mM ammonium formate solution (90:10, v/v as the mobile phase at a flow rate of 0.500 mL/min. The calibration curves were linear over the range of 5.02–1226.47 ng/mL with the lower limit of quantitation validated at 5.02 ng/mL. The analytes were found stable in human plasma through three freeze (−20 °C-thaw (ice-cold water bath cycles and under storage on bench-top in ice-cold water bath for at least 6.8 h, and also in the mobile phase at 10 °C for at least 57 h. The method has shown good reproducibility, as the intra- and inter-day precisions were within 3.0%, while the accuracies were within ±6.0% of nominal values. The validated LC–MS/MS method was applied for the evaluation of pharmacokinetic and bioequivalence parameters of lamotrigine after an oral administration of 50 mg lamotrigine tablet to thirty-two healthy adult male volunteers. Keywords: Lamotrigine, Liquid chromatography/tandem mass spectrometry, Solid phase extraction, Pharmacokinetic study

Validated method for the determination of perfluorinated compounds in placental tissue samples based on a simple extraction procedure followed by ultra-high performance liquid chromatography-tandem mass spectrometry analysis.

Science.gov (United States)

Martín, J; Rodríguez-Gómez, R; Zafra-Gómez, A; Alonso, E; Vílchez, J L; Navalón, A

2016-04-01

Xenobiotic exposure during pregnancy is inevitable. Determination of perfluorinated compounds (PFCs), chemicals described as environmental contaminants by Public Health Authorities due to their persistence, bioaccumulation and toxicity, is a challenge. In the present work, a method based on a simplified sample treatment involving freeze-drying, solvent extraction and dispersive clean-up of the extracts using C18 sorbents followed by an ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis was developed and validated for the determination of five perfluorinated carboxylic acids (C4-C8) and perfluorooctane sulfonate (PFOS) in placental tissue samples. The most influential parameters affecting the extraction method and clean-up were optimized using Design of Experiments (DOE). The method was validated using matrix-matched calibration. Found limits of detection (LODs) ranged from 0.03 to 2 ng g(-1) and limits of quantification (LOQs) from 0.08 to 6 ng g(-1), while inter- and intra-day variability was under 14% in all cases. Recovery rates for spiked samples ranged from 94% to 113%. The method was satisfactorily applied for the determination of compounds in human placental tissue samples collected at delivery from 25 randomly selected women. Copyright © 2015 Elsevier B.V. All rights reserved.

Method development and validation of liquid chromatography-tandem/mass spectrometry for aldosterone in human plasma: Application to drug interaction study of atorvastatin and olmesartan combination

Directory of Open Access Journals (Sweden)

Rakesh Das

2014-01-01

Full Text Available In the present investigation, a simple and sensitive liquid chromatography-tandem mass spectrometry (LC/MS/MS method was developed for the quantification of aldosterone (ALD a hormone responsible for blood pressure in human plasma. The developed method was validated and extended for application on human subjects to study drug interaction of atorvastatin (ATSV and olmesartan (OLM on levels of ALD. The ALD in plasma was extracted by liquid-liquid extraction with 5 mL dichloromethane/ethyl ether (60/40% v/v. The chromatographic separation of ALD was carried on Xterra, RP-Column C18 (150 mm× 4.6 mm × 3.5 μm at 30°C followed by four-step gradient program composed of methanol and water. Step 1 started with 35% methanol for first 1 min and changed linearly to 90% in next 1.5 min in Step 2. Step 3 lasted for next 2 min with 90% methanol. The method finally concluded with Step 4 to achieve initial concentration of methanol that is, 35% thus contributing the total method run time of 17.5 min. The flow rate was 0.25 mL/min throughout the process. The developed method was validated for specificity, accuracy, precision, stability, linearity, sensitivity, and recovery. The method was linear and found to be acceptable over the range of 50-800 ng/mL. The method was successfully applied for the drug interaction study of ATSV + OLM in combination against OLM treatment on blood pressure by quantifying changes in levels of ALD in hypertensive patients. The study revealed levels of ALD were significantly higher in ATSV + OLM treatment condition when compared to OLM as single treated condition. This reflects the reason of low effectiveness of ATSV + OLM in combination instead of synergistic activity.

Development and validation of a rapid multi-biomarker liquid chromatography/tandem mass spectrometry method to assess human exposure to mycotoxins.

Science.gov (United States)

Warth, Benedikt; Sulyok, Michael; Fruhmann, Philipp; Mikula, Hannes; Berthiller, Franz; Schuhmacher, Rainer; Hametner, Christian; Abia, Wilfred Angie; Adam, Gerhard; Fröhlich, Johannes; Krska, Rudolf

2012-07-15

Mycotoxins regularly occur in food worldwide and pose serious health risks to consumers. Since individuals can be exposed to a variety of these toxic secondary metabolites of fungi at the same time, there is a demand for proper analytical methods to assess human exposure by suitable biomarkers. This study reports on the development of a liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method for the quantitative measurement of 15 mycotoxins and key metabolites in human urine using polarity switching. Deoxynivalenol (DON), DON-3-O-glucuronide, DON-15-O-glucuronide (D15GlcA), de-epoxy DON, nivalenol (NIV), T-2 toxin, HT-2 toxin, zearalenone, zearalenone-14-O-glucuronide, α- and β-zearalenol, fumonisins B(1) and B(2) (FB(1), FB(2)), ochratoxin A (OTA) and aflatoxin M(1) (AFM(1)) were determined without the need for any cleanup using a rapid and simple dilute and shoot approach. Validation was performed in the range of 0.005-40 µg L(-1) depending on the analyte and expected urinary concentration levels. Apparent recoveries between 78 and 119% and interday precisions of 2-17% relative standard deviation (RSD) were achieved. The applicability of the method was demonstrated by the analysis of urine samples obtained from Cameroon. In naturally contaminated urine samples up to six biomarkers of exposure (AFM(1), DON, D15GlcA, NIV, FB(1), and OTA) were detected simultaneously. We conclude that the developed LC/MS/MS method is well suited to quantify multiple mycotoxin biomarkers in human urine down to the sub-ppb range within 18 min and without any prior cleanup. The co-occurrence of several mycotoxins in the investigated samples clearly emphasizes the great potential and importance of this method to assess exposure of humans and animals to naturally occurring mycotoxins. Copyright © 2012 John Wiley & Sons, Ltd.

A Selected Reaction Monitoring Mass Spectrometry Protocol for Validation of Proteomic Biomarker Candidates in Studies of Psychiatric Disorders.

Science.gov (United States)

Reis-de-Oliveira, Guilherme; Garcia, Sheila; Guest, Paul C; Cassoli, Juliana S; Martins-de-Souza, Daniel

2017-01-01

Most biomarker candidates arising from proteomic studies of psychiatric disorders have not progressed for use in clinical studies due to insufficient validation steps. Here we describe a selective reaction monitoring mass spectrometry (SRM-MS) approach that could be used as a follow-up validation tool of proteins identified in blood serum or plasma. This protocol specifically covers the stages of peptide selection and optimization. The increasing application of SRM-MS should enable fast, sensitive, and robust methods with the potential for use in clinical studies involving sampling of serum or plasma. Understanding the molecular mechanisms and identifying potential biomarkers for risk assessment, diagnosis, prognosis, and prediction of drug response goes toward the implementation of translational medicine strategies for improved treatment of patients with psychiatric disorders and other debilitating diseases.

Development and validation of a QuEChERS method coupled to liquid chromatography and high resolution mass spectrometry to determine pyrrolizidine and tropane alkaloids in honey.

Science.gov (United States)

Martinello, Marianna; Borin, Alice; Stella, Roberto; Bovo, Davide; Biancotto, Giancarlo; Gallina, Albino; Mutinelli, Franco

2017-11-01

Awareness about pyrrolizidine alkaloids (PAs) and tropane alkaloids (TAs) in food was recently raised by the European Food Safety Authority stressing the lack of data and gaps of knowledge required to improve the risk assessment strategy. The present study aimed at the elaboration and validation of a method to determine PAs and TAs in honey. QuEChERS sample treatment and liquid chromatography coupled to hybrid high resolution mass spectrometry, were used. The method resulted in good linearity (R 2 >0.99) and low limits of detection and quantification, ranging from 0.04 to 0.2µgkg -1 and from 0.1 to 0.7µgkg -1 respectively. Recoveries ranged from 92.3 to 114.8% with repeatability lying between 0.9 and 15.1% and reproducibility between 1.1 and 15.6%. These performances demonstrate the selectivity and sensitivity of the method for simultaneous trace detection and quantification of PAs and TAs in honey, verified through the analysis of forty commercial samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

International comparison of methods to test the validity of dead-time and pile-up corrections for high-precision. gamma. -ray spectrometry

Energy Technology Data Exchange (ETDEWEB)

Houtermans, H.; Schaerf, K.; Reichel, F. (International Atomic Energy Agency, Vienna (Austria)); Debertin, K. (Physikalisch-Technische Bundesanstalt, Braunschweig (Germany, F.R.))

1983-02-01

The International Atomic Energy Agency organized an international comparison of methods applied in high-precision ..gamma..-ray spectrometry for the correction of dead-time and pile-up losses. Results of this comparison are reported and discussed.

Validation of a liquid chromatography-tandem mass spectrometry method for the simultaneous determination of sulfonamides, trimethoprim and dapsone in muscle, egg, milk and honey.

Science.gov (United States)

Varenina, Ivana; Bilandžić, Nina; Kolanović, Božica Solomun; Božić, Đurđica; Sedak, Marija; Đokić, Maja; Varga, Ines

2016-01-01

A quantitative multi-residue method that includes 13 sulfonamides, trimethoprim and dapsone was developed and validated according to Commission Decision 2002/657/EC for muscle, milk egg and honey samples. For all matrices, the same extraction procedure was used. Samples were extracted with an acetone/dichloromethane mixture and cleaned up on aromatic sulfonic acid (SO3H) SPE cartridges. After elution and concentration steps, analytes were identified and quantified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Data were acquired according to the multiple reaction-monitoring approach (MRM) and analytes were quantified both by the isotope dilution and the matrix-matched approaches calculating the response factors for the scanned product ions. The developed method shows good linearity, specificity, precision (repeatability and within-laboratory reproducibility), and trueness. Estimated CCβ for sulfonamides ranged between 5.6 and 8.2 µg kg(-1) for eggs, between 11.1 and 69.9 µg kg(-1) for milk, between 64.7 and 87.9 µg kg(-1) for muscle, and between 2.7 and 5.3 µg kg(-1) for honey. CCβ values for dapsone were 3.1, 0.6, 0.7 and 1.5 µg kg(-1) and for trimethoprim were 3.1, 6.7, 81.7 and 3.0 µg kg(-1) calculated for eggs, milk, muscle and honey, respectively. Recovery for all matrices was in the range from 89.1% and 109.7%. In matrix effect testing, no significant deviations were found between different samples of muscle and milk; however, a matrix effect was observed when testing different types of honey. The validation results demonstrate that the method is suitable for routine veterinary drug analysis and confirmation of suspect samples.

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....

Development and validation of a liquid chromatography-tandem mass spectrometry method for topotecan determination in beagle dog plasma and its application in a bioequivalence study.

Science.gov (United States)

Ye, Ling; Shi, Jian; Wan, Shanhe; Yang, Xiaoshan; Wang, Ying; Zhang, Jiajie; Zheng, Dayong; Liu, Zhongqiu

2013-11-01

Topotecan (TPT) is an important anti-cancer drug that inhibits topoisomerase I. A sensitive and robust liquid chromatography-tandem mass spectrometry (LC-MS/MS) method that potentially determines TPT in beagle dog plasma is needed for a bioequivalence study of TPT formulations. We developed and validated LC-MS/MS to evaluate TPT in beagle dog plasma in terms of specificity, linearity, precision, accuracy, stability, extraction recovery and matrix effect. Plasma samples were treated with an Ostro(TM) sorbent plate (a robust and effective tool) to eliminate phospholipids and proteins before analysis. TPT and camptothecin (internal standard) were separated on an Acquity UPLC BEH C18 column (1.7 µm, 2.1 × 50 mm) with 0.1% formic acid and methanol as the mobile phase at a flow rate of 0.25 mL/min. TPT was analyzed using positive ion electrospray ionization in multiple-reaction monitoring mode. The obtained lower limit of quantitation was 1 ng/mL (signal-to-noise ratio > 10). The standard calibration curve for TPT was linear (correlation coefficient > 0.99) at the concentration range of 1-400 ng/mL. The intra-day and inter-day precision, accuracy, stability, extraction recovery and matrix effect of TPT were within the acceptable limits. The validated method was successfully applied in a bioequivalence study of TPT in healthy beagle dogs. Copyright © 2013 John Wiley & Sons, Ltd.

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.

Liquid chromatography tandem mass spectrometry method for simultaneous determination of metoprolol tartrate and ramipril in human plasma.

Science.gov (United States)

Gowda, K Veeran; Mandal, Uttam; Senthamil Selvan, P; Sam Solomon, W D; Ghosh, Animesh; Sarkar, Amlan Kanti; Agarwal, Sangita; Nageswar Rao, T; Pal, Tapan Kumar

2007-10-15

A simple, rapid, sensitive and specific liquid chromatography-tandem mass spectrometry method was developed and validated for quantification of metoprolol tartrate (MT) and ramipril, in human plasma. Both the drugs were extracted by liquid-liquid extraction with diethyl ether-dichloromethane (70:30, v/v). The chromatographic separation was performed on a reversed-phase C8 column with a mobile phase of 10 mM ammonium formate-methanol (3:97, v/v). The protonated analyte was quantitated in positive ionization by multiple reaction monitoring with a mass spectrometer. The method was validated over the concentration range of 5-500 ng/ml for metoprolol and ramipril in human plasma. The precursor to product ion transitions of m/z 268.0-103.10 and m/z 417.20-117.20 were used to measure metoprolol and ramipril, respectively.

Determination of methylmercury in marine biota samples with advanced mercury analyzer: method validation.

Science.gov (United States)

Azemard, Sabine; Vassileva, Emilia

2015-06-01

In this paper, we present a simple, fast and cost-effective method for determination of methyl mercury (MeHg) in marine samples. All important parameters influencing the sample preparation process were investigated and optimized. Full validation of the method was performed in accordance to the ISO-17025 (ISO/IEC, 2005) and Eurachem guidelines. Blanks, selectivity, working range (0.09-3.0ng), recovery (92-108%), intermediate precision (1.7-4.5%), traceability, limit of detection (0.009ng), limit of quantification (0.045ng) and expanded uncertainty (15%, k=2) were assessed. Estimation of the uncertainty contribution of each parameter and the demonstration of traceability of measurement results was provided as well. Furthermore, the selectivity of the method was studied by analyzing the same sample extracts by advanced mercury analyzer (AMA) and gas chromatography-atomic fluorescence spectrometry (GC-AFS). Additional validation of the proposed procedure was effectuated by participation in the IAEA-461 worldwide inter-laboratory comparison exercises. Copyright © 2014 Elsevier Ltd. All rights reserved.

A General Method for Targeted Quantitative Cross-Linking Mass Spectrometry.

Directory of Open Access Journals (Sweden)

Juan D Chavez

Full Text Available Chemical cross-linking mass spectrometry (XL-MS provides protein structural information by identifying covalently linked proximal amino acid residues on protein surfaces. The information gained by this technique is complementary to other structural biology methods such as x-ray crystallography, NMR and cryo-electron microscopy[1]. The extension of traditional quantitative proteomics methods with chemical cross-linking can provide information on the structural dynamics of protein structures and protein complexes. The identification and quantitation of cross-linked peptides remains challenging for the general community, requiring specialized expertise ultimately limiting more widespread adoption of the technique. We describe a general method for targeted quantitative mass spectrometric analysis of cross-linked peptide pairs. We report the adaptation of the widely used, open source software package Skyline, for the analysis of quantitative XL-MS data as a means for data analysis and sharing of methods. We demonstrate the utility and robustness of the method with a cross-laboratory study and present data that is supported by and validates previously published data on quantified cross-linked peptide pairs. This advance provides an easy to use resource so that any lab with access to a LC-MS system capable of performing targeted quantitative analysis can quickly and accurately measure dynamic changes in protein structure and protein interactions.

In house validation of a high resolution mass spectrometry Orbitrap-based method for multiple allergen detection in a processed model food.

Science.gov (United States)

Pilolli, Rosa; De Angelis, Elisabetta; Monaci, Linda

2018-02-13

In recent years, mass spectrometry (MS) has been establishing its role in the development of analytical methods for multiple allergen detection, but most analyses are being carried out on low-resolution mass spectrometers such as triple quadrupole or ion traps. In this investigation, performance provided by a high resolution (HR) hybrid quadrupole-Orbitrap™ MS platform for the multiple allergens detection in processed food matrix is presented. In particular, three different acquisition modes were compared: full-MS, targeted-selected ion monitoring with data-dependent fragmentation (t-SIM/dd2), and parallel reaction monitoring. In order to challenge the HR-MS platform, the sample preparation was kept as simple as possible, limited to a 30-min ultrasound-aided protein extraction followed by clean-up with disposable size exclusion cartridges. Selected peptide markers tracing for five allergenic ingredients namely skim milk, whole egg, soy flour, ground hazelnut, and ground peanut were monitored in home-made cookies chosen as model processed matrix. Timed t-SIM/dd2 was found the best choice as a good compromise between sensitivity and accuracy, accomplishing the detection of 17 peptides originating from the five allergens in the same run. The optimized method was validated in-house through the evaluation of matrix and processing effects, recoveries, and precision. The selected quantitative markers for each allergenic ingredient provided quantification of 60-100 μg ingred /g allergenic ingredient/matrix in incurred cookies.

Validation of an enzyme-linked immunosorbent assay screening method and a liquid chromatography-tandem mass spectrometry confirmation method for the identification and quantification of ketamine and norketamine in urine samples from Malaysia.

Science.gov (United States)

Harun, Norlida; Anderson, Robert A; Miller, Eleanor I

2009-01-01

An ELISA and a liquid chromatography-tandem mass spectrometry (LC-MS-MS) confirmation method were developed and validated for the identification and quantitation of ketamine and its major metabolite norketamine in urine samples. The Neogen ketamine microplate ELISA was optimized with respect to sample and enzyme conjugate volumes and the sample preincubation time before addition of the enzyme conjugate. The ELISA kit was validated to include an assessment of the dose-response curve, intra- and interday precision, limit of detection (LOD), and cross-reactivity. The sensitivity and specificity were calculated by comparison to the results from the validated LC-MS-MS confirmation method. An LC-MS-MS method was developed and validated with respect to LOD, lower limit of quantitation (LLOQ), linearity, recovery, intra- and interday precision, and matrix effects. The ELISA dose-response curve was a typical S-shaped binding curve, with a linear portion of the graph observed between 25 and 500 ng/mL for ketamine. The cross-reactivity of 200 ng/mL norketamine to ketamine was 2.1%, and no cross-reactivity was detected with 13 common drugs tested at 10,000 ng/mL. The ELISA LOD was calculated to be 5 ng/mL. Both intra- (n = 10) and interday (n = 50) precisions were below 5.0% at 25 ng/mL. The LOD for ketamine and norketamine was calculated statistically to be 0.6 ng/mL. The LLOQ values were also calculated statistically and were 1.9 ng/mL and 2.1 ng/mL for ketamine and norketamine, respectively. The test linearity was 0-1200 ng/mL with correlation coefficient (R(2)) > 0.99 for both analytes. Recoveries at 50, 500, and 1000 ng/mL range from 97.9% to 113.3%. Intra- (n = 5) and interday (n = 25) precisions between extracts for ketamine and norketamine were excellent (Royal Malaysian Police. Ketamine concentrations detected by LC-MS-MS ranged from 22 to 31,670 ng/mL, and norketamine concentrations ranged from 25 to 10,990 ng/mL. The concentrations of ketamine and norketamine

Development of a liquid chromatography–tandem mass spectrometry method for the determination of sulfonamides, trimethoprim and dapsone in honey and validation according to Commission Decision 2002/657/EC for banned compounds [corrected].

Science.gov (United States)

Economou, Anastasios; Petraki, Olympia; Tsipi, Despina; Botitsi, Eleni

2012-08-15

This work reports a sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for identification and quantification of seven sulfonamides, trimethoprim and dapsone in honey. The method is based on a solid-phase extraction (SPE) step of the target analytes with Oasis HLB cartridges after acidic hydrolysis of the honey sample to liberate the sugar-bound sulfonamides. Analysis was performed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the positive electro-spray ionization (ESI) mode with two different isotopically labeled internal standards with the view to improve the quantitative performance of the method. The method validation has been performed according to the Commission Decision 2002/657/EC; the average recoveries, measured at three concentration levels (1.5, 2.5 and 5.0 μg kg(-1)), have been estimated in the range 70 to 106% while the respective % relative standard deviations of the within-laboratory reproducibility ranged from 6 to 18%. Mean values of the expanded uncertainties calculated were in the range 22-41% at the 99% confidence level. Decision limit (CCα) and detection capability (CCβ) values were in the ranges 0.4-0.9 and 0.7-1.4 μg kg(-1), respectively. Matrix effects have been investigated demonstrating a moderate signal suppression/enhancement for most of the target compounds. The method described has been successfully applied to the analysis of honey samples; sulfamethoxazole, sulfathiazole and trimethoprim were detected in some cases. Copyright © 2012 Elsevier B.V. All rights reserved.

Method Development for Rapid Analysis of Natural Radioactive Nuclides Using Sector Field Inductively Coupled Plasma Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Lim, J.M.; Ji, Y.Y.; Lee, H.; Park, J.H.; Jang, M.; Chung, K.H.; Kang, M.J.; Choi, G.S. [Korea Atomic Energy Research Institute (Korea, Republic of)

2014-07-01

As an attempt to reduce the social costs and apprehension arising from radioactivity in the environment, an accurate and rapid assessment of radioactivity is highly desirable. Naturally occurring radioactive materials (NORM) are widely spread throughout the environment. The concern with radioactivity from these materials has therefore been growing for the last decade. In particular, radiation exposure in the industry when handling raw materials (e.g., coal mining and combustion, oil and gas production, metal mining and smelting, mineral sands (REE, Ti, Zr), fertilizer (phosphate), and building materials) has been brought to the public's attention. To decide the proper handling options, a rapid and accurate analytical method that can be used to evaluate the radioactivity of radionuclides (e.g., {sup 238}U, {sup 235}U, {sup 232}Th, {sup 226}Ra, and {sup 40}K) should be developed and validated. Direct measuring methods such as alpha spectrometry, a liquid scintillation counter (LSC), and mass-spectrometry are usually used for the measurement of radioactivity in NORM samples, and they encounter the most significant difficulties during pretreatment (e.g., purification, speciation, and dilution/enrichment). Since the pretreatment process consequently plays an important role in the measurement uncertainty, method development and validation should be performed. Furthermore, a-spectrometry has a major disadvantage of a long counting time, while it has a prominent measurement capability at a very low activity level of {sup 238}U, {sup 235}U, {sup 232}Th, and {sup 226}Ra. Contrary to the α-spectrometry method, a measurement technique using ICP-MS allow radioactivity in many samples to be measured in a short time period with a high degree of accuracy and precision. In this study, a method was developed for a rapid analysis of natural radioactive nuclides using ICP-MS. A sample digestion process was established using LiBO{sub 2} fusion and Fe co-precipitation. A magnetic

Method Development and Validation for UHPLC-MS-MS Determination of Hop Prenylflavonoids in Human Serum

OpenAIRE

Yuan, Yang; Qiu, Xi; Nikolic, Dejan; Dahl, Jeffrey H.; van Breemen, Richard B.

2012-01-01

Hops (Humulus lupulus L.) are used in the brewing of beer, and hop extracts containing prenylated compounds such as xanthohumol and 8-prenylnaringenin are under investigation as dietary supplements for cancer chemoprevention and for the management of hot flashes in menopausal women. To facilitate clinical studies of hop safety and efficacy, a selective, sensitive, and fast ultra-high pressure liquid chromatography tandem mass spectrometry (UHPLC-MS-MS) method was developed and validated for t...

A validated method for simultaneous screening and quantification of twenty-three benzodiazepines and metabolites plus zopiclone and zaleplone in whole blood by liquid-liquid extraction and ultra-performance liquid chromatography- tandem mass spectrometry

DEFF Research Database (Denmark)

Simonsen, Kirsten Wiese; Hermansson, Sigurd; Steentoft, Anni

2010-01-01

, oxazepam, temazepam, triazolam, zaleplon, and zopiclone. Whole blood from drug-free volunteers was used for all experiments. Blood samples (0.200 g) were extracted with ethyl acetate at pH 9. Target drugs were quantified using a Waters ACQUITY UPLC system coupled to a Waters Quattro Premier XE triple......An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS-MS) method for detection of 23 benzodiazepines and related compounds in whole blood was developed and validated. The method is used for screening and quantitation of benzodiazepines in whole blood received from autopsy...... quadrupole in positive electrospray ionization, multiple reaction monitoring mode. The use of deuterated internal standards for most compounds verified that the accuracy of the method was not influenced by matrix effects. Extraction recoveries were 73-108% for all analytes. Lower limits of quantification...

Validation of a hydride generation atomic absorption spectrometry methodology for determination of mercury in fish designed for application in the Brazilian national residue control plan.

Science.gov (United States)

Damin, Isabel C F; Santo, Maria A E; Hennigen, Rosmari; Vargas, Denise M

2013-01-01

In the present study, a method for the determination of mercury (Hg) in fish was validated according to ISO/IEC 17025, INMETRO (Brazil), and more recent European recommendations (Commission Decision 2007/333/EC and 2002/657/EC) for implementation in the Brazilian Residue Control Plan (NRCP) in routine applications. The parameters evaluated in the validation were investigated in detail. The results obtained for limit of detection and quantification were respectively, 2.36 and 7.88 μg kg(-1) of Hg. While the recovery varies between 90-96%. The coefficient of variation was of 4.06-8.94% for the repeatability. Furthermore, a comparison using an external proficiency testing scheme was realized. The results of method validated for the determination of the mercury in fish by Hydride generation atomic absorption spectrometry were considered suitable for implementation in routine analysis.

Full validation of a method for the determination of drugs of abuse in non-mineralized dental biofilm using liquid chromatography-tandem mass spectrometry and application to postmortem samples.

Science.gov (United States)

Henkel, Kerstin; Altenburger, Markus J; Auwärter, Volker; Neukamm, Merja A

2018-01-01

Alternative matrices play a major role in postmortem forensic toxicology, especially if common matrices (like body fluids or hair) are not available. Incorporation of illicit and medicinal drugs into non-mineralized dental biofilm (plaque) seems likely but has not been investigated so far. Analysis of plaque could therefore extend the spectrum of potentially used matrices in postmortem toxicology. For this reason, a rapid, simple and sensitive method for the extraction, determination and quantification of ten drugs of abuse from plaque using liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and fully validated. Amphetamine, methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxy-N-ethylamphetamine (MDEA), 3,4-methylenedioxyamphetamine (MDA), cocaine, benzoylecgonine, morphine, codeine and 6-acetylmorphine were extracted from 2mg of dried and powdered plaque via ultrasonication with acetonitrile. The extracts were analyzed on a triple-quadrupole linear ion trap mass spectrometer in scheduled multiple reaction monitoring mode (sMRM). The method was fully validated and proved accurate, precise, selective and specific with satisfactory linearity within the calibrated ranges. The lower limit of quantification was 10-15pgmg -1 for all compounds except for MDA (100pgmg -1 ) and amphetamine (200pgmg -1 ). The method has been successfully applied to three authentic postmortem samples with known drug history. Amphetamine, MDMA, cocaine, benzoylecgonine, morphine and codeine could be detected in these cases in concentrations ranging from 18pgmg -1 for cocaine to 1400pgmg -1 for amphetamine. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Method validation for determination of heavy metals in wine and slightly alcoholic beverages by ICP-MS

International Nuclear Information System (INIS)

Voica, Cezara; Dehelean, Adriana; Pamula, A

2009-01-01

The Organisation International de la Vigne et du Vin (OIV) fixed an uppermost level for some heavy metals in wine. Consequently, the need to determine very low concentration of elements that may be present in wine in trace and ultra trace levels occurred. Inductively coupled plasma mass spectrometry ICP-MS is considered an excellent tool for detailed characterization of the elementary composition of many samples, including samples of drinks. In this study a method of quantitative analysis for the determination of toxic metals (Cr, As, Cd, Ni, Hg, Pb) in wines and slightly alcoholic beverages by ICP-MS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, the minimum detection limit, the limit of quantification, accuracy and uncertainty.

Method validation for determination of heavy metals in wine and slightly alcoholic beverages by ICP-MS

Energy Technology Data Exchange (ETDEWEB)

Voica, Cezara; Dehelean, Adriana; Pamula, A, E-mail: cezara.voica@itim-cj.r [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania)

2009-08-01

The Organisation International de la Vigne et du Vin (OIV) fixed an uppermost level for some heavy metals in wine. Consequently, the need to determine very low concentration of elements that may be present in wine in trace and ultra trace levels occurred. Inductively coupled plasma mass spectrometry ICP-MS is considered an excellent tool for detailed characterization of the elementary composition of many samples, including samples of drinks. In this study a method of quantitative analysis for the determination of toxic metals (Cr, As, Cd, Ni, Hg, Pb) in wines and slightly alcoholic beverages by ICP-MS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, the minimum detection limit, the limit of quantification, accuracy and uncertainty.

Validated ultra-performance liquid chromatography-tandem mass spectrometry method for analyzing LSD, iso-LSD, nor-LSD, and O-H-LSD in blood and urine.

Science.gov (United States)

Chung, Angela; Hudson, John; McKay, Gordon

2009-06-01

The Royal Canadian Mounted Police Forensic Science and Identification Services was looking for a confirmatory method for lysergic acid diethylamide (LSD). As a result, an ultra-performance liquid chromatography-tandem mass spectrometry method was validated for the confirmation and quantitation of LSD, iso-LSD, N-demethyl-LSD (nor-LSD), and 2-oxo-3-hydroxy-LSD (O-H-LSD). Relative retention time and ion ratios were used as identification parameters. Limits of detection (LOD) in blood were 5 pg/mL for LSD and iso-LSD and 10 pg/mL for nor-LSD and O-H-LSD. In urine, the LOD was 10 pg/mL for all analytes. Limits of quantitation (LOQ) in blood and urine were 20 pg/mL for LSD and iso-LSD and 50 pg/mL for nor-LSD and O-H-LSD. The method was linear, accurate, and precise from 10 to 2000 pg/mL in blood and 20 to 2000 pg/mL in urine for LSD and iso-LSD and from 20 to 2000 pg/mL in blood and 50 to 2000 pg/mL in urine for nor-LSD and O-H-LSD with a coefficient of determination (R(2)) > or = 0.99. The method was applied to blinded biological control samples and biological samples taken from a suspected LSD user. This is the first reported detection of O-H-LSD in blood from a suspected LSD user.

The Determination of Composite Elements in Zircaloy-2 by X-Ray Fluorescence and Emission Spectrometry Method

International Nuclear Information System (INIS)

Dian Anggraini; Rosika Kriswarini; Yusuf N

2007-01-01

Analysis of composing elements in zircaloy-2 has been done by Emission Spectrometry method and X-Ray Fluorescence (XRF). The aim of the analysis is to verify conformity between composing elements in zircaloy-2 and the material certificate. Spectrometry Emission method has higher sensitivity in element determination of a material than that of XRF method, so can be estimated that emission spectrometry method has higher accuracy than that of XRF method. The result of qualitative analysis by Emission Spectrometry indicate that the composing elements in zircaloy-2 were Sn, Cr and Ni. However, the qualitative analysis result by XRF method indicated that the composing elements in zircaloy 2 were Sn, Cr, Ni and Fe. Fe element can not be analysed by Emission Spectrometry method because Emission Spectrometer did not equipped with Fe detector. The quantitative analysis result of the composing elements in the material with both methods showed that Sn, Cr and Ni concentration of zircaloy 2 existed in concentration ranges of the material certificate. Result of statistical test (F and t-test) of analysis result of both methods can be used for analyzing composing elements in zircaloy 2. Emission Spectrometry method was more sensitive and accurate for determining Cr and Ni element in zircaloy 2 than that of emission Spectrometry method but both methods had same accuracy. The precision of measurement of Sn, Cr and Ni element using XRF method was better than that of Emission spectrometry method. (author)

A validated inductively coupled plasma mass spectrometry (ICP-MS) method for the quantification of total platinum content in plasma, plasma ultrafiltrate, urine and peritoneal fluid.

Science.gov (United States)

Lemoine, Lieselotte; Thijssen, Elsy; Noben, Jean-Paul; Adriaensens, Peter; Carleer, Robert; Speeten, Kurt Van der

2018-04-15

Oxaliplatin is a platinum (Pt) 1 containing antineoplastic agent that is applied in current clinical practice for the treatment of colon and appendiceal neoplasms. A fully validated, highly sensitive, high throughput inductively coupled plasma mass spectrometry (ICP-MS) method is provided to quantify the total Pt content in plasma, plasma ultrafiltrate, urine and peritoneal fluid. In this ICP-MS approach, the only step of sample preparation is a 1000-fold dilution in 0.5% nitric acid, allowing the analysis of 17 samples per hour. Detection of Pt was achieved over a linear range of 0.01-100 ng/mL. The limit of quantification was 18.0 ng/mL Pt in plasma, 8.0 ng/mL in ultrafiltrate and 6.1 ng/mL in urine and peritoneal fluid. The ICP-MS method was further validated for inter-and intraday precision and accuracy (≤15%), recovery, robustness and stability. Short-term storage of the biofluids, for 14 days, can be performed at -4 °C, -24 °C and -80 °C. As to long-term stability, up to 5 months, storage at -80 °C is encouraged. Furthermore, a timeline assessing the total and unbound Pt fraction in plasma and ultrafiltrate over a period of 45 h is provided. Following an incubation period of 5 h at 37 °C, 19-21% of Pt was recovered in the ultrafiltrate, emphasizing the extensive and rapid binding of oxaliplatin-derived Pt to plasma proteins. The described method can easily be implemented in a routine setting for pharmacokinetic studies in patients treated with oxaliplatin-based hyperthermic intraperitoneal perioperative chemotherapy. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparison of in-situ gamma ray spectrometry measurements with conventional methods in determination natural and artificial nuclides in soil

International Nuclear Information System (INIS)

Al-Masri, M. S.; Doubal, A. W.

2010-12-01

Two nuclear analytical techniques (In-Situ Gamma ray spectrometry and laboratory gamma ray spectrometry) for determination of natural and artificial radionuclides in soil have been validated. The first technique depends on determination of radioactivity content of representative samples of the studied soil after laboratory preparation, while the second technique is based on direct determination of radioactivity content of soil using in-situ gamma-ray spectrometer. Analytical validation parameter such as detection limits, repeatability, reproducibility in addition to measurement uncertainties were estimated and compared for both techniques. Comparison results have shown that the determination of radioactivity in soil should apply the two techniques together where each of techniques is characterized by its low detection limit and uncertainty suitable for defined application of measurement. Radioactive isotopes in various locations were determined using the two methods by measuring 40 k, 238 U,and 137 Cs. The results showed that there are differences in attenuation factors due to soil moisture content differences; wet weight corrections should be applied when the two techniques are compared. (author)

Comparison of conventional liquid chromatography-tandem mass spectrometry versus microflow liquid chromatography-tandem mass spectrometry within the framework of full method validation for simultaneous quantification of 40 antidepressants and neuroleptics in whole blood.

Science.gov (United States)

Steuer, Andrea E; Poetzsch, Michael; Koenig, Magdalena; Tingelhoff, Eva; Staeheli, Sandra N; Roemmelt, Andreas T; Kraemer, Thomas

2015-02-13

Microflow liquid chromatography (MFLC) coupled to mass spectrometry (MS) is claimed to improve analysis throughput, reduce matrix effects and lower mobile phase consumption. This statement was checked within the framework of method validation of a multi-analyte procedure in clinical and forensic toxicology employing MFLC-MS/MS and conventional LC-MS/MS. 200 μL whole blood were spiked with 50 μL internal standard mixture and extracted by protein precipitation. The concentrated extract was separated into two vials. One was analyzed using a Thermo Fisher Ultimate liquid chromatography system coupled to an ABSciex 5500 QTrap mass spectrometer (LC-MS/MS) and one by an ABSciex Eksigent Microflow LC system coupled to an ABSciex 4500 linear ion trap quadrupole MS (MFLC-MS/MS). Both methods were fully validated and compared in terms of selectivity, stability, limits, calibration model, recovery (RE), matrix effects (ME), bias, imprecision and beta tolerance interval for 40 antidepressants and neuroleptics including 9 metabolites. Both methods had comparable LODs, LOQs and calibration models with some exceptions. The MFLC system showed slightly higher coefficients of variation (CVs) in the RE experiments. ME were reproducible in both systems but with lower CVs in the conventional LC system. Acceptance criteria for imprecision and bias were fulfilled for 32 analytes on the LC and for 28 analytes on the MFLC system. Beta tolerance intervals indicated better reproducibility in terms of narrower intervals for the conventional LC system. The advantages of the MFLC system were low mobile phase consumption, short run time, and better peak separation. The systems were comparable in terms of peak interference, LOD, ME, bias and imprecision. The advantages of the conventional LC system were more data points per peak, linear calibration models, stable retention times and better beta tolerance intervals. Due to higher robustness, the conventional LC system was finally chosen for

Rapid method for the sequential measurement of isotopes of Am and Pu in liquid matrices by alpha spectrometry

International Nuclear Information System (INIS)

Mantero Cabrera, J.

2014-01-01

: In radiological emergencies it's necessary a fast response from the laboratories in the quantification of certain radionuclides, in order to take decisions. In these cases, is the reaction time the key parameter to consider (without neglecting the quality of the measurement). In this work, it is shown a method for aqueous matrices that generates Pu and Am isotopes sources in one single day of work, to be measured subsequently by alpha spectrometry. The developed methodology has been validated through its application to reference samples and also taking part intercom- parison exercises, having in both cases, satisfactory results. This way, we check the validity of this fast method that let us generate in 24 hours (since the sample arrives our laboratory), one measurement with a Minimun Detectable Activity (MDA) of about 0.004Bq/L for Pu and Am isotopes in liquid matrices. [es

In-situ gamma spectrometry method for determination of environmental gamma dose

International Nuclear Information System (INIS)

Conti, Claudio de Carvalho

1995-07-01

This work tries to establish a methodology for germanium detectors calibration, normally used for in situ gamma ray spectrometry, for determining the environmental exposure rate in function of the energy of the incident photons. For this purpose a computer code has been developed, based on the stripping method, for the computational spectra analysis to calculate the contribution of the partial absorption of the gamma rays (Compton effect) in the active and nonactive parts of the detector. The resulting total absorption spectrum is then converted to fluence distribution in function of the energy for the photons reaching the detector, which is then used to calculate the exposure rate or kerma in air. The unfolding and fluency convention parameters are determined by detector calibration using point gamma sources. The method is validated by comparison of the results against the calculated exposure rate at a point of interest for the standards. This method is used for the direct measurement of the exposure rate distribution in function of the energy at the site, in situ measurement technic, leading to rapid results during an emergency situation and also used for indoor measurements. (author)

Development and validation of a hydrophilic interaction chromatography-mass spectrometry assay for taurine and methionine in matrices rich in carbohydrates.

Science.gov (United States)

de Person, Marine; Hazotte, Aurélie; Elfakir, Claire; Lafosse, Michel

2005-07-22

A new procedure based on hydrophilic interaction chromatography coupled to tandem mass spectrometry (ionisation process by pneumatically assisted electrospray in negative ion mode), is developed and validated for the simultaneous determination of underivatised taurine and methionine in beverages rich in carbohydrates such as energy drinks. No initial clean-up procedure and no sample derivatisation are required. Satisfactory analysis was obtained on an Astec apHera NH2 (150 mm x 4.6 mm; 5 microm) column with methanol-water (60/40) as mobile phase. The method was validated in terms of specificity, detection limits, linearity, accuracy, precision and stability, using threonine as internal standard. The potential effects of matrix and endogenous amino acid content were also examined. The limits of detection in the beverage varied from 20 microg L(-1) for taurine to 50 micro L(-1) for methionine.

Determination of methylmercury in marine sediment samples: Method validation and occurrence data

Energy Technology Data Exchange (ETDEWEB)

Carrasco, Luis; Vassileva, Emilia, E-mail: e.vasileva-veleva@iaea.org

2015-01-01

Highlights: • A method for MeHg determination at trace level in marine sediments is completely validated. • Validation is performed according to ISO-17025 and Eurachem guidelines. • The extraction efficiency of four sample preparation procedures is evaluated. • The uncertainty budget is used as a tool for evaluation of main uncertainty contributors. • Comparison with independent methods yields good agreement within stated uncertainty. - Abstract: The determination of methylmercury (MeHg) in sediment samples is a difficult task due to the extremely low MeHg/THg (total mercury) ratio and species interconversion. Here, we present the method validation of a cost-effective fit-for-purpose analytical procedure for the measurement of MeHg in sediments, which is based on aqueous phase ethylation, followed by purge and trap and hyphenated gas chromatography–pyrolysis–atomic fluorescence spectrometry (GC–Py–AFS) separation and detection. Four different extraction techniques, namely acid and alkaline leaching followed by solvent extraction and evaporation, microwave-assisted extraction with 2-mercaptoethanol, and acid leaching, solvent extraction and back extraction into sodium thiosulfate, were examined regarding their potential to selectively extract MeHg from estuarine sediment IAEA-405 certified reference material (CRM). The procedure based on acid leaching with HNO{sub 3}/CuSO{sub 4}, solvent extraction and back extraction into Na{sub 2}S{sub 2}O{sub 3} yielded the highest extraction recovery, i.e., 94 ± 3% and offered the possibility to perform the extraction of a large number of samples in a short time, by eliminating the evaporation step. The artifact formation of MeHg was evaluated by high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC–ICP–MS), using isotopically enriched Me{sup 201}Hg and {sup 202}Hg and it was found to be nonexistent. A full validation approach in line with ISO 17025 and

Determination of methylmercury in marine sediment samples: Method validation and occurrence data

International Nuclear Information System (INIS)

Carrasco, Luis; Vassileva, Emilia

2015-01-01

Highlights: • A method for MeHg determination at trace level in marine sediments is completely validated. • Validation is performed according to ISO-17025 and Eurachem guidelines. • The extraction efficiency of four sample preparation procedures is evaluated. • The uncertainty budget is used as a tool for evaluation of main uncertainty contributors. • Comparison with independent methods yields good agreement within stated uncertainty. - Abstract: The determination of methylmercury (MeHg) in sediment samples is a difficult task due to the extremely low MeHg/THg (total mercury) ratio and species interconversion. Here, we present the method validation of a cost-effective fit-for-purpose analytical procedure for the measurement of MeHg in sediments, which is based on aqueous phase ethylation, followed by purge and trap and hyphenated gas chromatography–pyrolysis–atomic fluorescence spectrometry (GC–Py–AFS) separation and detection. Four different extraction techniques, namely acid and alkaline leaching followed by solvent extraction and evaporation, microwave-assisted extraction with 2-mercaptoethanol, and acid leaching, solvent extraction and back extraction into sodium thiosulfate, were examined regarding their potential to selectively extract MeHg from estuarine sediment IAEA-405 certified reference material (CRM). The procedure based on acid leaching with HNO 3 /CuSO 4 , solvent extraction and back extraction into Na 2 S 2 O 3 yielded the highest extraction recovery, i.e., 94 ± 3% and offered the possibility to perform the extraction of a large number of samples in a short time, by eliminating the evaporation step. The artifact formation of MeHg was evaluated by high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC–ICP–MS), using isotopically enriched Me 201 Hg and 202 Hg and it was found to be nonexistent. A full validation approach in line with ISO 17025 and Eurachem guidelines was followed

Test and validation of the iterative code for the neutrons spectrometry and dosimetry: NSDUAZ

International Nuclear Information System (INIS)

Reyes H, A.; Ortiz R, J. M.; Reyes A, A.; Castaneda M, R.; Solis S, L. O.; Vega C, H. R.

2014-08-01

In this work was realized the test and validation of an iterative code for neutronic spectrometry known as Neutron Spectrometry and Dosimetry of the Universidad Autonoma de Zacatecas (NSDUAZ). This code was designed in a user graph interface, friendly and intuitive in the environment programming of LabVIEW using the iterative algorithm known as SPUNIT. The main characteristics of the program are: the automatic selection of the initial spectrum starting from the neutrons spectra catalog compiled by the International Atomic Energy Agency, the possibility to generate a report in HTML format that shows in graph and numeric way the neutrons flowing and calculates the ambient dose equivalent with base to this. To prove the designed code, the count rates of a spectrometer system of Bonner spheres were used with a detector of 6 LiI(Eu) with 7 polyethylene spheres with diameter of 0, 2, 3, 5, 8, 10 and 12. The count rates measured with two neutron sources: 252 Cf and 239 PuBe were used to validate the code, the obtained results were compared against those obtained using the BUNKIUT code. We find that the reconstructed spectra present an error that is inside the limit reported in the literature that oscillates around 15%. Therefore, it was concluded that the designed code presents similar results to those techniques used at the present time. (Author)

Validation of an ultra-high-performance liquid chromatography-tandem mass spectrometry method to quantify illicit drug and pharmaceutical residues in wastewater using accuracy profile approach.

Science.gov (United States)

Hubert, Cécile; Roosen, Martin; Levi, Yves; Karolak, Sara

2017-06-02

The analysis of biomarkers in wastewater has become a common approach to assess community behavior. This method is an interesting way to estimate illicit drug consumption in a given population: by using a back calculation method, it is therefore possible to quantify the amount of a specific drug used in a community and to assess the consumption variation at different times and locations. Such a method needs reliable analytical data since the determination of a concentration in the ngL -1 range in a complex matrix is difficult and not easily reproducible. The best analytical method is liquid chromatography - mass spectrometry coupling after solid-phase extraction or on-line pre-concentration. Quality criteria are not specially defined for this kind of determination. In this context, it was decided to develop an UHPLC-MS/MS method to analyze 10 illicit drugs and pharmaceuticals in wastewater treatment plant influent or effluent using a pre-concentration on-line system. A validation process was then carried out using the accuracy profile concept as an innovative tool to estimate the probability of getting prospective results within specified acceptance limits. Influent and effluent samples were spiked with known amounts of the 10 compounds and analyzed three times a day for three days in order to estimate intra-day and inter-day variations. The matrix effect was estimated for each compound. The developed method can provide at least 80% of results within ±25% limits except for compounds that are degraded in influent. Copyright © 2017 Elsevier B.V. All rights reserved.

Classification-based comparison of pre-processing methods for interpretation of mass spectrometry generated clinical datasets

Directory of Open Access Journals (Sweden)

Hoefsloot Huub CJ

2009-05-01

Full Text Available Abstract Background Mass spectrometry is increasingly being used to discover proteins or protein profiles associated with disease. Experimental design of mass-spectrometry studies has come under close scrutiny and the importance of strict protocols for sample collection is now understood. However, the question of how best to process the large quantities of data generated is still unanswered. Main challenges for the analysis are the choice of proper pre-processing and classification methods. While these two issues have been investigated in isolation, we propose to use the classification of patient samples as a clinically relevant benchmark for the evaluation of pre-processing methods. Results Two in-house generated clinical SELDI-TOF MS datasets are used in this study as an example of high throughput mass-spectrometry data. We perform a systematic comparison of two commonly used pre-processing methods as implemented in Ciphergen ProteinChip Software and in the Cromwell package. With respect to reproducibility, Ciphergen and Cromwell pre-processing are largely comparable. We find that the overlap between peaks detected by either Ciphergen ProteinChip Software or Cromwell is large. This is especially the case for the more stringent peak detection settings. Moreover, similarity of the estimated intensities between matched peaks is high. We evaluate the pre-processing methods using five different classification methods. Classification is done in a double cross-validation protocol using repeated random sampling to obtain an unbiased estimate of classification accuracy. No pre-processing method significantly outperforms the other for all peak detection settings evaluated. Conclusion We use classification of patient samples as a clinically relevant benchmark for the evaluation of pre-processing methods. Both pre-processing methods lead to similar classification results on an ovarian cancer and a Gaucher disease dataset. However, the settings for pre

MERCURY QUANTIFICATION IN SOILS USING THERMAL DESORPTION AND ATOMIC ABSORPTION SPECTROMETRY: PROPOSAL FOR AN ALTERNATIVE METHOD OF ANALYSIS

Directory of Open Access Journals (Sweden)

Liliane Catone Soares

2015-08-01

Full Text Available Despite the considerable environmental importance of mercury (Hg, given its high toxicity and ability to contaminate large areas via atmospheric deposition, little is known about its activity in soils, especially tropical soils, in comparison with other heavy metals. This lack of information about Hg arises because analytical methods for determination of Hg are more laborious and expensive compared to methods for other heavy metals. The situation is even more precarious regarding speciation of Hg in soils since sequential extraction methods are also inefficient for this metal. The aim of this paper is to present a technique of thermal desorption associated with atomic absorption spectrometry, TDAAS, as an efficient tool for quantitative determination of Hg in soils. The method consists of the release of Hg by heating, followed by its quantification by atomic absorption spectrometry. It was developed by constructing calibration curves in different soil samples based on increasing volumes of standard Hg2+ solutions. Performance, accuracy, precision, and quantification and detection limit parameters were evaluated. No matrix interference was detected. Certified reference samples and comparison with a Direct Mercury Analyzer, DMA (another highly recognized technique, were used in validation of the method, which proved to be accurate and precise.

Development of liquid chromatography-tandem mass spectrometry methods for the quantitation of Anisakis simplex proteins in fish.

Science.gov (United States)

Fæste, Christiane Kruse; Moen, Anders; Schniedewind, Björn; Haug Anonsen, Jan; Klawitter, Jelena; Christians, Uwe

2016-02-05

The parasite Anisakis simplex is present in many marine fish species that are directly used as food or in processed products. The anisakid larvae infect mostly the gut and inner organs of fish but have also been shown to penetrate into the fillet. Thus, human health can be at risk, either by contracting anisakiasis through the consumption of raw or under-cooked fish, or by sensitisation to anisakid proteins in processed food. A number of different methods for the detection of A. simplex in fish and products thereof have been developed, including visual techniques and PCR for larvae tracing, and immunological assays for the determination of proteins. The recent identification of a number of anisakid proteins by mass spectrometry-based proteomics has laid the groundwork for the development of two quantitative liquid chromatography-tandem mass spectrometry methods for the detection of A. simplex in fish that are described in the present study. Both, the label-free semi-quantitative nLC-nESI-Orbitrap-MS/MS (MS1) and the heavy peptide-applying absolute-quantitative (AQUA) LC-TripleQ-MS/MS (MS2) use unique reporter peptides derived from anisakid hemoglobin and SXP/RAL-2 protein as analytes. Standard curves in buffer and in salmon matrix showed limits of detection at 1μg/mL and 10μg/mL for MS1 and 0.1μg/mL and 2μg/mL for MS2. Preliminary method validation included the assessment of sensitivity, repeatability, reproducibility, and applicability to incurred and naturally-contaminated samples for both assays. By further optimization and full validation in accordance with current recommendations the LC-MS/MS methods could be standardized and used generally as confirmative techniques for the detection of A. simplex protein in fish. Copyright © 2016 Elsevier B.V. All rights reserved.

Validation by theoretical approach to the experimental estimation of efficiency for gamma spectrometry of gas in 100 ml standard flask

International Nuclear Information System (INIS)

Mohan, V.; Chudalayandi, K.; Sundaram, M.; Krishnamony, S.

1996-01-01

Estimation of gaseous activity forms an important component of air monitoring at Madras Atomic Power Station (MAPS). The gases of importance are argon 41 an air activation product and fission product noble gas xenon 133. For estimating the concentration, the experimental method is used in which a grab sample is collected in a 100 ml volumetric standard flask. The activity of gas is then computed by gamma spectrometry using a predetermined efficiency estimated experimentally. An attempt is made using theoretical approach to validate the experimental method of efficiency estimation. Two analytical models named relative flux model and absolute activity model were developed independently of each other. Attention is focussed on the efficiencies for 41 Ar and 133 Xe. Results show that the present method of sampling and analysis using 100 ml volumetric flask is adequate and acceptable. (author). 5 refs., 2 tabs

Method validation using weighted linear regression models for quantification of UV filters in water samples.

Science.gov (United States)

da Silva, Claudia Pereira; Emídio, Elissandro Soares; de Marchi, Mary Rosa Rodrigues

2015-01-01

This paper describes the validation of a method consisting of solid-phase extraction followed by gas chromatography-tandem mass spectrometry for the analysis of the ultraviolet (UV) filters benzophenone-3, ethylhexyl salicylate, ethylhexyl methoxycinnamate and octocrylene. The method validation criteria included evaluation of selectivity, analytical curve, trueness, precision, limits of detection and limits of quantification. The non-weighted linear regression model has traditionally been used for calibration, but it is not necessarily the optimal model in all cases. Because the assumption of homoscedasticity was not met for the analytical data in this work, a weighted least squares linear regression was used for the calibration method. The evaluated analytical parameters were satisfactory for the analytes and showed recoveries at four fortification levels between 62% and 107%, with relative standard deviations less than 14%. The detection limits ranged from 7.6 to 24.1 ng L(-1). The proposed method was used to determine the amount of UV filters in water samples from water treatment plants in Araraquara and Jau in São Paulo, Brazil. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of a multiresidue method for the determination of endocrine disrupters in fish fillet using gas chromatography-triple quadrupole tandem mass spectrometry.

Science.gov (United States)

Munaretto, Juliana S; Ferronato, Giovana; Ribeiro, Lucila C; Martins, Manoel L; Adaime, Martha B; Zanella, Renato

2013-11-15

Endocrine Disrupter Compounds (EDCs) are responsible for alterations in the endocrine system functions. Aquatic organisms are able to accumulate EDCs residues, being the major source of contamination for top predators and human consumers. This study aimed to develop and validate a method for the determination of 40 EDCs in fish fillet using modified QuEChERS and Gas Chromatography coupled with Mass Spectrometry in tandem (GC-MS/MS). A factorial design was used to optimize the extraction procedure. Method validation presented recoveries from 70.1% to 120.0% with RSDfish fillet from different species and residues of bisphenol A, chlorpyrifos and bifenthrin were detected. The proposed method proved to be effective for the determination of EDCs in fish fillet at very low concentration levels. © 2013 Elsevier B.V. All rights reserved.

New advanced in alpha spectrometry by liquid scintillation methods

International Nuclear Information System (INIS)

McDowell, W.J.; Case, G.N.

1979-01-01

Although the ability to count alpha particles by liquid scintillation methods has been long recognized, limited use has been made of the method because of problems of high background and alpha energy identification. In recent years some new developments in methods of introducing the alpha-emitting nuclide to the scintillator, in detector construction, and in electronics for processing the energy analog and time analog signals from the detector have allowed significant alleviation of the problems of alpha spectrometry by liquid scintillation. Energy resolutions of 200 to 300 keV full peak width at half maximum and background counts of 99% of all beta plus gamma interference is now possible. Alpha liquid scintillation spectrometry is now suitable for a wide range of applications, from the accurate quantitative determination of relatively large amounts of known nuclides in laboratory-generated samples to the detection and identification of very small, subpicocurie amounts of alpha emitters in environmental-type samples. Suitable nuclide separation procedures, sample preparation methods, and instrument configurations are available for a variety of analyses

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

Validation of a method to measure plutonium levels in marine sediments in Cuba

International Nuclear Information System (INIS)

Sibello Hernández, Rita Y.; Cartas Aguila, Héctor A.; Cozzella, María Letizia

2008-01-01

The main objective of this research was to develop and to validate a method of radiochemical separation of plutonium, suitable from the economic and practical point of view, in Cuba conditions. This method allowed to determine plutonium activity levels in the marine sediments from Cienfuegos Bay. The selected method of radiochemical separation was that of anionic chromatography and the measure technique was the quadrupole inductively coupled plasma mass spectrometry. The method was applied to a certified reference material, six repetitions were carried out and a good correspondence between the average measured value and the average certified value of plutonium was achieved, so the trueness of the method was demonstrated. It was also proven the precision of the method, since it was obtained a variation coefficient of 11% at 95% confidence level. The obtained results show that the presence of plutonium in the analyzed marine sediment samples is only due to the global radioactive fallout. (author)

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.

InSourcerer: a high-throughput method to search for unknown metabolite modifications by mass spectrometry.

Science.gov (United States)

Mrzic, Aida; Lermyte, Frederik; Vu, Trung Nghia; Valkenborg, Dirk; Laukens, Kris

2017-09-15

Using mass spectrometry, the analysis of known metabolite structures has become feasible in a systematic high-throughput fashion. Nevertheless, the identification of previously unknown structures remains challenging, partially because many unidentified variants originate from known molecules that underwent unexpected modifications. Here, we present a method for the discovery of unknown metabolite modifications and conjugate metabolite isoforms in a high-throughput fashion. The method is based on user-controlled in-source fragmentation which is used to induce loss of weakly bound modifications. This is followed by the comparison of product ions from in-source fragmentation and collision-induced dissociation (CID). Diagonal MS 2 -MS 3 matching allows the detection of unknown metabolite modifications, as well as substructure similarities. As the method relies heavily on the advantages of in-source fragmentation and its ability to 'magically' elucidate unknown modification, we have named it inSourcerer as a portmanteau of in-source and sorcerer. The method was evaluated using a set of 15 different cytokinin standards. Product ions from in-source fragmentation and CID were compared. Hierarchical clustering revealed that good matches are due to the presence of common substructures. Plant leaf extract, spiked with a mix of all 15 standards, was used to demonstrate the method's ability to detect these standards in a complex mixture, as well as confidently identify compounds already present in the plant material. Here we present a method that incorporates a classic liquid chromatography/mass spectrometry (LC/MS) workflow with fragmentation models and computational algorithms. The assumptions upon which the concept of the method was built were shown to be valid and the method showed that in-source fragmentation can be used to pinpoint structural similarities and indicate the occurrence of a modification. Copyright © 2017 John Wiley & Sons, Ltd.

Validation and uncertainty estimation of fast neutron activation analysis method for Cu, Fe, Al, Si elements in sediment samples

International Nuclear Information System (INIS)

Sunardi; Samin Prihatin

2010-01-01

Validation and uncertainty estimation of Fast Neutron Activation Analysis (FNAA) method for Cu, Fe, Al, Si elements in sediment samples has been conduced. The aim of the research is to confirm whether FNAA method is still matches to ISO/lEC 17025-2005 standard. The research covered the verification, performance, validation of FNM and uncertainty estimation. Standard of SRM 8704 and sediments were weighted for certain weight and irradiated with 14 MeV fast neutron and then counted using gamma spectrometry. The result of validation method for Cu, Fe, Al, Si element showed that the accuracy were in the range of 95.89-98.68 %, while the precision were in the range 1.13-2.29 %. The result of uncertainty estimation for Cu, Fe, Al, and Si were 2.67, 1.46, 1.71 and 1.20 % respectively. From this data, it can be concluded that the FNM method is still reliable and valid for element contents analysis in samples, because the accuracy is up to 95 % and the precision is under 5 %, while the uncertainty are relatively small and suitable for the range 95 % level of confidence where the uncertainty maximum is 5 %. (author)

Magnetic solid phase extraction and static headspace gas chromatography-mass spectrometry method for the analysis of polycyclic aromatic hydrocarbons.

Science.gov (United States)

Cai, Ying; Yan, Zhihong; Wang, Lijia; NguyenVan, Manh; Cai, Qingyun

2016-01-15

A magnetic solid phase extraction (MSPE) protocol combining a static headspace gas chromatography coupled to mass spectrometry (HS-GC-MS) method has been developed for extraction, and determination of 16 polycyclic aromatic hydrocarbons (PAHs) in drinking water samples. Magnetic nanoparticles (MNPs) were coated with 3-aminopropyltriethoxysilane and modified by cholesterol chloroformate. Transmission electron microscope, vibrating sample magnetometer, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy were used to characterize the cholesterol-functionalized sorbents, and the main parameters affecting the extraction as well as HS sampling, such as sorbent amount, extraction time, oven temperature and equilibration time have been investigated and established. Combination with HS sampling, the MSPE procedure was simple, fast and environmentally friendly, without need of any organic solvent. Method validation proved the feasibility of the developed sorbents for the quantitation of the investigated analytes at trace levels obtaining the limit of detection (S/N=3) ranging from 0.20 to 7.8 ng/L. Good values for intra and inter-day precision were obtained (RSDs ≤ 9.9%). The proposed method was successfully applied to drinking water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Hooked differential mobility spectrometry apparatus and method therefore

Science.gov (United States)

Shvartsburg, Alexandre A [Richland, WA; Tang, Keqi [Richland, WA; Ibrahim, Yehia M [Richland, WA; Smith, Richard D [Richland, WA

2009-02-17

Disclosed are a device and method for improved interfacing of differential mobility spectrometry (DMS) or field asymmetric waveform ion mobility spectrometry (FAIMS) analyzers of substantially planar geometry to subsequent or preceding instrument stages. Interfacing is achieved using curved DMS elements, where a thick ion beam emitted by planar DMS analyzers or injected into them for ion filtering is compressed to the gap median by DMS ion focusing effect in a spatially inhomogeneous electric field. Resulting thinner beams are more effectively transmitted through necessarily constrained conductance limit apertures to subsequent instrument stages operated at a pressure lower than DMS, and/or more effectively injected into planar DMS analyzers. The technology is synergetic with slit apertures, slit aperture/ion funnels, and high-pressure ion funnel interfaces known in the art which allow for increasing cross-sectional area of MS inlets. The invention may be used in integrated analytical platforms, including, e.g., DMS/MS, LC/DMS/MS, and DMS/IMS/MS that could replace and/or enhance current LC/MS methods, e.g., for proteomics research.

Development and validation of an ultra-performance liquid chromatography quadrupole time of flight mass spectrometry method for rapid quantification of free amino acids in human urine.

Science.gov (United States)

Joyce, Richard; Kuziene, Viktorija; Zou, Xin; Wang, Xueting; Pullen, Frank; Loo, Ruey Leng

2016-01-01

An ultra-performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-qTOF-MS) method using hydrophilic interaction liquid chromatography was developed and validated for simultaneous quantification of 18 free amino acids in urine with a total acquisition time including the column re-equilibration of less than 18 min per sample. This method involves simple sample preparation steps which consisted of 15 times dilution with acetonitrile to give a final composition of 25 % aqueous and 75 % acetonitrile without the need of any derivatization. The dynamic range for our calibration curve is approximately two orders of magnitude (120-fold from the lowest calibration curve point) with good linearity (r (2) ≥ 0.995 for all amino acids). Good separation of all amino acids as well as good intra- and inter-day accuracy (amino acids in the prepared urine samples was found to be stable for 72 h at 4 °C, after one freeze thaw cycle and for up to 4 weeks at -80 °C. We have applied this method to quantify the content of 18 free amino acids in 646 urine samples from a dietary intervention study. We were able to quantify all 18 free amino acids in these urine samples, if they were present at a level above the LOD. We found our method to be reproducible (accuracy and precision were typically <10 % for QCL, QCM and QCH) and the relatively high sample throughput nature of this method potentially makes it a suitable alternative for the analysis of urine samples in clinical setting.

Validation the quantification of beta emitters activity in urine by scintillation spectrometry in the liquid phase

International Nuclear Information System (INIS)

Sierra, I.; Hernandez, C.; Benito, P.; Lopez, C.

2013-01-01

In this paper the methodology used in the validation of the technique for quantifying activity of some beta emitters in urine ( 3 H, 1 4C, 3 5S, 3 2P and 9 0Sr) by scintillation spectrometry Liquid Phase (Liquid Scintillation Counting, LSC) is described in bio elimination Laboratory Service CIEMAT Radiation Dosimetry accredited since last year for carrying out assays measure radiation dose based on ISO forth above. (Author)

Valid methods: the quality assurance of test method development, validation, approval, and transfer for veterinary testing laboratories.

Science.gov (United States)

Wiegers, Ann L

2003-07-01

Third-party accreditation is a valuable tool to demonstrate a laboratory's competence to conduct testing. Accreditation, internationally and in the United States, has been discussed previously. However, accreditation is only I part of establishing data credibility. A validated test method is the first component of a valid measurement system. Validation is defined as confirmation by examination and the provision of objective evidence that the particular requirements for a specific intended use are fulfilled. The international and national standard ISO/IEC 17025 recognizes the importance of validated methods and requires that laboratory-developed methods or methods adopted by the laboratory be appropriate for the intended use. Validated methods are therefore required and their use agreed to by the client (i.e., end users of the test results such as veterinarians, animal health programs, and owners). ISO/IEC 17025 also requires that the introduction of methods developed by the laboratory for its own use be a planned activity conducted by qualified personnel with adequate resources. This article discusses considerations and recommendations for the conduct of veterinary diagnostic test method development, validation, evaluation, approval, and transfer to the user laboratory in the ISO/IEC 17025 environment. These recommendations are based on those of nationally and internationally accepted standards and guidelines, as well as those of reputable and experienced technical bodies. They are also based on the author's experience in the evaluation of method development and transfer projects, validation data, and the implementation of quality management systems in the area of method development.

Validation of an accelerated solvent extraction liquid chromatography-tandem mass spectrometry method for Pacific ciguatoxin-1 in fish flesh and comparison with the mouse neuroblastoma assay.

Science.gov (United States)

Wu, Jia Jun; Mak, Yim Ling; Murphy, Margaret B; Lam, James C W; Chan, Wing Hei; Wang, Mingfu; Chan, Leo L; Lam, Paul K S

2011-07-01

Ciguatera fish poisoning (CFP) is a global foodborne illness caused by consumption of seafood containing ciguatoxins (CTXs) originating from dinoflagellates such as Gambierdiscus toxicus. P-CTX-1 has been suggested to be the most toxic CTX, causing ciguatera at 0.1 μg/kg in the flesh of carnivorous fish. CTXs are structurally complex and difficult to quantify, but there is a need for analytical methods for CFP toxins in coral reef fishes to protect human health. In this paper, we describe a sensitive and rapid extraction method using accelerated solvent extraction combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the detection and quantification of P-CTX-1 in fish flesh. By the use of a more sensitive MS system (5500 QTRAP), the validated method has a limit of quantification (LOQ) of 0.01 μg/kg, linearity correlation coefficients above 0.99 for both solvent- and matrix-based standard solutions as well as matrix spike recoveries ranging from 49% to 85% in 17 coral reef fish species. Compared with previous methods, this method has better overall recovery, extraction efficiency and LOQ. Fish flesh from 12 blue-spotted groupers (Cephalopholis argus) was assessed for the presence of CTXs using HPLC-MS/MS analysis and the commonly used mouse neuroblastoma assay, and the results of the two methods were strongly correlated. This method is capable of detecting low concentrations of P-CTX-1 in fish at levels that are relevant to human health, making it suitable for monitoring of suspected ciguateric fish both in the environment and in the marketplace.

Determination of total arsenic in fish by hydride-generation atomic absorption spectrometry: method validation, traceability and uncertainty evaluation

Science.gov (United States)

Nugraha, W. C.; Elishian, C.; Ketrin, R.

2017-03-01

Fish containing arsenic compound is one of the important indicators of arsenic contamination in water monitoring. The high level of arsenic in fish is due to absorption through food chain and accumulated in their habitat. Hydride generation (HG) coupled with atomic absorption spectrometric (AAS) detection is one of the most popular techniques employed for arsenic determination in a variety of matrices including fish. This study aimed to develop a method for the determination of total arsenic in fish by HG-AAS. The method for sample preparation from American of Analytical Chemistry (AOAC) Method 999.10-2005 was adopted for acid digestion using microwave digestion system and AOAC Method 986.15 - 2005 for dry ashing. The method was developed and validated using Certified Reference Material DORM 3 Fish Protein for trace metals for ensuring the accuracy and the traceability of the results. The sources of uncertainty of the method were also evaluated. By using the method, it was found that the total arsenic concentration in the fish was 45.6 ± 1.22 mg.Kg-1 with a coverage factor of equal to 2 at 95% of confidence level. Evaluation of uncertainty was highly influenced by the calibration curve. This result was also traceable to International Standard System through analysis of Certified Reference Material DORM 3 with 97.5% of recovery. In summary, it showed that method of preparation and HG-AAS technique for total arsenic determination in fish were valid and reliable.

Development and validation of an LC-MS/MS method for the quantification of tiamulin, trimethoprim, tylosin, sulfadiazine and sulfamethazine in medicated feed.

Science.gov (United States)

Patyra, Ewelina; Nebot, Carolina; Gavilán, Rosa Elvira; Cepeda, Alberto; Kwiatek, Krzysztof

2018-01-22

A new multi-compound method for the analysis of veterinary drugs, namely tiamulin, trimethoprim, tylosin, sulfadiazine and sulfamethazine was developed and validated in medicated feeds. After extraction, the samples were centrifuged, diluted in Milli-Q water, filtered and analysed by high performance liquid chromatography coupled to tandem mass spectrometry. The separation of the analytes was performed on a biphenyl column with a gradient of 0.1% formic acid in acetonitrile and 0.1% formic acid in Milli-Q water. Quantitative validation was done in accordance with the guidelines laid down in European Commission Decision 2002/657/EC. Method performances were evaluated by the following parameters: linearity (R 2  tiamulin, tylosin and sulfamethazine were detected at the concentration levels declared by the manufacturers. The developed method can therefore be successfully used to routinely control the content and homogeneity of these antibacterial substances in medicated feed. Abbreviations AAFCO - Association of American Feed Control Officials; TYL - tylosin; TIAM - tiamulin fumarate; TRIM - trimethoprim; SDZ - sulfadiazine; SMZ - sulfamethazine; UV - ultraviolet detector; FLD - fluorescence detector; HPLC - high performance liquid chromatography; MS/MS - tandem mass spectrometry; LOD - limit of detection; LOQ - limit of quantification; CV - coefficient of variation; SD - standard deviation; U - uncertainty.

226Ra determination in phosphogypsum by alpha-particle spectrometry

International Nuclear Information System (INIS)

Aguado, J.L.; Bolivar, J.P.; Garcia-Tenorio, R.

1999-01-01

A radiochemical method for 226 Ra determination by alpha-particle spectrometry in environmental samples has been developed in our laboratory. The method has been validated by measurements in samples with known concentrations of this radionuclide and it has been applied in studies related to 226 Ra behaviour in phosphogypsum (the main by-product of producing phosphoric acid from phosphate rocks). (author)

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties.

Science.gov (United States)

Tiryaki, Osman

2016-10-02

This study was undertaken to validate the "quick, easy, cheap, effective, rugged and safe" (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.

Development and validation of a gas chromatography-negative chemical ionization tandem mass spectrometry method for the determination of ethyl glucuronide in hair and its application to forensic toxicology.

Science.gov (United States)

Kharbouche, Hicham; Sporkert, Frank; Troxler, Stéphanie; Augsburger, Marc; Mangin, Patrice; Staub, Christian

2009-08-01

Ethyl glucuronide (EtG) is a minor and direct metabolite of ethanol. EtG is incorporated into the growing hair allowing retrospective investigation of chronic alcohol abuse. In this study, we report the development and the validation of a method using gas chromatography-negative chemical ionization tandem mass spectrometry (GC-NCI-MS/MS) for the quantification of EtG in hair. EtG was extracted from about 30 mg of hair by aqueous incubation and purified by solid-phase extraction (SPE) using mixed mode extraction cartridges followed by derivation with perfluoropentanoic anhydride (PFPA). The analysis was performed in the selected reaction monitoring (SRM) mode using the transitions m/z 347-->163 (for the quantification) and m/z 347-->119 (for the identification) for EtG, and m/z 352-->163 for EtG-d(5) used as internal standard. For validation, we prepared quality controls (QC) using hair samples taken post mortem from 2 subjects with a known history of alcoholism. These samples were confirmed by a proficiency test with 7 participating laboratories. The assay linearity of EtG was confirmed over the range from 8.4 to 259.4 pg/mg hair, with a coefficient of determination (r(2)) above 0.999. The limit of detection (LOD) was estimated with 3.0 pg/mg. The lower limit of quantification (LLOQ) of the method was fixed at 8.4 pg/mg. Repeatability and intermediate precision (relative standard deviation, RSD%), tested at 4 QC levels, were less than 13.2%. The analytical method was applied to several hair samples obtained from autopsy cases with a history of alcoholism and/or lesions caused by alcohol. EtG concentrations in hair ranged from 60 to 820 pg/mg hair.

Development and validation of a multiresidue method for pesticide analysis in honey by UFLC-MS

Directory of Open Access Journals (Sweden)

Adriana M. Zamudio S.

2017-05-01

Full Text Available A method for the determination of pesticide residues in honey by ultra fast liquid chromatography coupled with mass spectrometry was developed. For this purpose, different variations of the QuECHERS method were performed: (i amount of sample, (ii type of salt to control pH, (iii buffer pH, and (iv different mixtures for cleaning-up. In addition, to demonstrate that the method is reliable, different validation parameters were studied: accuracy, limits of detection and quantification, linearity and selectivity. The results showed that by means of the changes introduced it was possible to get a more selective method that improves the accuracy of about 19 pesticides selected from the original method. It was found that the method is suitable for the analysis of 50 pesticides, out of 56. Furthermore, with the developed method recoveries between 70 and 120% and relative standard deviation below 15% were found.

Development and validation of an ultra high performance liquid chromatography tandem mass spectrometry method for simultaneous determination of sulfonamides, quinolones and benzimidazoles in bovine milk.

Science.gov (United States)

Hou, Xiao-Lin; Chen, Guo; Zhu, Li; Yang, Ting; Zhao, Jian; Wang, Lei; Wu, Yin-Liang

2014-07-01

A simple, sensitive and reliable analytical method was developed for the simultaneous determination of 38 veterinary drugs (18 sulfonamides, 11 quinolones and 9 benzimidazoles) and 8 metabolites of benzimidazoles in bovine milk by ultra high performance liquid chromatography-positive electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS). Samples were extracted with acidified acetonitrile, cleaned up with Oasis(®) MCX cartridges, and analyzed by LC-MS/MS on an Acquity UPLC(®) BEH C18 column with gradient elution. The method allows such multi-analyte measurements within a 13min runtime while the specificity is ensured through the MRM acquisition mode. The method was validated according to the European Commission Decision 2002/657/EC determining specificity, decision limit (CCα), detection capability (CCβ), recovery, precision, linearity and stability. For compounds which have MRLs in bovine milk, the CCα values fall into a range from 11 to 115μg/kg, and the CCβ values fall within a range of 12-125μg/kg. For compounds which have not MRLs in bovine milk, the CCα values fall into a range from 0.01 to 0.08μg/kg, and the CCβ values fall within a range of 0.02-0.11μg/kg. The mean recoveries of the 46 analytes were between 87 and 119%. The calculated RSD values of repeatability and within-laboratory reproducibility experiments were below 11% and 15% for the 46 compounds, respectively. The method was demonstrated to be suitable for the simultaneous determination of sulfonamides, quinolones and benzimidazoles in bovine milk. Copyright © 2014 Elsevier B.V. All rights reserved.

MASS SPECTROMETRY PROTEOMICS METHOD AS A RAPID SCREENING TOOL FOR BACTERIAL CONTAMINATION OF FOOD

Science.gov (United States)

2017-06-01

MASS SPECTROMETRY PROTEOMICS METHOD AS A RAPID SCREENING TOOL FOR BACTERIAL CONTAMINATION OF FOOD ECBC-TR...TITLE AND SUBTITLE Mass Spectrometry Proteomics Method as a Rapid Screening Tool for Bacterial Contamination of Food 5a. CONTRACT NUMBER 5b...the MSPM to correctly classify whether or not food samples were contaminated with Salmonella enterica serotype Newport in this blinded pilot study

Determination of 210Pb by direct gamma-ray spectrometry, beta counting via 210Bi and alpha-particle spectrometry via 210Po in coal, slag and ash samples from thermal power plant

International Nuclear Information System (INIS)

Seslak, Bojan; Vukanac, Ivana; Kandic, Aleksandar; Durasevic, Mirjana; Eric, Milic; Jevremovic, Aleksandar

2017-01-01

In order to compare three different techniques and estimate radiological impact, activity concentration of 210 Pb in coal, slag and ash samples from thermal power plant 'Nikola Tesla', Serbia, were measured, and results are presented in this study. Determination of 210 Pb was carried out in three ways: using HPGe gamma spectrometer and via in-growth of 210 Po and 210 Bi by alpha-particle spectrometry and proportional counting, respectively. The results obtained for three different techniques were compared. Statistical analysis and comparison of methods were carried out by combination of Z score and χ 2 statistical tests. Tests results, as well as values of measured activities concentrations obtained by alpha and gamma spectrometry, showed that gamma spectrometry is a valid alternative to time-consuming alpha spectrometry for low level activity measurements of 210 Pb. This remark is also valid even for gamma spectrometers with poor efficiency in low energy region. (author)

Development of a new ultra-high performance liquid chromatography - tandem mass spectrometry method for determination of ambroxol hydrochloride in serum with pharmacokinetic application

Directory of Open Access Journals (Sweden)

Vujović Maja M.

2016-01-01

Full Text Available Ambroxol hydrochloride is an expectorant agent, successfully applied in mucolytic therapy for acute and chronic bronchopulmonary diseases. The drug regulates not only mucus secretion but also showed antioxidant, anti-inflammatory and local anesthetic properties. To supplement the pharmacokinetic and toxicological studies of ambroxol, a rapid ultra-high performance liquid chromatography-tandem mass spectrometry method for the quantitation of ambroxol in rabbit serum was developed. A validation of the method was performed as per the ICH guidelines for the validation of bioanalytical methods. The chromatographic separation was achieved in a submicron Kinetex RP - C18 - column (2.1 mm x 50 mm, 1.3μm using the no buffer mobile phase. The ESI mass spectrometry in the MRM mode was used with a typical transitions m/z 378.9→263.8 for ambroxol and m/z 455.2→165.0 for IS. Linearity was determined with an average coefficient of determination >0.999 over the dynamic range from 0.5 - 200 ng/mL with LOD and LOQ of 0.25 ng/mL and 0.5 ng/mL, respectively. The results of the intra- and inter-day precision and accuracy determined in different days were all found to be within the acceptable limits ±15%. The present method was successfully applied to pharmacokinetic study in the rabbits after a single oral dose administration. [Projekat Ministarstva nauke Republike Srbije, br. 175045

Validation of a multi-residue method for the determination of several antibiotic groups in honey by LC-MS/MS.

Science.gov (United States)

Bohm, Detlef A; Stachel, Carolin S; Gowik, Petra

2012-07-01

The presented multi-method was developed for the confirmation of 37 antibiotic substances from the six antibiotic groups: macrolides, lincosamides, quinolones, tetracyclines, pleuromutilines and diamino-pyrimidine derivatives. All substances were analysed simultaneously in a single analytical run with the same procedure, including an extraction with buffer, a clean-up by solid-phase extraction, and the measurement by liquid chromatography tandem mass spectrometry in ESI+ mode. The method was validated on the basis of an in-house validation concept with factorial design by combination of seven factors to check the robustness in a concentration range of 5-50 μg kg(-1). The honeys used were of different types with regard to colour and origin. The values calculated for the validation parameters-decision limit CCα (range, 7.5-12.9 μg kg(-1)), detection capability CCβ (range, 9.4-19.9 μg kg(-1)), within-laboratory reproducibility RSD(wR) (tylvalosin with 21.4 %), repeatability RSD(r) (tylvalosin with 21.1%), and recovery (range, 92-106%)-were acceptable and in agreement with the criteria of Commission Decision 2002/657/EC. The validation results showed that the method was applicable for the residue analysis of antibiotics in honey to substances with and without recommended concentrations, although some changes had been tested during validation to determine the robustness of the method.

Research on 3-D terrain correction methods of airborne gamma-ray spectrometry survey

International Nuclear Information System (INIS)

Liu Yanyang; Liu Qingcheng; Zhang Zhiyong

2008-01-01

The general method of height correction is not effectual in complex terrain during the process of explaining airborne gamma-ray spectrometry data, and the 2-D terrain correction method researched in recent years is just available for correction of section measured. A new method of 3-D sector terrain correction is studied. The ground radiator is divided into many small sector radiators by the method, then the irradiation rate is calculated in certain survey distance, and the total value of all small radiate sources is regarded as the irradiation rate of the ground radiator at certain point of aero- survey, and the correction coefficients of every point are calculated which then applied to correct to airborne gamma-ray spectrometry data. The method can achieve the forward calculation, inversion calculation and terrain correction for airborne gamma-ray spectrometry survey in complex topography by dividing the ground radiator into many small sectors. Other factors are considered such as the un- saturated degree of measure scope, uneven-radiator content on ground, and so on. The results of for- ward model and an example analysis show that the 3-D terrain correction method is proper and effectual. (authors)

Computational methods for metabolomic data analysis of ion mobility spectrometry data-reviewing the state of the art

DEFF Research Database (Denmark)

Hauschild, Anne-Christin; Schneider, Till; Pauling, Josch

2012-01-01

that MCC/IMS coupled with sophisticated computational methods has the potential to successfully address a broad range of biomedical questions. While we can solve most of the data pre-processing steps satisfactorily, some computational challenges with statistical learning and model validation remain.......Ion mobility spectrometry combined with multi-capillary columns (MCC/IMS) is a well known technology for detecting volatile organic compounds (VOCs). We may utilize MCC/IMS for scanning human exhaled air, bacterial colonies or cell lines, for example. Thereby we gain information about the human...... of computational approaches for analyzing the huge amount of emerging data sets. Here, we will review the state of the art and highlight existing challenges. First, we address methods for raw data handling, data storage and visualization. Afterwards we will introduce de-noising, peak picking and other pre...

A simple source preparation method for alpha-ray spectrometry of volcanic rock sample

International Nuclear Information System (INIS)

Takahashi, Masaomi; Kurihara, Yuichi; Sato, Jun

2006-01-01

A simple source preparation method was developed for the alpha-ray spectrometry to determine U and Th in volcanic rockes. Isolation of U and Th from volcanic rocks was made by use of UTEVA-Spec. resin, extraction chromatograph material. U and Th were extracted by TTA-benzene solution and organic phase was evaporated drop by drop on a hot stainless steel planchet to dryness. This method was found to be effective for the preparation of sources for alpha-ray spectrometry. (author)

Catch and measure-mass spectrometry-based immunoassays in biomarker research.

Science.gov (United States)

Weiß, Frederik; van den Berg, Bart H J; Planatscher, Hannes; Pynn, Christopher J; Joos, Thomas O; Poetz, Oliver

2014-05-01

Mass spectrometry-based (MS) methods are effective tools for discovering protein biomarker candidates that can differentiate between physiological and pathophysiological states. Promising candidates are validated in studies comprising large patient cohorts. Here, targeted protein analytics are used to increase sample throughput. Methods involving antibodies, such as sandwich immunoassays or Western blots, are commonly applied at this stage. Highly-specific and sensitive mass spectrometry-based immunoassays that have been established in recent years offer a suitable alternative to sandwich immunoassays for quantifying proteins. Mass Spectrometric ImmunoAssays (MSIA) and Stable Isotope Standards and Capture by Anti-Peptide Antibodies (SISCAPA/iMALDI) are two prominent types of MS-based immunoassays in which the capture is done either at the protein or the peptide level. We present an overview of these emerging types of immunoassays and discuss their suitability for the discovery and validation of protein biomarkers. This article is part of a Special Issue entitled: Biomarkers: A Proteomic Challenge. © 2013.

Validation of an analytical method for the determination of total mercury in urine samples using cold vapor atomic absorption spectrometry (CV-AAS)

International Nuclear Information System (INIS)

Guilhen, Sabine Neusatz

2009-01-01

Mercury (Hg) is a toxic metal applied to a variety of products and processes, representing a risk to the health of occupationally or accidentally exposed subjects. Dental amalgam is a restorative material composed of metallic mercury, which use has been widely debated in the last decades. Due to the dubiety of the studies concerning dental amalgam, many efforts concerning this issue have been conducted. The Tropical Medicine Foundation (Tocantins, Brazil) has recently initiated a study to evaluate the environmental and occupational levels of exposure to mercury in dentistry attendants at public consulting rooms in the city of Araguaina (TO). In collaboration with this study, the laboratory of analysis at IPEN's Chemistry and Environment Center is undertaking the analysis of mercury levels in exposed subjects' urine samples using cold vapor atomic absorption spectrometry. This analysis requires the definition of a methodology capable of generating reliable results. Such methodology can only be implemented after a rigorous validation procedure. As part of this work, a series of tests were conducted in order to confirm the suitability of the selected methodology and to assert that the laboratory addresses all requirements needed for a successful implementation of the methodology. The following parameters were considered in order to test the method's performance: detection and quantitation limits, selectivity, sensitivity, linearity, accuracy and precision. The assays were carried out with certified reference material, which assures the traceability of the results. Taking into account the estimated parameters, the method can be considered suitable for the afore mentioned purpose. The mercury concentration found for the reference material was of (95,12 +- 11,70)mug.L -1 with a recovery rate of 97%. The method was also applied to 39 urine samples, six of which (15%) showing urinary mercury levels above the normal limit of 10μg.L -1 . The obtained results fall into a

Development of an improved high resolution mass spectrometry based multi-residue method for veterinary drugs in various food matrices.

Science.gov (United States)

Kaufmann, A; Butcher, P; Maden, K; Walker, S; Widmer, M

2011-08-26

Multi-residue methods for veterinary drugs or pesticides in food are increasingly often based on ultra performance liquid chromatography (UPLC) coupled to high resolution mass spectrometry (HRMS). Previous available time of flight (TOF) technologies, showing resolutions up to 15,000 full width at half maximum (FWHM), were not sufficiently selective for monitoring low residue concentrations in difficult matrices (e.g. hormones in tissue or antibiotics in honey). The approach proposed in this paper is based on a single stage Orbitrap mass spectrometer operated at 50,000 FWHM. Extracts (liver and kidney) which were produced according to a validated multi-residue method (time of flight detection based) could not be analyzed by Orbitrap because of extensive signal suppression. This required the improvement of established extraction and clean-up procedures. The introduced, more extensive deproteinzation steps and dedicated instrumental settings successfully eliminated these detrimental suppression effects. The reported method, covering more than 100 different veterinary dugs, was validated according to the EU Commission Decision 2002/657/EEC. Validated matrices include muscle, kidney, liver, fish and honey. Significantly better performance parameters (e.g. linearity, reproducibility and detection limits) were obtained when comparing the new method with the older, TOF based method. These improvements are attributed to the higher resolution (50,000 versus 12,000 FWHM) and the superior mass stability of the of the Orbitrap over the previously utilized TOF instrument. Copyright © 2010 Elsevier B.V. All rights reserved.

A general method for targeted quantitative cross-linking mass spectrometry

Science.gov (United States)

Chemical cross-linking mass spectrometry (XL-MS) provides protein structural information by identifying covalently linked proximal amino acid residues on protein surfaces. The information gained by this technique is complementary to other structural biology methods such as x-ray crystallography, NM...

Development and Validation of a Multiplexed Protein Quantitation Assay for the Determination of Three Recombinant Proteins in Soybean Tissues by Liquid Chromatography with Tandem Mass Spectrometry.

Science.gov (United States)

Hill, Ryan C; Oman, Trent J; Shan, Guomin; Schafer, Barry; Eble, Julie; Chen, Cynthia

2015-08-26

Currently, traditional immunochemistry technologies such as enzyme-linked immunosorbent assays (ELISA) are the predominant analytical tool used to measure levels of recombinant proteins expressed in genetically engineered (GE) plants. Recent advances in agricultural biotechnology have created a need to develop methods capable of selectively detecting and quantifying multiple proteins in complex matrices because of increasing numbers of transgenic proteins being coexpressed or "stacked" to achieve tolerance to multiple herbicides or to provide multiple modes of action for insect control. A multiplexing analytical method utilizing liquid chromatography with tandem mass spectrometry (LC-MS/MS) has been developed and validated to quantify three herbicide-tolerant proteins in soybean tissues: aryloxyalkanoate dioxygenase (AAD-12), 5-enol-pyruvylshikimate-3-phosphate synthase (2mEPSPS), and phosphinothricin acetyltransferase (PAT). Results from the validation showed high recovery and precision over multiple analysts and laboratories. Results from this method were comparable to those obtained with ELISA with respect to protein quantitation, and the described method was demonstrated to be suitable for multiplex quantitation of transgenic proteins in GE crops.

Development, validation and application of a micro-liquid chromatography-tandem mass spectrometry based method for simultaneous quantification of selected protein biomarkers of endothelial dysfunction in murine plasma.

Science.gov (United States)

Suraj, Joanna; Kurpińska, Anna; Olkowicz, Mariola; Niedzielska-Andres, Ewa; Smolik, Magdalena; Zakrzewska, Agnieszka; Jasztal, Agnieszka; Sitek, Barbara; Chlopicki, Stefan; Walczak, Maria

2018-02-05

The objective of this study was to develop and validate the method based on micro-liquid chromatography-tandem mass spectrometry (microLC/MS-MRM) for simultaneous determination of adiponectin (ADN), von Willebrand factor (vWF), soluble form of vascular cell adhesion molecule 1 (sVCAM-1), soluble form of intercellular adhesion molecule 1 (sICAM-1) and syndecan-1 (SDC-1) in mouse plasma. The calibration range was established from 2.5pmol/mL to 5000pmol/mL for ADN; 5pmol/mL to 5000pmol/mL for vWF; 0.375pmol/mL to 250pmol/mL for sVCAM-1 and sICAM-1; and 0.25pmol/mL to 250pmol/mL for SDC-1. The method was applied to measure the plasma concentration of selected proteins in mice fed high-fat diet (HFD), and revealed the pro-thrombotic status by increased concentration of vWF (1.31±0.17 nmol/mL (Control) vs 1.98±0.09 nmol/mL (HFD), p <0.05) and the dysregulation of adipose tissue metabolism by decreased concentration of ADN (0.62±0.08 nmol/mL (Control) vs 0.37±0.06 nmol/mL (HFD), p <0.05). In conclusion, the microLC/MS-MRM-based method allows for reliable measurements of selected protein biomarkers of endothelial dysfunction in mouse plasma. Copyright © 2017 Elsevier B.V. All rights reserved.

New method for determination of epichlorohydrin in epoxy-coated cans by oxolane derivatization and gas chromatography-mass spectrometry.

Science.gov (United States)

Sung, Jun Hyun; Lee, Young Ja; Park, Hyun Jin

2008-08-01

A new method was developed for the determination of epichlorohydrin (ECH) in food contact surface of epoxy-coated cans. The oxolane derivative, which produced by reaction of epoxy moiety in ECH with cyclopentanone in the presence of borontrifluoride-diethyletherate, was analyzed by gas chromatography (GC)/mass spectrometry (MS). 1,2-Epoxyhexane was used as internal standard (IS), which produced an oxolane derivative under the same reaction mechanism as ECH. The developed method was validated with 1 ng ml(-1) of limit of detection (LOD, surface area related 20 ng dm(-2)), >0.999 of linearity. Good precision, which was tested both in terms of intra-day repeatability and inter-day reproducibility, and 97.3-102.7% of good recoveries were obtained on three spiked levels of 5.2, 40.3 and 149.1 ng ml(-1). The excellent validation data suggests that this method is more simple, quick and effective than the official method in European Committee for Standardization (CEN) to determine the residual amount of ECH in food contact materials for food law compliance test. The residual amount of ECH for 13 epoxy-coated can samples was analyzed, and none of the samples was found to be detectable levels of ECH in epoxy-coated cans.

An analysis of nuclear fuel burnup in the AGR-1 TRISO fuel experiment using gamma spectrometry, mass spectrometry, and computational simulation techniques

International Nuclear Information System (INIS)

Harp, Jason M.; Demkowicz, Paul A.; Winston, Philip L.; Sterbentz, James W.

2014-01-01

Highlights: • The burnup of irradiated AGR-1 TRISO fuel was analyzed using gamma spectrometry. • The burnup of irradiated AGR-1 TRISO fuel was also analyzed using mass spectrometry. • Agreement between experimental results and neutron physics simulations was excellent. - Abstract: AGR-1 was the first in a series of experiments designed to test US TRISO fuel under high temperature gas-cooled reactor irradiation conditions. This experiment was irradiated in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL) and is currently undergoing post-irradiation examination (PIE) at INL and Oak Ridge National Laboratory. One component of the AGR-1 PIE is the experimental evaluation of the burnup of the fuel by two separate techniques. Gamma spectrometry was used to non-destructively evaluate the burnup of all 72 of the TRISO fuel compacts that comprised the AGR-1 experiment. Two methods for evaluating burnup by gamma spectrometry were developed, one based on the Cs-137 activity and the other based on the ratio of Cs-134 and Cs-137 activities. Burnup values determined from both methods compared well with the values predicted from simulations. The highest measured burnup was 20.1% FIMA (fissions per initial heavy metal atom) for the direct method and 20.0% FIMA for the ratio method (compared to 19.56% FIMA from simulations). An advantage of the ratio method is that the burnup of the cylindrical fuel compacts can be determined in small (2.5 mm) axial increments and an axial burnup profile can be produced. Destructive chemical analysis by inductively coupled mass spectrometry (ICP-MS) was then performed on selected compacts that were representative of the expected range of fuel burnups in the experiment to compare with the burnup values determined by gamma spectrometry. The compacts analyzed by mass spectrometry had a burnup range of 19.3% FIMA to 10.7% FIMA. The mass spectrometry evaluation of burnup for the four compacts agreed well with the gamma

New Isotope Analysis Method: Atom Trap Mass Spectrometry

International Nuclear Information System (INIS)

Ko, Kwang Hoon; Park, Hyun Min; Han, Jae Min; Kim, Taek Soo; Cha, Yong Ho; Lim, Gwon; Jeong, Do Young

2011-01-01

Trace isotope analysis has been an important role in science, archaeological dating, geology, biology and nuclear industry. Some fission products such as Sr-90, Cs-135 and Kr-85 can be released to the environment when nuclear accident occurs and the reprocessing factory operates. Thus, the analysis of artificially produced radioactive isotopes has been of interest in nuclear industry. But it is difficult to detect them due to low natural abundance less then 10 -10 . In general, radio-chemical method has been applied to detect ultra-trace radio isotopes. But this method has disadvantages of long measurement time for long lived radioisotopes and toxic chemical process for the purification. The Accelerator Mass Spectrometer has high isotope selectivity, but the system is huge and its selectivity is affected by isobars. The laser based method, such as RIMS (Resonance Ionization Mass Spectrometry) has the advantage of isobar-effect free characteristics. But the system size is still huge for high isotope selective system. Recently, ATTA (Atom Trap Trace Analysis) has been successfully applied to detect ultra-trace isotope, Kr-81 and Kr-85. ATTA is the isobar-effect free detection with high isotope selectivity and the system size is small. However, it requires steady atomic beam source during detection, and is not allowed simultaneous detection of several isotopes. In this presentation, we introduce new isotope detection method which is a coupled method of Atom Trap Mass Spectrometry (ATMS). We expect that it can overcome the disadvantage of ATTA while it has both advantages of ATTA and mass spectrometer. The basic concept and the system design will be presented. In addition, the experimental status of ATMS will also be presented

Performance assessment of two lysis methods for direct identification of yeasts from clinical blood cultures using MALDI-TOF mass spectrometry.

Science.gov (United States)

Jeddi, Fakhri; Yapo-Kouadio, Gisèle Cha; Normand, Anne-Cécile; Cassagne, Carole; Marty, Pierre; Piarroux, Renaud

2017-02-01

In cases of fungal infection of the bloodstream, rapid species identification is crucial to provide adapted therapy and thereby ameliorate patient outcome. Currently, the commercial Sepsityper kit and the sodium-dodecyl sulfate (SDS) method coupled with MALDI-TOF mass spectrometry are the most commonly reported lysis protocols for direct identification of fungi from positive blood culture vials. However, the performance of these two protocols has never been compared on clinical samples. Accordingly, we performed a two-step survey on two distinct panels of clinical positive blood culture vials to identify the most efficient protocol, establish an appropriate log score (LS) cut-off, and validate the best method. We first compared the performance of the Sepsityper and the SDS protocols on 71 clinical samples. For 69 monomicrobial samples, mass spectrometry LS values were significantly higher with the SDS protocol than with the Sepsityper method (P < .0001), especially when the best score of four deposited spots was considered. Next, we established the LS cut-off for accurate identification at 1.7, based on specimen DNA sequence data. Using this LS cut-off, 66 (95.6%) and 46 (66.6%) isolates were correctly identified at the species level with the SDS and the Sepsityper protocols, respectively. In the second arm of the survey, we validated the SDS protocol on an additional panel of 94 clinical samples. Ninety-two (98.9%) of 93 monomicrobial samples were correctly identified at the species level (median LS = 2.061). Overall, our data suggest that the SDS method yields more accurate species identification of yeasts, than the Sepsityper protocol. © The Author 2016. Published by Oxford University Press on behalf of The International Society for Human and Animal Mycology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Validation and Clinical Evaluation of a Novel Method To Measure Miltefosine in Leishmaniasis Patients Using Dried Blood Spot Sample Collection

Science.gov (United States)

Rosing, H.; Hillebrand, M. J. X.; Blesson, S.; Mengesha, B.; Diro, E.; Hailu, A.; Schellens, J. H. M.; Beijnen, J. H.

2016-01-01

To facilitate future pharmacokinetic studies of combination treatments against leishmaniasis in remote regions in which the disease is endemic, a simple cheap sampling method is required for miltefosine quantification. The aims of this study were to validate a liquid chromatography-tandem mass spectrometry method to quantify miltefosine in dried blood spot (DBS) samples and to validate its use with Ethiopian patients with visceral leishmaniasis (VL). Since hematocrit (Ht) levels are typically severely decreased in VL patients, returning to normal during treatment, the method was evaluated over a range of clinically relevant Ht values. Miltefosine was extracted from DBS samples using a simple method of pretreatment with methanol, resulting in >97% recovery. The method was validated over a calibration range of 10 to 2,000 ng/ml, and accuracy and precision were within ±11.2% and ≤7.0% (≤19.1% at the lower limit of quantification), respectively. The method was accurate and precise for blood spot volumes between 10 and 30 μl and for Ht levels of 20 to 35%, although a linear effect of Ht levels on miltefosine quantification was observed in the bioanalytical validation. DBS samples were stable for at least 162 days at 37°C. Clinical validation of the method using paired DBS and plasma samples from 16 VL patients showed a median observed DBS/plasma miltefosine concentration ratio of 0.99, with good correlation (Pearson's r = 0.946). Correcting for patient-specific Ht levels did not further improve the concordance between the sampling methods. This successfully validated method to quantify miltefosine in DBS samples was demonstrated to be a valid and practical alternative to venous blood sampling that can be applied in future miltefosine pharmacokinetic studies with leishmaniasis patients, without Ht correction. PMID:26787691

Determination of perfluorinated compounds in fish fillet homogenates: Method validation and application to fillet homogenates from the Mississippi River

International Nuclear Information System (INIS)

Malinsky, Michelle Duval; Jacoby, Cliffton B.; Reagen, William K.

2011-01-01

We report herein a simple protein precipitation extraction-liquid chromatography tandem mass spectrometry (LC/MS/MS) method, validation, and application for the analysis of perfluorinated carboxylic acids (C7-C12), perfluorinated sulfonic acids (C4, C6, and C8), and perfluorooctane sulfonamide (FOSA) in fish fillet tissue. The method combines a rapid homogenization and protein precipitation tissue extraction procedure using stable-isotope internal standard (IS) calibration. Method validation in bluegill (Lepomis macrochirus) fillet tissue evaluated the following: (1) method accuracy and precision in both extracted matrix-matched calibration and solvent (unextracted) calibration, (2) quantitation of mixed branched and linear isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) with linear isomer calibration, (3) quantitation of low level (ppb) perfluorinated compounds (PFCs) in the presence of high level (ppm) PFOS, and (4) specificity from matrix interferences. Both calibration techniques produced method accuracy of at least 100 ± 13% with a precision (%RSD) ≤18% for all target analytes. Method accuracy and precision results for fillet samples from nine different fish species taken from the Mississippi River in 2008 and 2009 are also presented.

Determination of perfluorinated compounds in fish fillet homogenates: Method validation and application to fillet homogenates from the Mississippi River

Energy Technology Data Exchange (ETDEWEB)

Malinsky, Michelle Duval, E-mail: mmalinsky@mmm.com [3M Environmental Laboratory, 3M Center, Building 0260-05-N-17, St. Paul, MN 55144-1000 (United States); Jacoby, Cliffton B.; Reagen, William K. [3M Environmental Laboratory, 3M Center, Building 0260-05-N-17, St. Paul, MN 55144-1000 (United States)

2011-01-10

We report herein a simple protein precipitation extraction-liquid chromatography tandem mass spectrometry (LC/MS/MS) method, validation, and application for the analysis of perfluorinated carboxylic acids (C7-C12), perfluorinated sulfonic acids (C4, C6, and C8), and perfluorooctane sulfonamide (FOSA) in fish fillet tissue. The method combines a rapid homogenization and protein precipitation tissue extraction procedure using stable-isotope internal standard (IS) calibration. Method validation in bluegill (Lepomis macrochirus) fillet tissue evaluated the following: (1) method accuracy and precision in both extracted matrix-matched calibration and solvent (unextracted) calibration, (2) quantitation of mixed branched and linear isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) with linear isomer calibration, (3) quantitation of low level (ppb) perfluorinated compounds (PFCs) in the presence of high level (ppm) PFOS, and (4) specificity from matrix interferences. Both calibration techniques produced method accuracy of at least 100 {+-} 13% with a precision (%RSD) {<=}18% for all target analytes. Method accuracy and precision results for fillet samples from nine different fish species taken from the Mississippi River in 2008 and 2009 are also presented.

Mass Spectrometry Coupled Experiments and Protein Structure Modeling Methods

Directory of Open Access Journals (Sweden)

Lee Sael

2013-10-01

Full Text Available With the accumulation of next generation sequencing data, there is increasing interest in the study of intra-species difference in molecular biology, especially in relation to disease analysis. Furthermore, the dynamics of the protein is being identified as a critical factor in its function. Although accuracy of protein structure prediction methods is high, provided there are structural templates, most methods are still insensitive to amino-acid differences at critical points that may change the overall structure. Also, predicted structures are inherently static and do not provide information about structural change over time. It is challenging to address the sensitivity and the dynamics by computational structure predictions alone. However, with the fast development of diverse mass spectrometry coupled experiments, low-resolution but fast and sensitive structural information can be obtained. This information can then be integrated into the structure prediction process to further improve the sensitivity and address the dynamics of the protein structures. For this purpose, this article focuses on reviewing two aspects: the types of mass spectrometry coupled experiments and structural data that are obtainable through those experiments; and the structure prediction methods that can utilize these data as constraints. Also, short review of current efforts in integrating experimental data in the structural modeling is provided.

Direct olive oil analysis by mass spectrometry: A comparison of different ambient ionization methods.

Science.gov (United States)

Lara-Ortega, Felipe J; Beneito-Cambra, Miriam; Robles-Molina, José; García-Reyes, Juan F; Gilbert-López, Bienvenida; Molina-Díaz, Antonio

2018-04-01

Analytical methods based on ambient ionization mass spectrometry (AIMS) combine the classic outstanding performance of mass spectrometry in terms of sensitivity and selectivity along with convenient features related to the lack of sample workup required. In this work, the performance of different mass spectrometry-based methods has been assessed for the direct analyses of virgin olive oil for quality purposes. Two sets of experiments have been setup: (1) direct analysis of untreated olive oil using AIMS methods such as Low-Temperature Plasma Mass Spectrometry (LTP-MS) or paper spray mass spectrometry (PS-MS); or alternatively (2) the use of atmospheric pressure ionization (API) mass spectrometry by direct infusion of a diluted sample through either atmospheric pressure chemical ionization (APCI) or electrospray (ESI) ionization sources. The second strategy involved a minimum sample work-up consisting of a simple olive oil dilution (from 1:10 to 1:1000) with appropriate solvents, which originated critical carry over effects in ESI, making unreliable its use in routine; thus, ESI required the use of a liquid-liquid extraction to shift the measurement towards a specific part of the composition of the edible oil (i.e. polyphenol rich fraction or lipid/fatty acid profile). On the other hand, LTP-MS enabled direct undiluted mass analysis of olive oil. The use of PS-MS provided additional advantages such as an extended ionization coverage/molecular weight range (compared to LTP-MS) and the possibility to increase the ionization efficiency towards nonpolar compounds such as squalene through the formation of Ag + adducts with carbon-carbon double bounds, an attractive feature to discriminate between oils with different degree of unsaturation. Copyright © 2017 Elsevier B.V. All rights reserved.

Validation and application of a high-performance liquid chromatography--tandem mass spectrometry assay for mosapride in human plasma.

Science.gov (United States)

Ramakrishna, N V S; Vishwottam, K N; Manoj, S; Koteshwara, M; Chidambara, J; Varma, D P

2005-09-01

A simple, rapid, sensitive and specific liquid chromatography-tandem mass spectrometry method was developed and validated for quantification of mosapride (I), a novel and potent gastroprokinetic agent that enhances the upper gastrointestinal motility by stimulating 5-HT(4) receptor. The analyte and internal standard, tamsulosin (II), were extracted by liquid-liquid extraction with diethyl ether-dichloromethane (70:30, v/v) using a Glas-Col Multi-Pulse Vortexer. The chromatographic separation was performed on a reversed-phase Waters symmetry C(18) column with a mobile phase of 0.03% formic acid-acetonitrile (10:90, v/v). The protonated analyte was quantitated in positive ionization by multiple reaction monitoring with a mass spectrometer. The mass transitions m/z 422.3 -->198.3 and m/z 409.1 -->228.1 were used to measure I and II, respectively. The assay exhibited a linear dynamic range of 0.5-100.0 ng/mL for mosapride in human plasma. The lower limit of quantitation was 500 pg/mL with a relative standard deviation of less than 15%. Acceptable precision and accuracy were obtained for concentrations over the standard curve ranges. A run time of 2.0 min for each sample made it possible to analyze a throughput of more than 400 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies. Copyright (c) 2005 John Wiley & Sons, Ltd.

Sensitive liquid chromatography-tandem mass spectrometry method for quantification of hydrochlorothiazide in human plasma.

Science.gov (United States)

Ramakrishna, N V S; Vishwottam, K N; Manoj, S; Koteshwara, M; Wishu, S; Varma, D P

2005-12-01

A simple, rapid, sensitive and specific liquid chromatography-tandem mass spectrometry method was developed and validated for quantification of hydrochlorothiazide (I), a common diuretic and anti-hypertensive agent. The analyte and internal standard, tamsulosin (II) were extracted by liquid-liquid extraction with diethyl ether-dichloromethane (70:30, v/v) using a Glas-Col Multi-Pulse Vortexer. The chromatographic separation was performed on a reversed-phase column (Waters symmetry C18) with a mobile phase of 10 mm ammonium acetate-methanol (15:85, v/v). The protonated analyte was quantitated in negative ionization by multiple reaction monitoring with a mass spectrometer. The mass transitions m/z 296.1 solidus in circle 205.0 and m/z 407.2 solidus in circle 184.9 were used to measure I and II, respectively. The assay exhibited a linear dynamic range of 0.5-200 ng/mL for hydrochlorothiazide in human plasma. The lower limit of quantitation was 500 pg/mL, with a relative standard deviation of less than 9%. Acceptable precision and accuracy were obtained for concentrations over the standard curve ranges. A run time of 2.5 min for each sample made it possible to analyze a throughput of more than 400 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies. (c) 2005 John Wiley & Sons, Ltd.

Demonstration of a collimated in situ method for determining depth distributions using gamma-ray spectrometry

CERN Document Server

Benke, R R

2002-01-01

In situ gamma-ray spectrometry uses a portable detector to quantify radionuclides in materials. The main shortcoming of in situ gamma-ray spectrometry has been its inability to determine radionuclide depth distributions. Novel collimator designs were paired with a commercial in situ gamma-ray spectrometry system to overcome this limitation for large area sources. Positioned with their axes normal to the material surface, the cylindrically symmetric collimators limited the detection of un attenuated gamma-rays from a selected range of polar angles (measured off the detector axis). Although this approach does not alleviate the need for some knowledge of the gamma-ray attenuation characteristics of the materials being measured, the collimation method presented in this paper represents an absolute method that determines the depth distribution as a histogram, while other in situ methods require a priori knowledge of the depth distribution shape. Other advantages over previous in situ methods are that this method d...

Glucose and glycerol concentrations and their tracer enrichment measurements using liquid chromatography tandem mass spectrometry

DEFF Research Database (Denmark)

Bornø, Andreas; Foged, Lene; van Hall, Gerrit

2014-01-01

The present study describes a new liquid chromatography tandem mass spectrometry method for high-throughput quantification of glucose and glycerol in human plasma using stable isotopically labeled internal standards and is suitable for simultaneous measurements of glucose and glycerol enrichments...... of variation were 2.0% and 9.7%, respectively. After derivatization, plasma samples were stable for at least 14 days. In conclusion, we have developed and validated a novel, accurate, and sensitive high-throughput liquid chromatography tandem mass spectrometry method for simultaneous determination of glucose...

Bioanalytical method development and validation for the determination of glycine in human cerebrospinal fluid by ion-pair reversed-phase liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Jiang, Jian; James, Christopher A; Wong, Philip

2016-09-05

A LC-MS/MS method has been developed and validated for the determination of glycine in human cerebrospinal fluid (CSF). The validated method used artificial cerebrospinal fluid as a surrogate matrix for calibration standards. The calibration curve range for the assay was 100-10,000ng/mL and (13)C2, (15)N-glycine was used as an internal standard (IS). Pre-validation experiments were performed to demonstrate parallelism with surrogate matrix and standard addition methods. The mean endogenous glycine concentration in a pooled human CSF determined on three days by using artificial CSF as a surrogate matrix and the method of standard addition was found to be 748±30.6 and 768±18.1ng/mL, respectively. A percentage difference of -2.6% indicated that artificial CSF could be used as a surrogate calibration matrix for the determination of glycine in human CSF. Quality control (QC) samples, except the lower limit of quantitation (LLOQ) QC and low QC samples, were prepared by spiking glycine into aliquots of pooled human CSF sample. The low QC sample was prepared from a separate pooled human CSF sample containing low endogenous glycine concentrations, while the LLOQ QC sample was prepared in artificial CSF. Standard addition was used extensively to evaluate matrix effects during validation. The validated method was used to determine the endogenous glycine concentrations in human CSF samples. Incurred sample reanalysis demonstrated reproducibility of the method. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Computational methods for protein identification from mass spectrometry data.

Directory of Open Access Journals (Sweden)

Leo McHugh

2008-02-01

Full Text Available Protein identification using mass spectrometry is an indispensable computational tool in the life sciences. A dramatic increase in the use of proteomic strategies to understand the biology of living systems generates an ongoing need for more effective, efficient, and accurate computational methods for protein identification. A wide range of computational methods, each with various implementations, are available to complement different proteomic approaches. A solid knowledge of the range of algorithms available and, more critically, the accuracy and effectiveness of these techniques is essential to ensure as many of the proteins as possible, within any particular experiment, are correctly identified. Here, we undertake a systematic review of the currently available methods and algorithms for interpreting, managing, and analyzing biological data associated with protein identification. We summarize the advances in computational solutions as they have responded to corresponding advances in mass spectrometry hardware. The evolution of scoring algorithms and metrics for automated protein identification are also discussed with a focus on the relative performance of different techniques. We also consider the relative advantages and limitations of different techniques in particular biological contexts. Finally, we present our perspective on future developments in the area of computational protein identification by considering the most recent literature on new and promising approaches to the problem as well as identifying areas yet to be explored and the potential application of methods from other areas of computational biology.

Determination of chlorine in coal by X-ray fluorescence spectrometry method

Energy Technology Data Exchange (ETDEWEB)

Marek, S.; Bojarska, K. [Central Mining Institute, Katowice (Poland). Dept. of Environmental Monitoring

1997-12-31

Determination of chlorine contents in coal is essential for both environmental protection and its technological use. The existing method of chlorine determination in coal are titration methods which have considerable errors particularly in the low concentration range. The elaborated method with the use of X-ray fluorescence spectrometry in a comparison to the other methods is much faster and has better precision and accuracy. The principle of the method lies in the measurement of X-ray fluorescence radiation intensity which is emitted by chlorine in a sample and its comparison with standards. The calibration of the elaborated XRF method is based on natural coals having various concentrations of chlorine within the whole range of its occurrence in Polish coals. Concentrations for the calibration purpose were obtained by the determination of chlorine contents in selected coals by atomic absorption spectrometry method. The procedure of sample preparation for direct X-ray measurements, instrumental measuring conditions and the way of calibration curve preparation are described in the paper. All X-ray measurements were done with a Phillips sequential X-ray fluorescence spectrometer. A double anode Cr-Au X-ray tube with maximum power 3000 MW was used as the excitation source. 5 figs., 4 tabs.

Fit for purpose validated method for the determination of the strontium isotopic signature in mineral water samples by multi-collector inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Brach-Papa, Christophe; Van Bocxstaele, Marleen; Ponzevera, Emmanuel [European Commission - Joint Research Centre - Institute for Reference Materials and Measurements, Retieseweg 111 - 2440 Geel (Belgium); Quetel, Christophe R. [European Commission - Joint Research Centre - Institute for Reference Materials and Measurements, Retieseweg 111 - 2440 Geel (Belgium)], E-mail: christophe.quetel@ec.europa.eu

2009-03-15

A robust method allowing the routine determination of n({sup 87}Sr)/n({sup 86}Sr) with at least five significant decimal digits for large sets of mineral water samples is described. It is based on 2 consecutive chromatographic separations of Sr associated to multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) measurements. Separations are performed using commercial pre-packed columns filled with 'Sr resin' to overcome isobaric interferences affecting the determination of strontium isotope ratios. The careful method validation scheme applied is described. It included investigations on all parameters influencing both chromatographic separations and MC-ICPMS measurements, and also the test on a synthetic sample made of an aliquot of the NIST SRM 987 certified reference material dispersed in a saline matrix to mimic complex samples. Correction for mass discrimination was done internally using the n({sup 88}Sr)/n({sup 86}Sr) ratio. For comparing mineral waters originating from different geological backgrounds or identifying counterfeits, calculations involved the well known consensus value (1/0.1194) {+-} 0 as reference. The typical uncertainty budget estimated for these results was 40 'ppm' relative (k = 2). It increased to 150 'ppm' (k = 2) for the establishment of stand alone results, taking into account a relative difference of about 126 'ppm' systematically observed between measured and certified values of the NIST SRM 987. In case there was suspicion of a deviation of the n({sup 88}Sr)/n({sup 86}Sr) ratio (worst case scenario) our proposal was to use the NIST SRM 987 value 8.37861 {+-} 0.00325 (k = 2) as reference, and assign a typical relative uncertainty budget of 300 'ppm' (k = 2). This method is thus fit for purpose and was applied to eleven French samples.

Development and Validation of a Liquid Chromatography-Tandem Mass Spectrometry Method Coupled with Dispersive Solid-Phase Extraction for Simultaneous Quantification of Eight Paralytic Shellfish Poisoning Toxins in Shellfish

Science.gov (United States)

Yang, Xianli; Zhou, Lei; Tan, Yanglan; Shi, Xizhi; Zhao, Zhiyong; Nie, Dongxia; Zhou, Changyan; Liu, Hong

2017-01-01

In this study, a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for simultaneous determination of eight paralytic shellfish poisoning (PSP) toxins, including saxitoxin (STX), neosaxitoxin (NEO), gonyautoxins (GTX1–4) and the N-sulfo carbamoyl toxins C1 and C2, in sea shellfish. The samples were extracted by acetonitrile/water (80:20, v/v) with 0.1% formic and purified by dispersive solid-phase extraction (dSPE) with C18 silica and acidic alumina. Qualitative and quantitative detection for the target toxins were conducted under the multiple reaction monitoring (MRM) mode by using the positive electrospray ionization (ESI) mode after chromatographic separation on a TSK-gel Amide-80 HILIC column with water and acetonitrile. Matrix-matched calibration was used to compensate for matrix effects. The established method was further validated by determining the linearity (R2 ≥ 0.9900), average recovery (81.52–116.50%), sensitivity (limits of detection (LODs): 0.33–5.52 μg·kg−1; limits of quantitation (LOQs): 1.32–11.29 μg·kg−1) and precision (relative standard deviation (RSD) ≤ 19.10%). The application of this proposed approach to thirty shellfish samples proved its desirable performance and sufficient capability for simultaneous determination of multiclass PSP toxins in sea foods. PMID:28661471

A fast, comprehensive screening method for doping agents in urine by gas chromatography-triple quadrupole mass spectrometry.

Science.gov (United States)

Van Eenoo, Peter; Van Gansbeke, Wim; De Brabanter, Nik; Deventer, Koen; Delbeke, Frans T

2011-05-27

The use of performance enhancing drugs in sports is prohibited. For the detection of misuse of such substances gas chromatography or liquid chromatography coupled to mass spectrometry are the most frequently used detection techniques. In this work the development and validation of a fast gas chromatography tandem mass spectrometric method for the detection of a wide range of doping agents is described. The method can determine 13 endogenous steroids (the steroid profile), 19-norandrosterone, salbutamol and 11-nor-Δ9-tetrahydrocannabinol.9carboxylic acid in the applicable ranges and to detect qualitatively over 140 substances in accordance with the minimum required performance levels of the World Anti-Doping Agency in 1ml of urine. The classes of substances included in the method are anabolic steroids, β2-agonists, stimulants, narcotics, hormone antagonists and modulators and beta-blockers. Moreover, using a short capillary column and hydrogen as a carrier gas the run time of the method is less than 8min. Copyright © 2010 Elsevier B.V. All rights reserved.

Validation of the method for determination of plutonium isotopes in urine samples and its application in a nuclear facility at Otwock

Directory of Open Access Journals (Sweden)

Rzemek Katarzyna

2015-03-01

Full Text Available The studies aimed at determining low activities of alpha radioactive elements are widely recognized as essential for the human health, because of their high radiotoxicity in case of internal contamination. Some groups of workers of nuclear facility at Otwock are potentially exposed to contamination with plutonium isotopes. For this reason, the method for determination of plutonium isotopes has been introduced and validated in Radiation Protection Measurements Laboratory (LPD of the National Centre for Nuclear Research (NCBJ. In this method the plutonium is isolated from a sample by coprecipitation with phosphates and separated on a AG 1-X2 Resin. After electrodeposition, the sample is measured by alpha spectrometry. Validation was performed in order to assess parameters such as: selectivity, accuracy (trueness and precision and linearity of the method. The results of plutonium determination in urine samples of persons potentially exposed to internal contamination are presented in this work.

Improved sample preparation method for environmental plutonium analysis by ICP-SFMS and alpha-spectrometry

International Nuclear Information System (INIS)

Varga, Z.; Stefanka, Z.; Suranyi, G.; Vajda, N.

2007-01-01

A rapid and simple sample preparation method for plutonium determination in environmental samples by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) and alpha-spectrometry is described. The developed procedure involves a selective CaF 2 co-precipitation for preconcentration followed by extraction chromatographic separation. The proposed method effectively eliminates the possible interferences in mass spectrometric analysis and also removes interfering radionuclides that may disturb alpha-spectrometric measurement. For 239 Pu, 240 Pu and 241 Pu limits of detection of 9.0 fg x g -1 (0.021 mBq), 1.7 fg x g -1 (0.014 mBq) and 3.1 fg x g -1 (11.9 mBq) were achieved by ICP-SFMS, respectively, and 0.02 mBq by alpha-spectrometry. Results of certified reference materials agreed well with the recommended values. (author)

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.

In-house validation of a liquid chromatography-tandem mass spectrometry method for the determination of selective androgen receptor modulators (SARMS) in bovine urine.

Science.gov (United States)

Schmidt, Kathrin S; Mankertz, Joachim

2018-06-01

A sensitive and robust LC-MS/MS method allowing the rapid screening and confirmation of selective androgen receptor modulators in bovine urine was developed and successfully validated according to Commission Decision 2002/657/EC, chapter 3.1.3 'alternative validation', by applying a matrix-comprehensive in-house validation concept. The confirmation of the analytes in the validation samples was achieved both on the basis of the MRM ion ratios as laid down in Commission Decision 2002/657/EC and by comparison of their enhanced product ion (EPI) spectra with a reference mass spectral library by making use of the QTRAP technology. Here, in addition to the MRM survey scan, EPI spectra were generated in a data-dependent way according to an information-dependent acquisition criterion. Moreover, stability studies of the analytes in solution and in matrix according to an isochronous approach proved the stability of the analytes in solution and in matrix for at least the duration of the validation study. To identify factors that have a significant influence on the test method in routine analysis, a factorial effect analysis was performed. To this end, factors considered to be relevant for the method in routine analysis (e.g. operator, storage duration of the extracts before measurement, different cartridge lots and different hydrolysis conditions) were systematically varied on two levels. The examination of the extent to which these factors influence the measurement results of the individual analytes showed that none of the validation factors exerts a significant influence on the measurement results.

Rapid and accurate liquid chromatography and tandem mass spectrometry method for the simultaneous quantification of ten metabolic reactions catalyzed by hepatic cytochrome P450 enzymes.

Science.gov (United States)

Shi, Rong; Ma, Bingliang; Wu, Jiasheng; Wang, Tianming; Ma, Yueming

2015-10-01

The hepatic cytochrome P450 enzymes play a central role in the biotransformation of endogenous and exogenous substances. A sensitive high-throughput liquid chromatography with tandem mass spectrometry assay was developed and validated for the simultaneous quantification of the products of ten metabolic reactions catalyzed by hepatic cytochrome P450 enzymes. After the substrates were incubated separately, the samples were pooled and analyzed by liquid chromatography with tandem mass spectrometry using an electrospray ionization source in the positive and negative ion modes. The method exhibited linearity over a broad concentration range, insensitivity to matrix effects, and high accuracy, precision, and stability. The novel method was successfully applied to study the kinetics of phenacetin-O deethylation, coumarin-7 hydroxylation, bupropion hydroxylation, taxol-6 hydroxylation, omeprazole-5 hydroxylation, dextromethorphan-O demethylation, tolbutamide-4 hydroxylation, chlorzoxazone-6 hydroxylation, testosterone-6β hydroxylation, and midazolam-1 hydroxylation in rat liver microsomes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of perfluorinated compounds in fish fillet homogenates: method validation and application to fillet homogenates from the Mississippi River.

Science.gov (United States)

Malinsky, Michelle Duval; Jacoby, Cliffton B; Reagen, William K

2011-01-10

We report herein a simple protein precipitation extraction-liquid chromatography tandem mass spectrometry (LC/MS/MS) method, validation, and application for the analysis of perfluorinated carboxylic acids (C7-C12), perfluorinated sulfonic acids (C4, C6, and C8), and perfluorooctane sulfonamide (FOSA) in fish fillet tissue. The method combines a rapid homogenization and protein precipitation tissue extraction procedure using stable-isotope internal standard (IS) calibration. Method validation in bluegill (Lepomis macrochirus) fillet tissue evaluated the following: (1) method accuracy and precision in both extracted matrix-matched calibration and solvent (unextracted) calibration, (2) quantitation of mixed branched and linear isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) with linear isomer calibration, (3) quantitation of low level (ppb) perfluorinated compounds (PFCs) in the presence of high level (ppm) PFOS, and (4) specificity from matrix interferences. Both calibration techniques produced method accuracy of at least 100±13% with a precision (%RSD) ≤18% for all target analytes. Method accuracy and precision results for fillet samples from nine different fish species taken from the Mississippi River in 2008 and 2009 are also presented. Copyright © 2010 Elsevier B.V. All rights reserved.

Determination of calcium, magnesium, sodium, and potassium in foodstuffs by using a microsampling flame atomic absorption spectrometric method after closed-vessel microwave digestion: method validation.

Science.gov (United States)

Chekri, Rachida; Noël, Laurent; Vastel, Christelle; Millour, Sandrine; Kadar, Ali; Guérin, Thierry

2010-01-01

This paper describes a validation process in compliance with the NFIEN ISO/IEC 17025 standard for the determination of the macrominerals calcium, magnesium, sodium, and potassium in foodstuffs by microsampling with flame atomic absorption spectrometry after closed-vessel microwave digestion. The French Standards Commission (Agence Francaise de Normalisation) standards NF V03-110, NF EN V03-115, and XP T-90-210 were used to evaluate this method. The method was validated in the context of an analysis of the 1322 food samples of the second French Total Diet Study (TDS). Several performance criteria (linearity, LOQ, specificity, trueness, precision under repeatability conditions, and intermediate precision reproducibility) were evaluated. Furthermore, the method was monitored by several internal quality controls. The LOQ values obtained (25, 5, 8.3, and 8.3 mg/kg for Ca, Mg, Na, and K, respectively) were in compliance with the needs of the TDS. The method provided accurate results as demonstrated by a repeatability CV (CVr) of < 7% and a reproducibility CV (CVR) of < 12% for all the elements. Therefore, the results indicated that this method could be used in the laboratory for the routine determination of these four elements in foodstuffs with acceptable analytical performance.

Determination of mercury in hair: Comparison between gold amalgamation-atomic absorption spectrometry and mass spectrometry.

Science.gov (United States)

Domanico, Francesco; Forte, Giovanni; Majorani, Costanza; Senofonte, Oreste; Petrucci, Francesco; Pezzi, Vincenzo; Alimonti, Alessandro

2017-09-01

Mercury is a heavy metal that causes serious health problems in exposed subjects. The most toxic form, i.e., methylmercury (MeHg), is mostly excreted through human hair. Numerous analytical methods are available for total Hg analysis in human hair, including cold vapour atomic fluorescence spectrometry (CV-AFS), inductively coupled plasma mass spectrometry (ICP-MS) and thermal decomposition amalgamation atomic absorption spectrometry (TDA-AAS). The aim of the study was to compare the TDA-AAS with the ICP-MS in the Hg quantification in human hair. After the washing procedure to minimize the external contamination, from each hair sample two aliquots were taken; the first was used for direct analysis of Hg by TDA-AAS and the second was digested for Hg determination by the ICP-MS. Results indicated that the two data sets were fully comparable (median; TDA-AAS, 475ngg -1 ; ICP-MS, 437ngg -1 ) and were not statistically different (Mann-Whitney test; p=0.44). The two techniques presented results with a good coefficient of correlation (r=0.94) despite different operative ranges and method limits. Both techniques satisfied internal performance requirements and the parameters for method validation resulting sensitive, precise and reliable. Finally, the use of the TDA-AAS can be considered instead of the ICP-MS in hair analysis in order to reduce sample manipulation with minor risk of contamination, less time consuming due to the absence of the digestion step and cheaper analyses. Copyright © 2016 Elsevier GmbH. All rights reserved.

A rugged and transferable method for determining blood cadmium, mercury, and lead with inductively coupled plasma-mass spectrometry

International Nuclear Information System (INIS)

McShane, William J.; Pappas, R. Steven; Wilson-McElprang, Veronica; Paschal, Dan

2008-01-01

A simple, high-throughput method for determining total cadmium, mercury, and lead in blood in cases of suspected exposure, using inductively coupled plasma-mass spectrometry (ICP-MS), has been developed and validated. One part matrix-matched standards, blanks, or aliquots of blood specimens were diluted with 49 parts of a solution containing 0.25% (w/w) tetramethylammonium hydroxide; 0.05% v/v Triton X-100 (blood cell membranes and protein solubilization); 0.01% (w/v) ammonium pyrolidinedithiocarbamate (mercury memory effect prevention and oxidation state stabilization, solubilization by complexation of all three metals); 1% v/v isopropanol (signal enhancement); and 10 μg/L iridium (internal standard). Thus the final dilution factor is 1 + 49. The method provides the basis for the determination of total cadmium, mercury, and lead for assessment of environmental, occupational, accidental ingestion or elevated exposures from other means. Approximately 80 specimens, including blanks, calibration standards, and quality control materials can be processed in an 8-h day. The method has been evaluated by examining reference materials from the National Institute of Standards and Technology, as well as by participation in six rounds of proficiency testing intercomparisons led by the Wadsworth Center of the New York State Department of Health. This method was developed for the purpose of increasing U.S. emergency response laboratory capacity. To this end, 33 U.S. state, and 1 district health department laboratories have validated this method in their own laboratories

A rugged and transferable method for determining blood cadmium, mercury, and lead with inductively coupled plasma-mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

McShane, William J. [Battelle-Centers for Disease Control and Prevention, Division of Laboratory Sciences, Emergency Response and Air Toxicants Branch, 4770 Buford Highway, MS F-44, Atlanta, GA 30341 (United States)], E-mail: WMcShane@cdc.gov; Pappas, R. Steven [Centers for Disease Control and Prevention, Division of Laboratory Sciences, Emergency Response and Air Toxicants, 4770 Buford Highway, MS F-44, Atlanta, GA 30341 (United States)], E-mail: RPappas@cdc.gov; Wilson-McElprang, Veronica [Battelle-Centers for Disease Control and Prevention, Division of Laboratory Sciences, Emergency Response and Air Toxicants Branch, 4770 Buford Highway, MS F-44, Atlanta, GA 30341 (United States)], E-mail: VWilsonMcelprang@cdc.gov; Paschal, Dan [Centers for Disease Control and Prevention, Division of Laboratory Sciences, Emergency Response and Air Toxicants, 4770 Buford Highway, MS F-44, Atlanta, GA 30341 (United States)], E-mail: DPaschal@cdc.gov

2008-06-15

A simple, high-throughput method for determining total cadmium, mercury, and lead in blood in cases of suspected exposure, using inductively coupled plasma-mass spectrometry (ICP-MS), has been developed and validated. One part matrix-matched standards, blanks, or aliquots of blood specimens were diluted with 49 parts of a solution containing 0.25% (w/w) tetramethylammonium hydroxide; 0.05% v/v Triton X-100 (blood cell membranes and protein solubilization); 0.01% (w/v) ammonium pyrolidinedithiocarbamate (mercury memory effect prevention and oxidation state stabilization, solubilization by complexation of all three metals); 1% v/v isopropanol (signal enhancement); and 10 {mu}g/L iridium (internal standard). Thus the final dilution factor is 1 + 49. The method provides the basis for the determination of total cadmium, mercury, and lead for assessment of environmental, occupational, accidental ingestion or elevated exposures from other means. Approximately 80 specimens, including blanks, calibration standards, and quality control materials can be processed in an 8-h day. The method has been evaluated by examining reference materials from the National Institute of Standards and Technology, as well as by participation in six rounds of proficiency testing intercomparisons led by the Wadsworth Center of the New York State Department of Health. This method was developed for the purpose of increasing U.S. emergency response laboratory capacity. To this end, 33 U.S. state, and 1 district health department laboratories have validated this method in their own laboratories.

Determination of platinum in human subcellular microsamples by inductively coupled plasma mass spectrometry

DEFF Research Database (Denmark)

Björn, Erik; Nygren, Yvonne; Nguyen, Tam T. T. N.

2007-01-01

A fast and robust method for the determination of platinum in human subcellular microsamples by inductively coupled plasma mass spectrometry was developed, characterized, and validated. Samples of isolated DNA and exosome fractions from human ovarian (2008) and melanoma (T289) cancer cell lines w...

Comments on “innovative method for carbon dioxide determination in human postmortem cardiac gas samples using headspace-gas chromatography–mass spectrometry and stable labeled isotope as internal standard” by Varlet et al

Energy Technology Data Exchange (ETDEWEB)

Saffaj, T., E-mail: taoufiq.saffaj@usmba.ac.ma [Centre Universitaire Régional d’Interface, Université Sidi Mohamed Ben Abdellah, BP 2626, route d’Imouzzer, Fes Morocco (Morocco); Laboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, BP 2202, route d’Imouzzer, Fes Morocco (Morocco); Ihssane, B. [Laboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, BP 2202, route d’Imouzzer, Fes Morocco (Morocco)

2014-01-31

Graphical abstract: -- Highlights: •We comment on the validation results of the method for CO{sub 2} analysis in cardiac samples. •We demonstrate that the total error of the method exceeds the acceptance limits. •We show that the method is not valid according to the new SFSTP guideline. -- Abstract: Varlet et al. recently proposed a headspace-gas chromatography–mass spectrometry (HS-GC–MS) method applicable for the routine determination of CO{sub 2} in gaseous biologic matrices. This developed bioanalytical method was fully validated according to the SFSTP 1997 guidelines using the accuracy profile as a graphical decision-making tool.In this letter, we discuss the validity of HS-GC–MS method based on the newest SFSTP guideline. In particular, we demonstrate by the estimation of the β-expectation tolerance interval that the error total exceeds the acceptance limits (30%) for the second concentration level (0.5 μmol mL{sup −1} vial HS). Furthermore, we show through the risk profile that the probability to have future results inside the ±30% acceptance limits is smaller than 95%.

[Validation of an in-house method for the determination of zinc in serum: Meeting the requirements of ISO 17025].

Science.gov (United States)

Llorente Ballesteros, M T; Navarro Serrano, I; López Colón, J L

2015-01-01

The aim of this report is to propose a scheme for validation of an analytical technique according to ISO 17025. According to ISO 17025, the fundamental parameters tested were: selectivity, calibration model, precision, accuracy, uncertainty of measurement, and analytical interference. A protocol has been developed that has been applied successfully to quantify zinc in serum by atomic absorption spectrometry. It is demonstrated that our method is selective, linear, accurate, and precise, making it suitable for use in routine diagnostics. Copyright © 2015 SECA. Published by Elsevier Espana. All rights reserved.

Liquid chromatography-tandem mass spectrometry multiresidue method for the analysis of quaternary ammonium compounds in cheese and milk products: Development and validation using the total error approach.

Science.gov (United States)

Slimani, Kahina; Féret, Aurélie; Pirotais, Yvette; Maris, Pierre; Abjean, Jean-Pierre; Hurtaud-Pessel, Dominique

2017-09-29

Quaternary ammonium compounds (QACs) are both cationic surfactants and biocidal substances widely used as disinfectants in the food industry. A sensitive and reliable method for the analysis of benzalkonium chlorides (BACs) and dialkyldimethylammonium chlorides (DDACs) has been developed that enables the simultaneous quantitative determination of ten quaternary ammonium residues in dairy products below the provisional maximum residue level (MRL), set at 0.1mgkg -1 . To the best of our knowledge, this method could be the one applicable to milk and to three major processed milk products selected, namely processed or hard pressed cheeses, and whole milk powder. The method comprises solvent extraction using a mixture of acetonitrile and ethyl acetate, without any further clean-up. Analyses were performed by liquid chromatography coupled with electrospray tandem mass spectrometry detection (LC-ESI-MS/MS) operating in positive mode. A C18 analytical column was used for chromatographic separation, with a mobile phase composed of acetonitrile and water both containing 0.3% formic acid; and methanol in the gradient mode. Five deuterated internal standards were added to obtain the most accurate quantification. Extraction recoveries were satisfactory and no matrix effects were observed. The method was validated using the total error approach in accordance with the NF V03-110 standard in order to characterize the trueness, repeatability, intermediate precision and analytical limits within the range of 5-150μgkg -1 for all matrices. These performance criteria, calculated by e.noval ® 3.0 software, were satisfactory and in full accordance with the proposed provisional MRL and with the recommendations in the European Union SANTE/11945/2015 regulatory guidelines. The limit of detection (LOD) was low (ammoniums in foodstuffs from dairy industries at residue levels, and could be used for biocide residues monitoring plans and to measure the exposition consumer to biocides products

Lipidomic analysis of biological samples: Comparison of liquid chromatography, supercritical fluid chromatography and direct infusion mass spectrometry methods.

Science.gov (United States)

Lísa, Miroslav; Cífková, Eva; Khalikova, Maria; Ovčačíková, Magdaléna; Holčapek, Michal

2017-11-24

Lipidomic analysis of biological samples in a clinical research represents challenging task for analytical methods given by the large number of samples and their extreme complexity. In this work, we compare direct infusion (DI) and chromatography - mass spectrometry (MS) lipidomic approaches represented by three analytical methods in terms of comprehensiveness, sample throughput, and validation results for the lipidomic analysis of biological samples represented by tumor tissue, surrounding normal tissue, plasma, and erythrocytes of kidney cancer patients. Methods are compared in one laboratory using the identical analytical protocol to ensure comparable conditions. Ultrahigh-performance liquid chromatography/MS (UHPLC/MS) method in hydrophilic interaction liquid chromatography mode and DI-MS method are used for this comparison as the most widely used methods for the lipidomic analysis together with ultrahigh-performance supercritical fluid chromatography/MS (UHPSFC/MS) method showing promising results in metabolomics analyses. The nontargeted analysis of pooled samples is performed using all tested methods and 610 lipid species within 23 lipid classes are identified. DI method provides the most comprehensive results due to identification of some polar lipid classes, which are not identified by UHPLC and UHPSFC methods. On the other hand, UHPSFC method provides an excellent sensitivity for less polar lipid classes and the highest sample throughput within 10min method time. The sample consumption of DI method is 125 times higher than for other methods, while only 40μL of organic solvent is used for one sample analysis compared to 3.5mL and 4.9mL in case of UHPLC and UHPSFC methods, respectively. Methods are validated for the quantitative lipidomic analysis of plasma samples with one internal standard for each lipid class. Results show applicability of all tested methods for the lipidomic analysis of biological samples depending on the analysis requirements

Simultaneous determination of ramipril, ramiprilat and telmisartan in human plasma using liquid chromatography tandem mass spectrometry.

Science.gov (United States)

Gupta, V K; Jain, Rajeev; Lukram, Ojitkumar; Agarwal, Shilpi; Dwivedi, Ashish

2011-01-15

A rapid and sensitive liquid chromatography tandem mass spectrometry method has been developed and validated for the simultaneous determination of ramipril, ramiprilat and telmisartan in human plasma. The solid-phase extraction technique was used for the extraction of ramipril, ramiprilat and telmisartan from human plasma. Trandolaprilat and hydrochlorothiazide were used as the internal standards (ISs). Chromatography was performed on a Hypurity C18, 5 μm, 50 mm × 4.6mm column, with the mobile phase consisting of ammonium acetate and acetonitrile (in a 20:80 ratio), followed by detection using mass spectrometry. The method involves a simple reversed isocratic chromatography condition and mass spectrometry detection, which enables detection at sub-nanogram levels. The method was validated and the lower limit of quantification for ramipril, ramiprilat and telmisartan was found to be 0.1 ng mL(-1), 0.1 ng mL(-1) and 2 ng mL(-1), respectively. The mean recovery for ramipril, ramiprilat and telmisartan ranged from 90.1 to 104.1%. This method increased the sensitivity and selectivity; resulting in high-throughput analysis of ramipril, ramiprilat and telmisartan using two different ISs in a single experiment for bioequivalence studies, with a chromatographic run time of 1.5 min only. Copyright © 2010 Elsevier B.V. All rights reserved.

Validation of a Multiresidue Analysis Method for 379 Pesticides in Human Serum Using Liquid Chromatography-Tandem Mass Spectrometry.

Science.gov (United States)

Shin, Yongho; Lee, Jonghwa; Lee, Jiho; Lee, Junghak; Kim, Eunhye; Liu, Kwang-Hyeon; Lee, Hye Suk; Kim, Jeong-Han

2018-04-04

A screening method for simultaneous analysis of 379 pesticides in human serum was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Electrospray ionization with positive/negative switching mode of LC-MS/MS was adopted, and scheduled multiple reaction monitoring for each target compound was established. The limit of quantitation was 10 ng/mL for 94.5% of the total pesticides, and the correlation coefficients of calibration were ≥0.990 for 93.9% of the pesticides. For the sample preparation, scaled-down QuEChERS were used. Serum (100 μL) was extracted with acetonitrile (400 μL), partitioned with magnesium sulfate (40 mg) and sodium chloride (10 mg), and the upper layer was used for analysis without further cleanup steps. For the accuracy and precision tests, most of the pesticides showed excellent results in intra- and interday conditions. In the recovery tests at 10, 50, and 250 ng/mL, 85.8-91.8% of all target compounds satisfied the recovery range of 70-120% (relative standard deviation ≤20%).

Validation for chromatographic and electrophoretic methods

OpenAIRE

Ribani, Marcelo; Bottoli, Carla Beatriz Grespan; Collins, Carol H.; Jardim, Isabel Cristina Sales Fontes; Melo, Lúcio Flávio Costa

2004-01-01

The validation of an analytical method is fundamental to implementing a quality control system in any analytical laboratory. As the separation techniques, GC, HPLC and CE, are often the principal tools used in such determinations, procedure validation is a necessity. The objective of this review is to describe the main aspects of validation in chromatographic and electrophoretic analysis, showing, in a general way, the similarities and differences between the guidelines established by the dif...

Ion counting method and it's operational characteristics in gas chromatography-mass spectrometry

International Nuclear Information System (INIS)

Fujii, Toshihiro

1976-01-01

Ion counting method with continuous channel electron multiplier which affords the direct detection of very small ion currents and it's operational characteristics were studied in gas chromatography-mass spectrometry. Then this method was applied to the single ion detection technique of GC-MS. A detection limit was measured, using various standard samples of low level concentration. (auth.)

Methods for the analysis of the overlapped peaks in analytical gamma-spectrometry

International Nuclear Information System (INIS)

Sterlinski, S.; Wasek, M.

1989-01-01

A new simple method for the quantitative analysis of the doublet peaks in Ge(Li) or HPGe gamma-spectrometry is presented. No assumptions on the shape of the peaks in gamma-ray spectra being measured are required. Special feature of the method proposed is its usefulness for the analysis of closed doublets. 7 refs., 6 figs. (author)

Computational and statistical methods for high-throughput mass spectrometry-based PTM analysis

DEFF Research Database (Denmark)

Schwämmle, Veit; Vaudel, Marc

2017-01-01

Cell signaling and functions heavily rely on post-translational modifications (PTMs) of proteins. Their high-throughput characterization is thus of utmost interest for multiple biological and medical investigations. In combination with efficient enrichment methods, peptide mass spectrometry analy...

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.

Analytical difficulties facing today's regulatory laboratories: issues in method validation.

Science.gov (United States)

MacNeil, James D

2012-08-01

The challenges facing analytical laboratories today are not unlike those faced in the past, although both the degree of complexity and the rate of change have increased. Challenges such as development and maintenance of expertise, maintenance and up-dating of equipment, and the introduction of new test methods have always been familiar themes for analytical laboratories, but international guidelines for laboratories involved in the import and export testing of food require management of such changes in a context which includes quality assurance, accreditation, and method validation considerations. Decisions as to when a change in a method requires re-validation of the method or on the design of a validation scheme for a complex multi-residue method require a well-considered strategy, based on a current knowledge of international guidance documents and regulatory requirements, as well the laboratory's quality system requirements. Validation demonstrates that a method is 'fit for purpose', so the requirement for validation should be assessed in terms of the intended use of a method and, in the case of change or modification of a method, whether that change or modification may affect a previously validated performance characteristic. In general, method validation involves method scope, calibration-related parameters, method precision, and recovery. Any method change which may affect method scope or any performance parameters will require re-validation. Some typical situations involving change in methods are discussed and a decision process proposed for selection of appropriate validation measures. © 2012 John Wiley & Sons, Ltd.

Multiclass mycotoxin analysis in edible oils using a simple solvent extraction method and liquid chromatography with tandem mass spectrometry.

Science.gov (United States)

Eom, Taeyong; Cho, Hyun-Deok; Kim, Junghyun; Park, Mihee; An, Jinyoung; Kim, Moosung; Kim, Sheen-Hee; Han, Sang Beom

2017-11-01

A simple and rapid method for the simultaneous determination of 11 mycotoxins - aflatoxins B 1 , B 2 , G 1 and G 2 ; fumonisins B 1 , B 2 and B 3 ; ochratoxin A; zearalenone; deoxynivalenol; and T-2 toxin - in edible oils was established using liquid chromatography tandem mass spectrometry (LC-MS/MS). In this study, QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe), QuEChERS with dispersive liquid-liquid microextraction, and solvent extraction were examined for sample preparation. Among these methods, solvent extraction with a mixture of formic acid/acetonitrile (5/95, v/v) successfully extracted all target mycotoxins. Subsequently, a defatting process using n-hexane was employed to remove the fats present in the edible oil samples. Mass spectrometry was carried out using electrospray ionisation in polarity switching mode with multiple reaction monitoring. The developed LC-MS/MS method was validated by assessing the specificity, linearity, recovery, limit of quantification (LOQ), accuracy and precision with reference to Commission Regulation (EC) 401/2006. Mycotoxin recoveries of 51.6-82.8% were achieved in addition to LOQs ranging from 0.025 ng/g to 1 ng/g. The edible oils proved to be relatively uncomplicated matrices and the developed method was applied to 9 edible oil samples, including soybean oil, corn oil and rice bran oil, to evaluate potential mycotoxin contamination. The levels of detection were significantly lower than the international regulatory standards. Therefore, we expect that our developed method, based on simple, two-step sample preparation process, will be suitable for the large-scale screening of mycotoxin contamination in edible oils.

Validation of 226Ra, 228Ra and 210Pb measurements in soil and sediment samples through high resolution gamma ray spectrometry

International Nuclear Information System (INIS)

Dias, Danila Carrijo da Silva; Silva, Nivaldo Carlos da; Bonifacio, Rodrigo Leandro; Guerrero, Eder Tadeu Zenun

2013-01-01

Radionuclides found in ore extraction waste materials are a great source of concern regarding public health and environmental safety. One technique to determine the concentration of substances is high resolution gamma ray spectrometry using HPGe. Validating a measurement technique is essential to warrant high levels of quality to any scientific work. The Laboratory of Pocos de Caldas of the Brazilian Commission for Nuclear Energy partakes into a Quality Management System project, seeking Accreditation under ISO/IEC 17025 through the validation of techniques of chemical and radiometric analysis of environmental samples from water, soil and sediment. The focus of the Radon Laboratory at LAPOC is validation of Ra-226, Ra-228 and Pb-210 concentration determinations in soil and sediment through a gamma spectrometer system. The stages of this validation process included sample reception and preparation, detector calibration and sample analyses. Dried samples were sealed in metallic containers and analyzed after radioactive equilibrium between Ra-226 and daughters Pb-214 and Bi-214. Gamma spectrometry was performed using CANBERRA HPGe detector and gamma spectrum software Genie 2000. The photo peaks used for Ra-226 determination were 609 keV and 1020 keV of Bi-214 and 351 keV of Pb-214. For the Ra-228 determination a photopeak of 911 keV was used from its short half-life daughter Ac-228 (T1/2 = 6.12 h). For Pb-210, the photopeak of 46.5 keV was used, which, due to the low energy, self-absorption correction was needed. Parameters such as precision, bias/accuracy, linearity, detection limit and uncertainty were evaluated for that purpose. The results have pointed to satisfying results. (author)

Multivariate analysis method for energy calibration and improved mass assignment in recoil spectrometry

International Nuclear Information System (INIS)

El Bouanani, Mohamed; Hult, Mikael; Persson, Leif; Swietlicki, Erik; Andersson, Margaretha; Oestling, Mikael; Lundberg, Nils; Zaring, Carina; Cohen, D.D.; Dytlewski, Nick; Johnston, P.N.; Walker, S.R.; Bubb, I.F.; Whitlow, H.J.

1994-01-01

Heavy ion recoil spectrometry is rapidly becoming a well established analysis method, but the associated data analysis processing is still not well developed. The pronounced nonlinear response of silicon detectors for heavy ions leads to serious limitation and complication in mass gating, which is the principal factor in obtaining energy spectra with minimal cross talk between elements. To overcome the above limitation, a simple empirical formula with an associated multiple regression method is proposed for the absolute energy calibration of the time of flight-energy dispersive detector telescope used in recoil spectrometry. A radical improvement in mass assignment was realized, which allows a more accurate and improved depth profiling with the important feature of making the data processing much easier. ((orig.))

A candidate liquid chromatography mass spectrometry reference method for the quantification of the cardiac marker 1-32 B-type natriuretic peptide.

Science.gov (United States)

Torma, Attila F; Groves, Kate; Biesenbruch, Sabine; Mussell, Chris; Reid, Alan; Ellison, Steve; Cramer, Rainer; Quaglia, Milena

2017-08-28

B-type natriuretic peptide (BNP) is a 32 amino acid cardiac hormone routinely measured by immunoassays to diagnose heart failure. While it is reported that immunoassay results can vary up to 45%, no attempt of standardization and/or harmonization through the development of certified reference materials (CRMs) or reference measurement procedures (RMPs) has yet been carried out. B-type natriuretic peptide primary calibrator was quantified traceably to the International System of Units (SI) by both amino acid analysis and tryptic digestion. A method for the stabilization of BNP in plasma followed by protein precipitation, solid phase extraction (SPE) and liquid chromatography (LC) mass spectrometry (MS) was then developed and validated for the quantification of BNP at clinically relevant concentrations (15-150 fmol/g). The candidate reference method was applied to the quantification of BNP in a number of samples from the UK NEQAS Cardiac Markers Scheme to demonstrate its applicability to generate reference values and to preliminary evaluate the commutability of a potential CRM. The results from the reference method were consistently lower than the immunoassay results and discrepancy between the immunoassays was observed confirming previous data. The application of the liquid chromatography-mass spectrometry (LC-MS) method to the UK NEQAS samples and the correlation of the results with the immunoassay results shows the potential of the method to support external quality assessment schemes, to improve understanding of the bias of the assays and to establish RMPs for BNP measurements. Furthermore, the method has the potential to be multiplexed for monitoring circulating truncated forms of BNP.

Neutron spectrometry and dosimetry using NSDAAN

International Nuclear Information System (INIS)

Martinez B, M. R.; Vega C, H. R.; Ortiz R, J. M.

2009-10-01

The reconstruction of neutron spectra from count rates of a Bonner spheres spectrometric system is performed using various methods such as Monte Carlo methods, the parameterization and iterative methods. The weight of the Bonner spheres spectrometric system, the procedure for the reconstruction of the spectra, the need of an experienced user, the high consumer of time, the need of use a reconstruction code as the BUNKI, SAND, among others, and the resolution of the spectrum are some problems that this system presents. This has motivated the development of complementary procedures such as maximum entropy, genetic algorithms and artificial neural networks. In previous work, has reported a new method called robust design methodology of artificial neural networks, to construct various network topologies capable of solving the problems of neutron spectrometry and dosimetry, however, due to the newness of this technology, be noted that there are not tools to end-user that allow test and validate the designed networks. This paper presents a software for the neutron spectrometry and dosimetry, designed from the information extracted of an artificial neural network designed by robust design methodology of artificial neural networks. This tool has the following characteristics: was designed in a user graphical interface easy to use, requires not knowledge of neural networks or neutron spectrometry by the user; execution speed of the application; unlike the deconvolution codes are not required to select an initial spectrum for the spectrum reconstruction; as an additional element to this tool, besides the spectrum, the calculation is performed simultaneous to H(10), E, H p , s (10,θ) from just counting rates from a Bonner spheres spectrometric system. (author)

Determination of Sodium, Potassium, Magnesium, and Calcium Minerals Level in Fresh and Boiled Broccoli and Cauliflower by Atomic Absorption Spectrometry

Science.gov (United States)

Nerdy

2018-01-01

Vegetables from the cabbage family vegetables consumed by many people, which is known healthful, by eaten raw, boiled, or cooked (stir fry or soup). Vegetables like broccoli and cauliflower contain vitamins, minerals, and fiber. This study aims to determine the decrease percentage of sodium, potassium, magnesium, and calcium minerals level caused by boiled broccoli and cauliflower by atomic absorption spectrometry. Boiled broccoli and cauliflower prepared by given boiled treatment in boiling water for 3 minutes. Fresh and boiled broccoli and cauliflower carried out dry destruction, followed by quantitative analysis of sodium, potassium, magnesium, and calcium minerals respectively at a wavelength of 589.0 nm; 766.5 nm; 285.2 nm; and 422.7 nm, using atomic absorption spectrometry methods. After the determination of the sodium, potassium, magnesium, and calcium minerals level followed by validation of analytical methods with accuracy, precision, linearity, range, limit of detection (LOD), and limit of quantitation (LOQ) parameters. Research results show a decrease in the sodium, potassium, magnesium, and calcium minerals level in boiled broccoli and cauliflower compared with fresh broccoli and cauliflower. Validation of analytical methods gives results that spectrometry methods used for determining sodium, potassium, magnesium, and calcium minerals level are valid. It concluded that the boiled gives the effect of decreasing the minerals level significantly in broccoli and cauliflower.

Simultaneous determination of estrogens and progestogens in honey using high performance liquid chromatography-tandem mass spectrometry

Science.gov (United States)

This work describes the development and validation of a method for the simultaneous determination of 13 estrogens and progestogens in honey by high performance liquid chromatography-tandem mass spectrometry. The target compounds were preconcentrated by solid phase extraction. Pretreatment variables ...

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

A Validated Method for the Detection and Quantitation of Synthetic ...

African Journals Online (AJOL)

NICOLAAS

A LC-HRMS (liquid chromatography coupled with high resolution mass spectrometry) method for the ... its ease of availability, from head shops (shops selling predomi- ..... cannabinoids in whole blood in plastic containers with several common ...

Method for predicting peptide detection in mass spectrometry

Science.gov (United States)

Kangas, Lars [West Richland, WA; Smith, Richard D [Richland, WA; Petritis, Konstantinos [Richland, WA

2010-07-13

A method of predicting whether a peptide present in a biological sample will be detected by analysis with a mass spectrometer. The method uses at least one mass spectrometer to perform repeated analysis of a sample containing peptides from proteins with known amino acids. The method then generates a data set of peptides identified as contained within the sample by the repeated analysis. The method then calculates the probability that a specific peptide in the data set was detected in the repeated analysis. The method then creates a plurality of vectors, where each vector has a plurality of dimensions, and each dimension represents a property of one or more of the amino acids present in each peptide and adjacent peptides in the data set. Using these vectors, the method then generates an algorithm from the plurality of vectors and the calculated probabilities that specific peptides in the data set were detected in the repeated analysis. The algorithm is thus capable of calculating the probability that a hypothetical peptide represented as a vector will be detected by a mass spectrometry based proteomic platform, given that the peptide is present in a sample introduced into a mass spectrometer.

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.

Current role of liquid chromatography coupled to mass spectrometry in clinical toxicology screening methods.

Science.gov (United States)

Viette, Véronique; Fathi, Marc; Rudaz, Serge; Hochstrasser, Denis; Veuthey, Jean-Luc

2011-07-01

Abstract Toxicological screening is the analysis of a biological specimen to detect and identify compounds in patients admitted to the hospital with acute intoxication of unknown origin. The screening of a wide range of toxicologically relevant compounds in biological samples is a serious challenge for clinical laboratories. The high selectivity and sensitivity of liquid chromatography coupled to mass spectrometry or tandem mass spectrometry technology provides an attractive alternative to the current methods. For these reasons, an increasing number of applications for multi-target screening or general screening of unknown compounds in biological matrices are being published. This paper is an overview of sample clean-up, chromatographic separation and mass spectrometry detection procedures which can be combined to obtain screening methods adapted to the constraints and needs of various laboratories, and none specifically in clinical toxicology. Currently the techniques are in the hands of specialists, principally in academic institutes. However, the evolution in technology should allow application of the techniques as a tool in toxicology laboratories and thus more widespread exploitation of their potential.

Analytical techniques and method validation for the measurement of selected semivolatile and nonvolatile organofluorochemicals in air.

Science.gov (United States)

Reagen, William K; Lindstrom, Kent R; Thompson, Kathy L; Flaherty, John M

2004-09-01

The widespread use of semi- and nonvolatile organofluorochemicals in industrial facilities, concern about their persistence, and relatively recent advancements in liquid chromatography/mass spectrometry (LC/MS) technology have led to the development of new analytical methods to assess potential worker exposure to airborne organofluorochemicals. Techniques were evaluated for the determination of 19 organofluorochemicals and for total fluorine in ambient air samples. Due to the potential biphasic nature of most of these fluorochemicals when airborne, Occupational Safety and Health Administration (OSHA) versatile sampler (OVS) tubes were used to simultaneously trap fluorochemical particulates and vapors from workplace air. Analytical methods were developed for OVS air samples to quantitatively analyze for total fluorine using oxygen bomb combustion/ion selective electrode and for 17 organofluorochemicals using LC/MS and gas chromatography/mass spectrometry (GC/MS). The experimental design for this validation was based on the National Institute of Occupational Safety and Health (NIOSH) Guidelines for Air Sampling and Analytical Method Development and Evaluation, with some revisions of the experimental design. The study design incorporated experiments to determine analytical recovery and stability, sampler capacity, the effect of some environmental parameters on recoveries, storage stability, limits of detection, precision, and accuracy. Fluorochemical mixtures were spiked onto each OVS tube over a range of 0.06-6 microg for each of 12 compounds analyzed by LC/MS and 0.3-30 microg for 5 compounds analyzed by GC/MS. These ranges allowed reliable quantitation at 0.001-0.1 mg/m3 in general for LC/MS analytes and 0.005-0.5 mg/m3 for GC/MS analytes when 60 L of air are sampled. The organofluorochemical exposure guideline (EG) is currently 0.1 mg/m3 for many analytes, with one exception being ammonium perfluorooctanoate (EG is 0.01 mg/m3). Total fluorine results may be used

Method validation for high resolution sector field inductively coupled plasma mass spectrometry determination of the emerging contaminants in the open ocean: Rare earth elements as a case study

Science.gov (United States)

Wysocka, Irena; Vassileva, Emilia

2017-02-01

Analytical procedure for the determination of fourteen rare earth elements (REEs) in the seawater samples has been developed and validated. The elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) at ultra-trace level were measured by high resolution sector field inductively coupled plasma mass spectrometry (HR ICP-SFMS) after off-line analytes pre-concentration and matrix separation. The sample pre-treatment was carried out by commercially available automated system seaFAST-pico™, which is a low-pressure ion chromatography technique, based on solid phase extraction principles. Efficient elimination of seawater matrix and up to 50-fold pre-concentration of REEs enabled their accurate and precise quantification at ng L- 1 level. A validation approach in line with the requirements of ISO/IEC 17025 standard and Eurachem guidelines were followed. With this in mind, selectivity, working range, linearity, recovery (from 92% to 102%), repeatability (1%-4%), intermediate precision (2%-6%), limits of detection (0.001-0.08 ng L- 1) were systematically assessed. The total uncertainty associated to each result was estimated and the main sources of uncertainty sorted out. All major contributions to the combined uncertainty of the obtained results were identified and propagated together, following the ISO/GUM guidelines. The relative expanded uncertainty was estimated at range from 10.4% to 11.6% (k = 2). Demonstration of traceability of measurement results was also presented. Due to the low limits of detection, this method enables the determination of ultra-low levels of REEs in the open seawater as well as small variations in their concentrations. The potential of the proposed analytical procedure, based on combination of seaFAST-pico™ for sample preparation and HR ICP-SFMS, was demonstrated by direct analysis of seawater form different regions of the world.

Development and validation of a reversed phase liquid chromatographic method for analysis of oxytetracycline and related impurities.

Science.gov (United States)

Kahsay, Getu; Shraim, Fairouz; Villatte, Philippe; Rotger, Jacques; Cassus-Coussère, Céline; Van Schepdael, Ann; Hoogmartens, Jos; Adams, Erwin

2013-03-05

A simple, robust and fast high-performance liquid chromatographic method is described for the analysis of oxytetracycline and its related impurities. The principal peak and impurities are all baseline separated in 20 min using an Inertsil C₈ (150 mm × 4.6 mm, 5 μm) column kept at 50 °C. The mobile phase consists of a gradient mixture of mobile phases A (0.05% trifluoroacetic acid in water) and B (acetonitrile-methanol-tetrahydrofuran, 80:15:5, v/v/v) pumped at a flow rate of 1.3 ml/min. UV detection was performed at 254 nm. The developed method was validated for its robustness, sensitivity, precision and linearity in the range from limit of quantification (LOQ) to 120%. The limits of detection (LOD) and LOQ were found to be 0.08 μg/ml and 0.32 μg/ml, respectively. This method allows the separation of oxytetracycline from all known and 5 unknown impurities, which is better than previously reported in the literature. Moreover, the simple mobile phase composition devoid of non-volatile buffers made the method suitable to interface with mass spectrometry for further characterization of unknown impurities. The developed method has been applied for determination of related substances in oxytetracycline bulk samples available from four manufacturers. The validation results demonstrate that the method is reliable for quantification of oxytetracycline and its impurities. Copyright © 2012 Elsevier B.V. All rights reserved.

In-situ spectrometry of 137Cs in the soil by unfolding method

International Nuclear Information System (INIS)

Fueloep, M.; Ragan, P.; Krnac, S.

1995-01-01

This contribution is aimed to the possibility of improving the in-situ gamma spectrometry to be independent on a knowledge about a depth distribution of 137 Cs in soil and sufficiently sensitive for the measurement of the post-Chernobyl 137 Cs at present, as well. The depth distribution of 137 Cs averaged over a large area of soil is obtained by unfolding of the detector responses to primary and in soil forward scattered photons. The proposed method employs detector with and without collimator. The 137 Cs distributions obtained in-situ measurements are analysed, and comparisons are made to the results obtained with soil sampling and with standard in-situ spectrometry, as well. 5 figs., 1 tab., 4 refs

Confirmatory analysis method for zeranol, its metabolites and related mycotoxins in urine by liquid chromatography-negative ion electrospray tandem mass spectrometry

International Nuclear Information System (INIS)

Bennekom, E.O. van; Brouwer, L.; Laurant, E.H.M.; Hooijerink, H.; Nielen, M.W.F.

2002-01-01

The determination of the banned anabolic substance zeranol and the metabolites taleranol and zearalanone in bovine urine is complicated by the occurrence of the structurally-related mycotoxin zearalenone and the corresponding α- and β-zearalenol metabolites which possess similar estrogenic properties. A liquid chromatography-negative ion electrospray tandem mass spectrometric method is presented for the confirmatory analysis of all six resorcylic acid lactones ('zeranols') in urine samples using deuterium-labelled internal standards. The method was validated as a confirmatory method for bovine urine samples according to new draft EU guidelines and showed good precision and linearity, and CCα and CCβ values of 0.02-0.30 and -1 , respectively. The applicability was demonstrated by comparing the results of an incurred sample with previous results on the same sample obtained by gas chromatography high resolution mass spectrometry. Preliminary data show that following a simple matrix solid phase dispersion clean-up, liver samples from poultry will be amenable to this method as well

Development of QuEChERS-based extraction and liquid chromatography-tandem mass spectrometry method for quantifying flumethasone residues in beef muscle.

Science.gov (United States)

Park, Ki Hun; Choi, Jeong-Heui; Abd El-Aty, A M; Cho, Soon-Kil; Park, Jong-Hyouk; Kwon, Ki Sung; Park, Hee Ra; Kim, Hyung Soo; Shin, Ho-Chul; Kim, Mi Ra; Shim, Jae-Han

2012-12-01

A rapid, specific, and sensitive method based on liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) in the positive ion mode using multiple reaction monitoring (MRM) was developed and validated to quantify flumethasone residues in beef muscle. Methods were compared between the original as well as the EN quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based extraction. Good linearity was achieved at concentration levels of 5-30 μg/kg. Estimated recovery rates at spiking levels of 5 and 10 μg/kg ranged from 72.1 to 84.6%, with relative standard deviations (RSDs)noise ratios (S/Ns) of 3 and 10, respectively. The method was successfully applied to analyze real samples obtained from large markets throughout the Korean Peninsula. The method proved to be sensitive and reliable and, thus, rendered an appropriate means for residue analysis studies. Copyright © 2012 Elsevier Ltd. All rights reserved.

Inter-laboratory validation of an inexpensive streamlined method to measure inorganic arsenic in rice grain.

Science.gov (United States)

Chaney, Rufus L; Green, Carrie E; Lehotay, Steven J

2018-05-04

With the establishment by CODEX of a 200 ng/g limit of inorganic arsenic (iAs) in polished rice grain, more analyses of iAs will be necessary to ensure compliance in regulatory and trade applications, to assess quality control in commercial rice production, and to conduct research involving iAs in rice crops. Although analytical methods using high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) have been demonstrated for full speciation of As, this expensive and time-consuming approach is excessive when regulations are based only on iAs. We report a streamlined sample preparation and analysis of iAs in powdered rice based on heated extraction with 0.28 M HNO 3 followed by hydride generation (HG) under control of acidity and other simple conditions. Analysis of iAs is then conducted using flow-injection HG and inexpensive ICP-atomic emission spectroscopy (AES) or other detection means. A key innovation compared with previous methods was to increase the acidity of the reagent solution with 4 M HCl (prior to reduction of As 5+ to As 3+ ), which minimized interferences from dimethylarsinic acid. An inter-laboratory method validation was conducted among 12 laboratories worldwide in the analysis of six shared blind duplicates and a NIST Standard Reference Material involving different types of rice and iAs levels. Also, four laboratories used the standard HPLC-ICP-MS method to analyze the samples. The results between the methods were not significantly different, and the Horwitz ratio averaged 0.52 for the new method, which meets official method validation criteria. Thus, the simpler, more versatile, and less expensive method may be used by laboratories for several purposes to accurately determine iAs in rice grain. Graphical abstract Comparison of iAs results from new and FDA methods.

Validation of a method for simultaneous determination of nitroimidazoles, benzimidazoles and chloramphenicols in swine tissues by ultra-high performance liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Xia, Xi; Wang, Yuanyuan; Wang, Xia; Li, Yun; Zhong, Feng; Li, Xiaowei; Huang, Yaoling; Ding, Shuangyang; Shen, Jianzhong

2013-05-31

This paper presents a sensitive and confirmatory multi-residue method for the analysis of 23 veterinary drugs and metabolites belonging to three classes (nitroimidazoles, benzimidazoles, and chloramphenicols) in porcine muscle, liver, and kidney. After extracted with ethyl acetate and basic ethyl acetate sequentially, the crude extracts were defatted with hexane and further purified using Oasis MCX solid-phase extraction cartridges. Rapid determination was carried out by ultra-high performance liquid chromatography-electrospray ionization tandem mass spectrometry. Data acquisition was performed under positive and negative mode simultaneously. Recoveries based on matrix-matched calibrations for meat, liver, and kidney ranged from 50.6 to 108.1%. The method quantification limits were in the range of 3-100ng/kg. Copyright © 2012 Elsevier B.V. All rights reserved.

Development and validation of an ICP-MS method applied to the determination of uranium in urine

International Nuclear Information System (INIS)

Ferreira, Isabela M. de S.; Castro, Marcelo X. de; Fidelis, Valdir dos S.; Santos, Osvaldir P.

2013-01-01

The objective of this study is to propose a new methodology for uranium analyses in urine using inductively coupled plasma - mass spectrometry (ICP-MS). The urine samples were provided by nuclear facility workers, specifically, employees of the Industrias Nucleares do Brasil - INB, the company responsible for the production of nuclear fuel in Brazil. At nuclear fuel facility sites, ensure the safety of employees is essential due to the risks involved in such activity, mainly exposure to radiation. On account of that, there are federal laws that limit the ionizing radiation exposure among workers. The verification of compliance with the requirements in technical regulation is performed through monitoring programs. In vitro bioassay is a method to monitor the individual worker by the analysis of radionuclides in excreta samples (urine or feces). The determination of uranium in urine was performed without any sample pretreatment and the method was validated by observing a series of operational parameters set by the INMETRO DOQ-CGCRE-008 guide - Guideline on Validation of Analytical Methods. A limit of detection of 0.9 ng L -1 was achieved. For the evaluation of the trueness/recovery of the method, a NIST Standard Reference Material - SRM 2670a - Toxic Elements in Urine (Freeze-Dried) was used. The calculation of relative error for the Certified Reference Material was 1.96%. The reproducibility of the developed method was confirmed through intercomparison analyses. Through the evaluation of performance parameters, the ability of the developed method of determining uranium with high sensitivity and reproducibility was verified, enabling the use in either environmental or occupational exposures. (author)

The former Semipalatinsk Test Site survey by field γ-spectrometry method

International Nuclear Information System (INIS)

Pakhomov, S.A.; Dubasov, Yu.V.; Biryukov, E.I.; Gavrilin, S.S.; Ilyin, L.I.

2001-01-01

Full text: Field γ-spectrometry method is the most productive method of getting an information on gamma-irradiating radionuclides contents in objects under survey. For many years the Radium Institute was the most active participant of works on radiation survey of the Semipalatinsk Test Site, field γ-spectrometry method including. In field γ-spectrometry method realization the existence of corresponding apparatus, and methodic software is supposed to be allowing to carry out both measurement, recording of γ-spectrometry energetic characteristics in field conditions and final treatment (using corresponding physical models) ensuring obtaining the information on radionuclides' contents. Different variants of such apparatus were developed and made at the Radium Institute. Under conditions of complex spectral structure and high intensity existence a portable variant of Ge(Li)-detector spectrometer fed by alkaline accumulators and allowing to record a spectrum at high load was elaborated. For walk γ-survey in common with the University two variants of portable spectrometers 'Skif-3' were elaborated: one of them with a standard scintillation detector on the base of Nal(Ti) crystal, having the size of 63x63 mm, and the other is an 'X-ray' detector of large dimension on the base of CsI crystal with a diameter of 165 mm, designated for soft gamma-irradiation registration, 241 Am including. During 8 hours of independent works 'Skif-3' is able to record into internal memory up to 100 spectra with an exposure up to 9999 s. At 10 min exposure in its sensitivity of 241 Am finding (10 Bq/kg) a spectrometer 'Skif-3' excels a portable spectrometer 'InSpector' (Canberra) working with the exposure of 1 hour. For automobile measurements a car spectrometer was elaborated fed. from car board supply and having four detectors based on NaI crystals with the dimensions 200x110 mm and total volume of about 121. For express treatment of a 'Skif-3' spectrometer scintillation spectra special

Application of gamma ray spectrometry for evaluation of transfer factors in environmental matrices

International Nuclear Information System (INIS)

Rao, D.D.

2008-01-01

Gamma Ray Spectrometry (GRS) is performed using a variety of radiation detectors, to identify and determine radioactivity concentration of gamma emitting radionuclides qualitatively, in a wide range of samples. The samples can be of a high inventory power plant origin, NORM category or low level environmental samples, around a power plant. The method is usually applied to non-destructive analysis of environmental samples. However, it can also be applied to destructive analysis i.e. following extraction/separation of the analyte from the sample, if there is a need to pre-concentrate the analyte. The accuracy and precision of the method, depends on the quality of calibration, correction methods employed, stability of the system components, computational algorithms used, analysis of sources of uncertainties etc. The transfer factors among the environmental matrices are simple ratios, but the methodologies used in generating the respective concentrations have to be appropriately documented, including the validity of measurements. Validation mechanisms can include the results of international inter-comparison exercises, the certificates of standards issued by quality-accredited international laboratories. A few parameters involved in the qualitative analysis of gamma spectrometry are discussed here

Development and validation of a liquid chromatography tandem mass spectrometry method for the determination of cannabinoids and phase I and II metabolites in meconium.

Science.gov (United States)

Prego-Meleiro, Pablo; Lendoiro, Elena; Concheiro, Marta; Cruz, Angelines; López-Rivadulla, Manuel; de Castro, Ana

2017-05-12

A liquid chromatography-tandem mass spectrometry (LC-MSMS) method was developed and fully validated for the determination of Δ 9 -tetrahydrocannabinol (THC), 11-hydroxyTHC (OHTHC), 11-nor-9-carboxyTHC (THCCOOH), 8-β-11-dihydroxyTHC (diOHTHC), cannabinol, cannabidiol, and THC and THCCOOH glucuronides in 0.25±0.02g meconium. Samples were homogenized in methanol and subjected to cation exchange solid-phase extraction. Chromatographic separation was performed on a Kinetex C18 column (50 mm×2.1mm, 2.6μm) at 35°C, with a gradient of 0.1% formic acid in water and acetonitrile at a flow rate of 0.3 mL/min; total run time was 10min. Two transitions per analyte were monitored in MRM mode. The method was specific and sensitive; LOD was from 1 to 2ng/g, and LOQ from 4 to 10ng/g; linearity ranged from 4 to 400 ng/g for all the analytes, except for THC glucuronide (10-400ng/g); intra-assay, inter-assay and total imprecision were <11.2%, <13.45% and <15.6%, respectively; accuracy ranged from 93.9% to 109.0% of the target concentration; matrix effect, extraction and process efficiency ranged from -26.4% to -71.4%, 49.9% to 69.5% and 14.3% to 45.0%, respectively. The inclusion of THC and THCCOOH glucuronides avoided the need for the hydrolysis process, thus facilitating sample pretreatment. Application of the method to 19 authentic meconium specimens from uncontrolled pregnancies or women suspicious of drug consumption revealed fetal cannabis exposure in 4 newborns. THCCOOH (24.1-288.8ng/g), diOHTHC (53.2-332.4ng/g), THC (4.2-7.7ng/g), CBN (30.7-93.3ng/g) and CBD (7.1-251.5ng/g) were detected in all cases; THCCOOH glucuronide (190.2-306.8ng/g) in 3 cases; and OHTHC (11.9ng/g) in the remaining one; however, THC glucuronide was not identified in any specimen. Copyright © 2017 Elsevier B.V. All rights reserved.

Liquid chromatography-tandem mass spectrometry method for the analysis of N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine, a biocidal disinfectant, in dairy products.

Science.gov (United States)

Slimani, Kahina; Pirotais, Yvette; Maris, Pierre; Abjean, Jean-Pierre; Hurtaud-Pessel, Dominique

2018-10-01

A novel and reliable method to quantify residual levels of N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine in dairy products using ion-pairing reversed-phase liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and fully validated. Sample extraction was done with salting-out technique using acetonitrile and sodium chloride. For LC-MS/MS, the analyte was detected using positive electrospray ionization (ESI+) and two multiple reaction monitoring (MRM) transitions were monitored. The method was validated in the 5-150 µg kg -1 range using total error approach. Thus, performance criteria of the method were evaluated. Relative standard deviations for trueness and precision were lower than 10%; with the exception of hard pressed cheese at 5 µg kg -1 for precision. The limit of quantification (LOQ) was around 5-7 µg kg -1 depending on the matrix of interest. The method was successfully applied to accurately quantify N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine in 146 various dairy products with a maximum contamination level of 225 µg kg -1 in cheese. Copyright © 2018 Elsevier Ltd. All rights reserved.

An improved method for statistical analysis of raw accelerator mass spectrometry data

International Nuclear Information System (INIS)

Gutjahr, A.; Phillips, F.; Kubik, P.W.; Elmore, D.

1987-01-01

Hierarchical statistical analysis is an appropriate method for statistical treatment of raw accelerator mass spectrometry (AMS) data. Using Monte Carlo simulations we show that this method yields more accurate estimates of isotope ratios and analytical uncertainty than the generally used propagation of errors approach. The hierarchical analysis is also useful in design of experiments because it can be used to identify sources of variability. 8 refs., 2 figs

Liquid chromatography – tandem mass spectrometry method for the determination of ten tetracycline residues in muscle samples

Directory of Open Access Journals (Sweden)

Gajda Anna

2015-09-01

Full Text Available A liquid chromatography – tandem mass spectrometry (LC-MS/MS method for the determination of oxytetracycline (OTC, 4-epi oxytetracycline (4-epi OTC, tetracycline (TC, 4-epi tetracycline (4-epi TC, chlortetracycline (CTC, 4-epi chlortetracycline (4-epi CTC, doxycycline (DC, minocycline (MINO, methacycline (META and rolitetracycline (ROLI residues in muscles was developed. The procedure consisted of an oxalic acid extraction followed by protein removal with trichloroacetic acid. Further solid phase clean-up on polymeric (Strata X reversed phase columns was performed to obtain an extract suitable for LC-MS/MS analysis. The tetracyclines were separated on a C 18 analytical column with mobile phase consisting of 0.01% formic acid in acetonitrile and 0.01% formic acid in water in gradient mode. The method was validated according to the Commission Decision 2002/657/EC. The recoveries of all target compounds were 91.8% – 103.6%. The decision limits were from 109.0 to 119.8 μg/kg and detection capability varied within the range of 122.2 to 137.6 μg/kg, depending on the analyte.

Development and Validation of a Dissolution Test Method for ...

African Journals Online (AJOL)

Purpose: To develop and validate a dissolution test method for dissolution release of artemether and lumefantrine from tablets. Methods: A single dissolution method for evaluating the in vitro release of artemether and lumefantrine from tablets was developed and validated. The method comprised of a dissolution medium of ...

Practical procedure for method validation in INAA- A tutorial

International Nuclear Information System (INIS)

Petroni, Robson; Moreira, Edson G.

2015-01-01

This paper describes the procedure employed by the Neutron Activation Laboratory at the Nuclear and Energy Research Institute (LAN, IPEN - CNEN/SP) for validation of Instrumental Neutron Activation Analysis (INAA) methods. According to recommendations of ISO/IEC 17025 the method performance characteristics (limit of detection, limit of quantification, trueness, repeatability, intermediate precision, reproducibility, selectivity, linearity and uncertainties budget) were outline in an easy, fast and convenient way. The paper presents step by step how to calculate the required method performance characteristics in a process of method validation, what are the procedures, adopted strategies and acceptance criteria for the results, that is, how to make a method validation in INAA. In order to exemplify the methodology applied, obtained results for the method validation of mass fraction determination of Co, Cr, Fe, Rb, Se and Zn in biological matrix samples, using an internal reference material of mussel tissue were presented. It was concluded that the methodology applied for validation of INAA methods is suitable, meeting all the requirements of ISO/IEC 17025, and thereby, generating satisfactory results for the studies carried at LAN, IPEN - CNEN/SP. (author)

Practical procedure for method validation in INAA- A tutorial

Energy Technology Data Exchange (ETDEWEB)

Petroni, Robson; Moreira, Edson G., E-mail: robsonpetroni@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2015-07-01

This paper describes the procedure employed by the Neutron Activation Laboratory at the Nuclear and Energy Research Institute (LAN, IPEN - CNEN/SP) for validation of Instrumental Neutron Activation Analysis (INAA) methods. According to recommendations of ISO/IEC 17025 the method performance characteristics (limit of detection, limit of quantification, trueness, repeatability, intermediate precision, reproducibility, selectivity, linearity and uncertainties budget) were outline in an easy, fast and convenient way. The paper presents step by step how to calculate the required method performance characteristics in a process of method validation, what are the procedures, adopted strategies and acceptance criteria for the results, that is, how to make a method validation in INAA. In order to exemplify the methodology applied, obtained results for the method validation of mass fraction determination of Co, Cr, Fe, Rb, Se and Zn in biological matrix samples, using an internal reference material of mussel tissue were presented. It was concluded that the methodology applied for validation of INAA methods is suitable, meeting all the requirements of ISO/IEC 17025, and thereby, generating satisfactory results for the studies carried at LAN, IPEN - CNEN/SP. (author)

Spiked environmental matrix for use as a reference material for gamma-ray spectrometry: Production and homogeneity test

International Nuclear Information System (INIS)

Sobiech-Matura, K.; Máté, B.; Altzitzoglou, T.

2016-01-01

The application of a spiking method for reference material production and its utilisation for a food matrix is presented. The raw rice powder was tested by means of γ-ray spectrometry and spiked with a "1"3"7Cs solution. The spiked material was mixed and tested for homogeneity. The future use of the rice powder reference material after the entire characterisation cycle will be for γ-ray spectrometry method validation. - Highlights: • Spiking blank substance with a traceable radioactive solution • Spiked reference material for γ-ray emitting radionuclides in food matrix • Results of the homogeneity tests are presented

Validation of the Rotation Ratios Method

International Nuclear Information System (INIS)

Foss, O.A.; Klaksvik, J.; Benum, P.; Anda, S.

2007-01-01

Background: The rotation ratios method describes rotations between pairs of sequential pelvic radiographs. The method seems promising but has not been validated. Purpose: To validate the accuracy of the rotation ratios method. Material and Methods: Known pelvic rotations between 165 radiographs obtained from five skeletal pelvises in an experimental material were compared with the corresponding calculated rotations to describe the accuracy of the method. The results from a clinical material of 262 pelvic radiographs from 46 patients defined the ranges of rotational differences compared. Repeated analyses, both on the experimental and the clinical material, were performed using the selected reference points to describe the robustness and the repeatability of the method. Results: The reference points were easy to identify and barely influenced by pelvic rotations. The mean differences between calculated and real pelvic rotations were 0.0 deg (SD 0.6) for vertical rotations and 0.1 deg (SD 0.7) for transversal rotations in the experimental material. The intra- and interobserver repeatability of the method was good. Conclusion: The accuracy of the method was reasonably high, and the method may prove to be clinically useful

The Method of Manufactured Universes for validating uncertainty quantification methods

KAUST Repository

Stripling, H.F.; Adams, M.L.; McClarren, R.G.; Mallick, B.K.

2011-01-01

The Method of Manufactured Universes is presented as a validation framework for uncertainty quantification (UQ) methodologies and as a tool for exploring the effects of statistical and modeling assumptions embedded in these methods. The framework

Method and apparatuses for ion cyclotron spectrometry

Science.gov (United States)

Dahl, David A [Idaho Falls, ID; Scott, Jill R [Idaho Falls, ID; McJunkin, Timothy R [Idaho Falls, ID

2012-03-06

An ion cyclotron spectrometer may include a vacuum chamber that extends at least along a z-axis and means for producing a magnetic field within the vacuum chamber so that a magnetic field vector is generally parallel to the z-axis. The ion cyclotron spectrometer may also include means for producing a trapping electric field within the vacuum chamber. The trapping electric field may comprise a field potential that, when taken in cross-section along the z-axis, includes at least one section that is concave down and at least one section that is concave up so that ions traversing the field potential experience a net magnetron effect on a cyclotron frequency of the ions that is substantially equal to zero. Other apparatuses and a method for performing ion cyclotron spectrometry are also disclosed herein.

Simultaneous analysis of fourteen tertiary amine stimulants in human urine for doping control purposes by liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry

International Nuclear Information System (INIS)

Lu Jianghai; Wang San; Dong Ying; Wang Xiaobing; Yang Shuming; Zhang Jianli; Deng Jing; Qin Yang; Xu Youxuan; Wu Moutian; Ouyang Gangfeng

2010-01-01

A method for the simultaneous screening and confirmation of the presence of fourteen tertiary amine stimulants in human urine by gas chromatography-mass spectrometry (GC-MS) in combination with liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed and validated. Solid phase extraction (SPE) and liquid-liquid extraction (LLE) approaches were utilized for the pre-treatment of the urine samples. The study indicated that the capillary temperature played a significant role in the signal abundances of the protonated molecules of cropropamide and crotethamide under positive ion electrospray ionization (ESI) conditions. In addition, comparison studies of two different pre-treatment approaches as well as the two ionization modes were conducted. The LODs of the developed method for all the analytes were lower than the minimum required performance limit (MRPL) as set forth in the World Anti-Doping Agency (WADA) technical document for laboratories. The human urine sample obtained after oral administration of prolintane.HCl was successfully analyzed by the developed method, which demonstrated the applicability and reliability of the method for routine doping control analysis.

Review and evaluation of spark source mass spectrometry as an analytical method

International Nuclear Information System (INIS)

Beske, H.E.

1981-01-01

The analytical features and most important fields of application of spark source mass spectrometry are described with respect to the trace analysis of high-purity materials and the multielement analysis of technical alloys, geochemical and cosmochemical, biological and radioactive materials, as well as in environmental analysis. Comparisons are made to other analytical methods. The distribution of the method as well as opportunities for contract analysis are indicated and developmental tendencies discussed. (orig.) [de

Methods of measurement of integral and differential linearity distortions of spectrometry sets

International Nuclear Information System (INIS)

Fuan, Jacques; Grimont, Bernard; Marin, Roland; Richard, Jean-Pierre

1969-05-01

The objective of this document is to describe different measurement methods, and more particularly to present a software for the processing of obtained results in order to avoid interpretation by the investigator. In a first part, the authors define the parameters of integral and differential linearity, outlines their importance in measurements performed by spectrometry, and describe the use of these parameters. In the second part, they propose various methods of measurement of these linearity parameters, report experimental applications of these methods and compare the obtained results

Method validation in pharmaceutical analysis: from theory to practical optimization

Directory of Open Access Journals (Sweden)

Jaqueline Kaleian Eserian

2015-01-01

Full Text Available The validation of analytical methods is required to obtain high-quality data. For the pharmaceutical industry, method validation is crucial to ensure the product quality as regards both therapeutic efficacy and patient safety. The most critical step in validating a method is to establish a protocol containing well-defined procedures and criteria. A well planned and organized protocol, such as the one proposed in this paper, results in a rapid and concise method validation procedure for quantitative high performance liquid chromatography (HPLC analysis.   Type: Commentary

Validation of NAA Method for Urban Particulate Matter

International Nuclear Information System (INIS)

Woro Yatu Niken Syahfitri; Muhayatun; Diah Dwiana Lestiani; Natalia Adventini

2009-01-01

Nuclear analytical techniques have been applied in many countries for determination of environmental pollutant. Method of NAA (neutron activation analysis) representing one of nuclear analytical technique of that has low detection limits, high specificity, high precision, and accuracy for large majority of naturally occurring elements, and ability of non-destructive and simultaneous determination of multi-elemental, and can handle small sample size (< 1 mg). To ensure quality and reliability of the method, validation are needed to be done. A standard reference material, SRM NIST 1648 Urban Particulate Matter, has been used to validate NAA method. Accuracy and precision test were used as validation parameters. Particulate matter were validated for 18 elements: Ti, I, V, Br, Mn, Na, K, Cl, Cu, Al, As, Fe, Co, Zn, Ag, La, Cr, and Sm,. The result showed that the percent relative standard deviation of the measured elemental concentrations are found to be within ranged from 2 to 14,8% for most of the elements analyzed whereas Hor rat value in range 0,3-1,3. Accuracy test results showed that relative bias ranged from -11,1 to 3,6%. Based on validation results, it can be stated that NAA method is reliable for characterization particulate matter and other similar matrix samples to support air quality monitoring. (author)

Development and validation of a liquid chromatography-tandem mass spectrometry method for the simultaneous quantification of tamoxifen, anastrozole, and letrozole in human plasma and its application to a clinical study.

Science.gov (United States)

Beer, Beate; Schubert, Birthe; Oberguggenberger, Anne; Meraner, Verena; Hubalek, Michael; Oberacher, Herbert

2010-10-01

There is substantial evidence that circulating estrogens promote the proliferation of breast cancer. Consequently, adjuvant hormonal treatment strategies targeting estrogen action have been established. Such hormonal therapies include selective estrogen receptor modulators, such as tamoxifen, which interfere at the estrogen receptors directly, or non-steroidal aromatase inhibitors, such as anastrozole and letrozole, which inhibit estrogen synthesis through blocking the aromatase, a key enzyme of estrogen production. Despite considerable therapeutic success, in several cases, the use of these drugs is limited by side effects that have been described to significantly impair the adherence of patients to endocrine treatment. However, objective data concerning patient adherence and its clinical relevance are limited. One promising approach to check patient-reported adherence is drug monitoring in human plasma. Therefore, a liquid chromatography-tandem mass spectrometry method to determine the plasma concentrations of tamoxifen, anastrozole, and letrozole has been developed and fully validated according to guidelines for clinical and forensic toxicology. The validation criteria evaluated were selectivity, linearity, accuracy and precision, limit of quantification, recovery and matrix effects, sample stability, and carryover. The six-point calibration curves showed linearity over the range of concentrations from 25 to 500 ng/ml for tamoxifen, 5 to 200 ng/ml for anastrozole, and 10 to 300 ng/ml for letrozole. The intra- and inter-day precision and accuracies were always better than 15%. The validated procedure was successfully applied to a clinical study (Patient-Reported Outcomes in Breast Cancer Patients undergoing Endocrine Therapy, PRO-BETh). A major aim of PRO-BETh study is the comprehensive evaluation of adherence to treatment in pre- and post-menopausal women with breast cancer. Plasma samples of 310 breast cancer patients undergoing anti-estrogen therapy were

Development and Single-Laboratory Validation of a Liquid Chromatography Tandem Mass Spectrometry Method for Quantitation of Tetrodotoxin in Mussels and Oysters.

Science.gov (United States)

Turner, Andrew D; Boundy, Michael J; Rapkova, Monika Dhanji

2017-09-01

In recent years, evidence has grown for the presence of tetrodotoxin (TTX) in bivalve mollusks, leading to the potential for consumers of contaminated products to be affected by Tetrodotoxin Shellfish Poisoning (TSP). A single-laboratory validation was conducted for the hydrophilic interaction LC (HILIC) tandem MS (MS/MS) analysis of TTX in common mussels and Pacific oysters-the bivalve species that have been found to contain TTXs in the United Kingdom in recent years. The method consists of a single-step dispersive extraction in 1% acetic acid, followed by a carbon SPE cleanup step before dilution and instrumental analysis. The full method was developed as a rapid tool for the quantitation of TTX, as well as for the associated analogs 4-epi-TTX; 5,6,11-trideoxy TTX; 11-nor TTX-6-ol; 5-deoxy TTX; and 4,9-anhydro TTX. The method can also be run as the acquisition of TTX together with paralytic shellfish toxins. Results demonstrated acceptable method performance characteristics for specificity, linearity, recovery, ruggedness, repeatability, matrix variability, and within-laboratory reproducibility for the analysis of TTX. The LOD and LOQ were fit-for-purpose in comparison to the current action limit for TTX enforced in The Netherlands. In addition, aspects of method performance (LOD, LOQ, and within-laboratory reproducibility) were found to be satisfactory for three other TTX analogs (11-nor TTX-6-ol, 5-deoxy TTX, and 4,9-anhydro TTX). The method was found to be practical and suitable for use in regulatory testing, providing rapid turnaround of sample analysis. Plans currently underway on a full collaborative study to validate a HILIC-MS/MS method for paralytic shellfish poisoning toxins will be extended to include TTX in order to generate international acceptance, ultimately for use as an alternative official control testing method should regulatory controls be adopted.

Development of a liquid chromatography tandem mass spectrometry method for iothalamate measurement to assess renal function for potential kidney donation.

Science.gov (United States)

Rhea, Jeanne M; Ritchie, James C; Molinaro, Ross J

2013-05-01

Chronic kidney disease often goes undetected due to the insensitivity of current methods to accurately assess glomerular filtration rate (GFR) in early stages of renal dysfunction. The clearance of exogenously introduced iothalamate, a commonly used radiopaque agent, is an alternative to inulin clearance for the assessment of renal function and its use in calculating GFR can serve as a screening tool for kidney transplant donors. A method was developed to measure iothalamate in plasma and urine samples by HPLC combined with electrospray positive ionization tandem mass spectrometry (MS/MS). Iothalamate is isolated from plasma by methanol extraction and urine using a quick-spin filtration approach, then monitored by multiple reaction monitoring using the hydrogen adduct mass transitions. Iohexol was used as an internal standard. Iothalamate was measured within an analytical run time of 5 min, with a lower limit of quantification of 18.75 ng/ml. The intraassay and interassay variations of the plasma and urine iothalamate assays were both calculated using the patient's urine flow rate and plasma and urine iothalamate values. Linear correlations tested by LC-MS/MS and an accepted capillary electrophoresis (CE) assay showed similar results (GFR, r=0.92, Sy/x=10.3). We developed and validated an LC-MS/MS method for quantitating iothalamate in plasma and urine to calculate GFR used for screening potential kidney donors in our hospital system. A less sensitive mass spectrometry system does not sacrifice analytical or clinical sensitivity for measuring GFR. Copyright © 2012 Elsevier B.V. All rights reserved.

Validation of method in instrumental NAA for food products sample

International Nuclear Information System (INIS)

Alfian; Siti Suprapti; Setyo Purwanto

2010-01-01

NAA is a method of testing that has not been standardized. To affirm and confirm that this method is valid. it must be done validation of the method with various sample standard reference materials. In this work. the validation is carried for food product samples using NIST SRM 1567a (wheat flour) and NIST SRM 1568a (rice flour). The results show that the validation method for testing nine elements (Al, K, Mg, Mn, Na, Ca, Fe, Se and Zn) in SRM 1567a and eight elements (Al, K, Mg, Mn, Na, Ca, Se and Zn ) in SRM 1568a pass the test of accuracy and precision. It can be conclude that this method has power to give valid result in determination element of the food products samples. (author)

Human Factors methods concerning integrated validation of nuclear power plant control rooms; Metodutveckling foer integrerad validering

Energy Technology Data Exchange (ETDEWEB)

Oskarsson, Per-Anders; Johansson, Bjoern J.E.; Gonzalez, Natalia (Swedish Defence Research Agency, Information Systems, Linkoeping (Sweden))

2010-02-15

The frame of reference for this work was existing recommendations and instructions from the NPP area, experiences from the review of the Turbic Validation and experiences from system validations performed at the Swedish Armed Forces, e.g. concerning military control rooms and fighter pilots. These enterprises are characterized by complex systems in extreme environments, often with high risks, where human error can lead to serious consequences. A focus group has been performed with representatives responsible for Human Factors issues from all Swedish NPP:s. The questions that were discussed were, among other things, for whom an integrated validation (IV) is performed and its purpose, what should be included in an IV, the comparison with baseline measures, the design process, the role of SSM, which methods of measurement should be used, and how the methods are affected of changes in the control room. The report brings different questions to discussion concerning the validation process. Supplementary methods of measurement for integrated validation are discussed, e.g. dynamic, psychophysiological, and qualitative methods for identification of problems. Supplementary methods for statistical analysis are presented. The study points out a number of deficiencies in the validation process, e.g. the need of common guidelines for validation and design, criteria for different types of measurements, clarification of the role of SSM, and recommendations for the responsibility of external participants in the validation process. The authors propose 12 measures for taking care of the identified problems

Reactor gamma spectrometry: status

International Nuclear Information System (INIS)

Gold, R.; Kaiser, B.J.

1979-01-01

Current work is described for Compton Recoil Gamma-Ray Spectrometry including developments in experimental technique as well as recent reactor spectrometry measurements. The current status of the method is described concerning gamma spectromoetry probe design and response characteristics. Emphasis is given to gamma spectrometry work in US LWR and BR programs. Gamma spectrometry in BR environments are outlined by focussing on start-up plans for the Fast Test Reactor (FTR). Gamma spectrometry results are presented for a LWR pressure vessel mockup in the Poolside Critical Assembly (PCA) at Oak Ridge National Laboratory

A method for the complete analysis of NORM building materials by γ-ray spectrometry using HPGe detectors.

Science.gov (United States)

Quintana, B; Pedrosa, M C; Vázquez-Canelas, L; Santamaría, R; Sanjuán, M A; Puertas, F

2018-04-01

A methodology including software tools for analysing NORM building materials and residues by low-level gamma-ray spectrometry has been developed. It comprises deconvolution of gamma-ray spectra using the software GALEA with focus on the natural radionuclides and Monte Carlo simulations for efficiency and true coincidence summing corrections. The methodology has been tested on a range of building materials and validated against reference materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Capsule Typing of Haemophilus influenzae by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry.

Science.gov (United States)

Månsson, Viktor; Gilsdorf, Janet R; Kahlmeter, Gunnar; Kilian, Mogens; Kroll, J Simon; Riesbeck, Kristian; Resman, Fredrik

2018-03-01

Encapsulated Haemophilus influenzae strains belong to type-specific genetic lineages. Reliable capsule typing requires PCR, but a more efficient method would be useful. We evaluated capsule typing by using matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. Isolates of all capsule types (a-f and nontypeable; n = 258) and isogenic capsule transformants (types a-d) were investigated. Principal component and biomarker analyses of mass spectra showed clustering, and mass peaks correlated with capsule type-specific genetic lineages. We used 31 selected isolates to construct a capsule typing database. Validation with the remaining isolates (n = 227) showed 100% sensitivity and 92.2% specificity for encapsulated strains (a-f; n = 61). Blinded validation of a supplemented database (n = 50) using clinical isolates (n = 126) showed 100% sensitivity and 100% specificity for encapsulated strains (b, e, and f; n = 28). MALDI-TOF mass spectrometry is an accurate method for capsule typing of H. influenzae.

Development and validation of a LC-MS/MS method for the determination of clebopride and its application to a pharmacokinetics study in healthy Chinese volunteers.

Science.gov (United States)

Tan, Zhirong; Ouyang, Dongsheng; Chen, Yao; Zhou, Gan; Cao, Shan; Wang, Yicheng; Peng, Xiujuan; Zhou, Honghao

2010-08-01

A sensitive and specific liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS/MS) method has been developed and validated for the identification and quantification of clebopride in human plasma using itopride as an internal standard. The method involves a simple liquid-liquid extraction. The analytes were separated by isocratic gradient elution on a CAPCELL MG-III C(18) (5 microm, 150 mm x 2.1 mm i.d.) column and analyzed in multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI) interface using the respective [M+H](+) ions, m/z 373.9-->m/z184.0 for clebopride, m/z 359.9-->m/z71.5 for itopride. The method was validated over the concentration range of 69.530-4450.0 pg/ml for clebopride. Within- and between-batch precision (RSD%) was all within 6.83% and accuracy ranged from -8.16 to 1.88%. The LLOQ was 69.530 pg/ml. The extraction recovery was on an average 77% for clebopride. The validated method was used to study the pharmacokinetics profile of clebopride in human plasma after oral administration of clebopride. Copyright 2010. Published by Elsevier B.V.

Liquid chromatography tandem mass spectrometry determination of total budesonide levels in dog plasma after inhalation exposure.

Science.gov (United States)

Berg, Seija; Melamies, Marika; Rajamäki, Minna; Vainio, Outi; Peltonen, Kimmo

2012-01-01

A sensitive and selective method to quantify budesonide in dog plasma samples was developed and fully validated. Liquid-liquid extraction was followed by solid-phase extraction and liquid chromatography-tandem mass spectrometry with electrospray ionization. After reconstitution of the analytes in the mobile phase, samples were analysed by reversed-phase liquid chromatography with isocratic elution. d8-Budesonide was used as an internal standard, and characteristic transitions of d8-budesonide and budesonide were used for quantification. The method was validated with respect to selectivity, specificity, linearity, recovery, repeatability, reproducibility and limits of detection and quantification. The validated method was successfully applied to monitor the plasma levels of budesonide in dogs exposed to clinical doses of inhaled and intravenous drug.

Liquid chromatography-tandem mass spectrometry method for the determination of thiosulfate in human blood and urine as an indicator of hydrogen sulfide poisoning.

Science.gov (United States)

Maseda, Chikatoshi; Hayakawa, Akira; Okuda, Katsuhiro; Asari, Masaru; Tanaka, Hiroki; Yamada, Hiromi; Jin, Shigeki; Horioka, Kie; Matoba, Kotaro; Shiono, Hiroshi; Matsubara, Kazuo; Shimizu, Keiko

2017-01-01

Being a stable metabolite of hydrogen sulfide, thiosulfate has been utilized as an index for hydrogen sulfide poisoning (HSP). Thiosulfate analysis is mainly performed using gas chromatography/mass spectrometry (GC-MS) due to its high sensitivity and specificity. The GC-MS analysis requires two-step derivatizations of thiosulfate, and the derivative is not stable in solution as it has a disulfide moiety. To resolve this stability issue, we developed a novel analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for monitoring the pentafluorobenzyl derivative of thiosulfate (the first reaction product of the GC-MS method) in this study. The established method exhibited high reproducibility despite being a more simplified and rapid procedure compare to the GC-MS method. Phenyl 4-hydroxybenzoate was used as an internal standard because 1,3,5-tribromobenzene which had been used in the GC-MS method was not suitable compound for LC-MS/MS with Electrospray ionization (ESI) negative detection. The linear regression of the peak area ratios versus concentrations was fitted over the concentration ranges of 0.5-250μM and 0.25-250μM in blood and urine, respectively. The validation results satisfied the acceptance criteria for intra- and inter-day accuracy and precision. Blood and urine samples from 12 suspected HSP cases were tested using this method. The thiosulfate concentration detected in the sample coincided well with that determined at the scene of each HSP accident. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

A need for determination of arsenic species at low levels in cereal-based food and infant cereals. Validation of a method by IC-ICPMS.

Science.gov (United States)

Llorente-Mirandes, Toni; Calderón, Josep; Centrich, Francesc; Rubio, Roser; López-Sánchez, José Fermín

2014-03-15

The present study arose from the need to determine inorganic arsenic (iAs) at low levels in cereal-based food. Validated methods with a low limit of detection (LOD) are required to analyse these kinds of food. An analytical method for the determination of iAs, methylarsonic acid (MA) and dimethylarsinic acid (DMA) in cereal-based food and infant cereals is reported. The method was optimised and validated to achieve low LODs. Ion chromatography-inductively coupled plasma mass spectrometry (IC-ICPMS) was used for arsenic speciation. The main quality parameters were established. To expand the applicability of the method, different cereal products were analysed: bread, biscuits, breakfast cereals, wheat flour, corn snacks, pasta and infant cereals. The total and inorganic arsenic content of 29 cereal-based food samples ranged between 3.7-35.6 and 3.1-26.0 μg As kg(-1), respectively. The present method could be considered a valuable tool for assessing inorganic arsenic contents in cereal-based foods. Copyright © 2013 Elsevier Ltd. All rights reserved.

Analysis of processing contaminants in edible oils. Part 2. Liquid chromatography-tandem mass spectrometry method for the direct detection of 3-monochloropropanediol and 2-monochloropropanediol diesters.

Science.gov (United States)

MacMahon, Shaun; Begley, Timothy H; Diachenko, Gregory W

2013-05-22

A method was developed and validated for the detection of fatty acid diesters of 2-monochloropropanediol (2-MCPD) and 3-monochloropropanediol (3-MCPD) in edible oils. These analytes are potentially carcinogenic chemical contaminants formed during edible oil processing. After separation from oil matrices using a two-step solid-phase extraction (SPE) procedure, the target compounds are quantitated using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). The first chromatographic conditions have been developed that separate intact diesters of 2-MCPD and 3-MCPD, allowing for their individual quantitation. The method has been validated for 28 3-MCPD diesters of lauric, myristic, palmitic, linolenic, linoleic, oleic, and stearic acids in coconut, olive, and palm oils, as well as 3 2-MCPD diesters, using an external calibration curve. The range of average recoveries and relative standard deviations (RSDs) across the three oil matrices at three spiking concentrations are 88-118% (2-16% RSD) with maximum limits of quantitation of 30 ng/g (ppb).

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

International Nuclear Information System (INIS)

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

1981-01-01

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

Single-laboratory validation of a method for the determination of select volatile organic compounds in foods by using vacuum distillation with gas chromatography/mass spectrometry.

Science.gov (United States)

Nyman, Patricia J; Limm, William; Begley, Timothy H; Chirtel, Stuart J

2014-01-01

Recent studies showed that headspace and purge and trap methods have limitations when used to determine volatile organic compounds (VOCs) in foods, including matrix effects and artifact formation from precursors present in the sample matrix or from thermal decomposition. U.S. Environmental Protection Agency Method 8261A liberates VOCs from the sample matrix by using vacuum distillation at room temperature. The method was modified and validated for the determination of furan, chloroform, benzene, trichloroethene, toluene, and sytrene in infant formula, canned tuna (in water), peanut butter, and an orange beverage (orange-flavored noncarbonated beverage). The validation studies showed that the LOQ values ranged from 0.05 ng/g toluene in infant formula to 5.10 ng/g toluene in peanut butter. Fortified recoveries were determined at the first, second, and third standard additions, and concentrations ranged from 0.07 to 6.9 ng/g. When quantified by the method of standard additions, the recoveries ranged from 56 to 218% at the first standard addition and 89 to 117% at the third. The validated method was used to conduct a survey of the targeted VOCs in 18 foods. The amounts found ranged from none detected to 73.8 ng/g furan in sweet potato baby food.

Analysis of Veterinary Drug and Pesticide Residues Using the Ethyl Acetate Multiclass/Multiresidue Method in Milk by Liquid Chromatography-Tandem Mass Spectrometry

Directory of Open Access Journals (Sweden)

Husniye Imamoglu

2016-01-01

Full Text Available A rapid and simple multiclass, ethyl acetate (EtOAc multiresidue method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS detection was developed for the determination and quantification of 26 veterinary drugs and 187 total pesticide residues in milk. Sample preparation was a simple procedure based on liquid–liquid extraction with ethyl acetate containing 0.1% acetic acid, followed by centrifugation and evaporation of the supernatant. The residue was dissolved in ethyl acetate with 0.1% acetic acid and centrifuged prior to LC-MS/MS analysis. Chromatographic separation of analytes was performed on an Inertsil X-Terra C18 column with acetic acid in methanol and water gradient. The repeatability and reproducibility were in the range of 2 to 13% and 6 to 16%, respectively. The average recoveries ranged from 75 to 120% with the RSD (n=18. The developed method was validated according to the criteria set in Commission Decision 2002/657/EC and SANTE/11945/2015. The validated methodology represents a fast and cheap alternative for the simultaneous analysis of veterinary drug and pesticide residues which can be easily extended to other compounds and matrices.

ASTM Validates Air Pollution Test Methods

Science.gov (United States)

Chemical and Engineering News, 1973

1973-01-01

The American Society for Testing and Materials (ASTM) has validated six basic methods for measuring pollutants in ambient air as the first part of its Project Threshold. Aim of the project is to establish nationwide consistency in measuring pollutants; determining precision, accuracy and reproducibility of 35 standard measuring methods. (BL)

Spectrum unfolding in X-ray spectrometry using the maximum entropy method

International Nuclear Information System (INIS)

Fernandez, Jorge E.; Scot, Viviana; Di Giulio, Eugenio

2014-01-01

The solution of the unfolding problem is an ever-present issue in X-ray spectrometry. The maximum entropy technique solves this problem by taking advantage of some known a priori physical information and by ensuring an outcome with only positive values. This method is implemented in MAXED (MAXimum Entropy Deconvolution), a software code contained in the package UMG (Unfolding with MAXED and GRAVEL) developed at PTB and distributed by NEA Data Bank. This package contains also the code GRAVEL (used to estimate the precision of the solution). This article introduces the new code UMESTRAT (Unfolding Maximum Entropy STRATegy) which applies a semi-automatic strategy to solve the unfolding problem by using a suitable combination of MAXED and GRAVEL for applications in X-ray spectrometry. Some examples of the use of UMESTRAT are shown, demonstrating its capability to remove detector artifacts from the measured spectrum consistently with the model used for the detector response function (DRF). - Highlights: ► A new strategy to solve the unfolding problem in X-ray spectrometry is presented. ► The presented strategy uses a suitable combination of the codes MAXED and GRAVEL. ► The applied strategy provides additional information on the Detector Response Function. ► The code UMESTRAT is developed to apply this new strategy in a semi-automatic mode

Validation of a food frequency questionnaire to determine vitamin D intakes using the method of triads.

Science.gov (United States)

Weir, R R; Carson, E L; Mulhern, M S; Laird, E; Healy, M; Pourshahidi, L K

2016-04-01

Dietary sources of vitamin D (both natural and fortified) are increasingly contributing to consumers' vitamin D intake and status. Therefore, the present study aimed to validate a vitamin D food frequency questionnaire (FFQ) for the assessment of habitual vitamin D intake. A total of 49 apparently healthy consenting adults (aged 18-64 years) from the local community were sampled at the end of winter. Dietary intakes were recorded using a 4-day weighed food record (4d-WFR) and a 17-item FFQ based on foods known to contribute to dietary vitamin D intake. Fasting vitamin D status was quantified by serum 25-hydroxyvitamin D [25(OH)D] using liquid chromatography tandem mass spectrometry. The method of triads was applied using these three measurements to determine the overall validity of the FFQ. Vitamin D intakes from 4d-WFR ranged between 0.42 and 31.65 μg day(-1), whereas intakes determined from the FFQ ranged from 1.03 to 36.08 μg day(-1). Serum 25(OH)D concentrations ranged between 12.89 and 279.00 nmol L(-1). The mean (SD) difference between the FFQ and 4d-WFR was +1.62 ( 3.86). There were strong correlations between the vitamin D intake estimated by the FFQ and that from the 4d-WFR (r = 0.562) and also with serum 25(OH)D concentrations (r = 0.567). Vitamin D intake estimated from the 4d-WFR was also strongly correlated with serum 25(OH)D concentrations (r = 0.411). The overall validity coefficient calculated using the method of triads was high (0.881). The vitamin D FFQ has been validated for use in future studies aiming to assess habitual vitamin D intake. © 2015 The British Dietetic Association Ltd.

Method and equipment for γ background compensation in neutron spectrometry

International Nuclear Information System (INIS)

Holman, M.; Marik, P.

1986-01-01

The compensation of background gamma radiation in neutron spectrometry is based on the measurement of the total energy spectrum of all protons and electrons, and of the energy spectrum of those protons and neutrons which are in coincidence with the discriminating signal derived from the integral of the counting rate distribution by pulse shape. The benefits of the method consist in the possibility of using standard single-parameter apparatus, in considerably smaller demands on the memory capacity and the possibility of a substantially finer division of the spectrum and more accurate compensation of the background than has been the case with methods used so far. A practical application is shown in a block diagram. (J.B.)

The Validation of NAA Method Used as Test Method in Serpong NAA Laboratory

International Nuclear Information System (INIS)

Rina-Mulyaningsih, Th.

2004-01-01

The Validation Of NAA Method Used As Test Method In Serpong NAA Laboratory. NAA Method is a non standard testing method. The testing laboratory shall validate its using method to ensure and confirm that it is suitable with application. The validation of NAA methods have been done with the parameters of accuracy, precision, repeatability and selectivity. The NIST 1573a Tomato Leaves, NIES 10C Rice flour unpolished and standard elements were used in this testing program. The result of testing with NIST 1573a showed that the elements of Na, Zn, Al and Mn are met from acceptance criteria of accuracy and precision, whereas Co is rejected. The result of testing with NIES 10C showed that Na and Zn elements are met from acceptance criteria of accuracy and precision, but Mn element is rejected. The result of selectivity test showed that the value of quantity is between 0.1-2.5 μg, depend on the elements. (author)

Toward a Unified Validation Framework in Mixed Methods Research

Science.gov (United States)

Dellinger, Amy B.; Leech, Nancy L.

2007-01-01

The primary purpose of this article is to further discussions of validity in mixed methods research by introducing a validation framework to guide thinking about validity in this area. To justify the use of this framework, the authors discuss traditional terminology and validity criteria for quantitative and qualitative research, as well as…

Development and validation of a dried blood spot assay for the quantification of ribavirin using liquid chromatography coupled to mass spectrometry

Science.gov (United States)

Jimmerson, Leah C.; Zheng, Jia-Hua; Bushman, Lane R.; MacBrayne, Christine E.; Anderson, Peter L.; Kiser, Jennifer J.

2014-01-01

Efficient, inexpensive and sensitive assays for the measurement of drugs are of interest for pharmacokinetic and pharmacodynamics (PK-PD) analysis. Dried blood spots (DBS) are a unique bioanaltyical matrix with the potential to fulfill this interest for the measurement of numerous analytes. Here we describe the development and validation of a reversed-phase high performance liquid chromatographic (LC), tandem mass spectrometry (MS/MS) assay for the determination of ribavirin (RBV) in DBS. A 3mm punch from spotted and dried whole blood was extracted in methanol utilizing isotopically labeled internal standard for LC-MS/MS analysis. Validation was performed over a range of 0.05 μg/mL to 10.0 μg/mL and the method was shown to be precise (coefficient of variation ≤ 15%) and accurate (within ±15% of control). These acceptance criteria were met for hematocrit ranges of 20-54%, for center versus edge punches and for spot volumes from 10-60 μL. RBV was stable for up to 140 days at room temperature and −20°C as well as for three freeze/thaw cycles. Correlation of RBV in DBS versus in plasma yielded r2 ≥ 0.98 demonstrating that DBS can be used as an alternative to plasma for PK-PD studies in human subjects. PMID:24291608

Confirmatory analysis method for zeranol, its metabolites and related mycotoxins in urine by liquid chromatography-negative ion electrospray tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Bennekom, E.O. van; Brouwer, L.; Laurant, E.H.M.; Hooijerink, H.; Nielen, M.W.F

2002-11-25

The determination of the banned anabolic substance zeranol and the metabolites taleranol and zearalanone in bovine urine is complicated by the occurrence of the structurally-related mycotoxin zearalenone and the corresponding {alpha}- and {beta}-zearalenol metabolites which possess similar estrogenic properties. A liquid chromatography-negative ion electrospray tandem mass spectrometric method is presented for the confirmatory analysis of all six resorcylic acid lactones ('zeranols') in urine samples using deuterium-labelled internal standards. The method was validated as a confirmatory method for bovine urine samples according to new draft EU guidelines and showed good precision and linearity, and CC{alpha} and CC{beta} values of 0.02-0.30 and <1.0 ng ml{sup -1}, respectively. The applicability was demonstrated by comparing the results of an incurred sample with previous results on the same sample obtained by gas chromatography high resolution mass spectrometry. Preliminary data show that following a simple matrix solid phase dispersion clean-up, liver samples from poultry will be amenable to this method as well.

A standards-based method for compositional analysis by energy dispersive X-ray spectrometry using multivariate statistical analysis: application to multicomponent alloys.

Science.gov (United States)

Rathi, Monika; Ahrenkiel, S P; Carapella, J J; Wanlass, M W

2013-02-01

Given an unknown multicomponent alloy, and a set of standard compounds or alloys of known composition, can one improve upon popular standards-based methods for energy dispersive X-ray (EDX) spectrometry to quantify the elemental composition of the unknown specimen? A method is presented here for determining elemental composition of alloys using transmission electron microscopy-based EDX with appropriate standards. The method begins with a discrete set of related reference standards of known composition, applies multivariate statistical analysis to those spectra, and evaluates the compositions with a linear matrix algebra method to relate the spectra to elemental composition. By using associated standards, only limited assumptions about the physical origins of the EDX spectra are needed. Spectral absorption corrections can be performed by providing an estimate of the foil thickness of one or more reference standards. The technique was applied to III-V multicomponent alloy thin films: composition and foil thickness were determined for various III-V alloys. The results were then validated by comparing with X-ray diffraction and photoluminescence analysis, demonstrating accuracy of approximately 1% in atomic fraction.

Analytical models approximating individual processes: a validation method.

Science.gov (United States)

Favier, C; Degallier, N; Menkès, C E

2010-12-01

Upscaling population models from fine to coarse resolutions, in space, time and/or level of description, allows the derivation of fast and tractable models based on a thorough knowledge of individual processes. The validity of such approximations is generally tested only on a limited range of parameter sets. A more general validation test, over a range of parameters, is proposed; this would estimate the error induced by the approximation, using the original model's stochastic variability as a reference. This method is illustrated by three examples taken from the field of epidemics transmitted by vectors that bite in a temporally cyclical pattern, that illustrate the use of the method: to estimate if an approximation over- or under-fits the original model; to invalidate an approximation; to rank possible approximations for their qualities. As a result, the application of the validation method to this field emphasizes the need to account for the vectors' biology in epidemic prediction models and to validate these against finer scale models. Copyright © 2010 Elsevier Inc. All rights reserved.

Liquid chromatography-electrospray ionization tandem mass spectrometry and dynamic multiple reaction monitoring method for determining multiple pesticide residues in tomato.

Science.gov (United States)

Andrade, G C R M; Monteiro, S H; Francisco, J G; Figueiredo, L A; Botelho, R G; Tornisielo, V L

2015-05-15

A quick and sensitive liquid chromatography-electrospray ionization tandem mass spectrometry method, using dynamic multiple reaction monitoring and a 1.8-μm particle size analytical column, was developed to determine 57 pesticides in tomato in a 13-min run. QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for samples preparations and validations was carried out in compliance with EU SANCO guidelines. The method was applied to 58 tomato samples. More than 84% of the compounds investigated showed limits of detection equal to or lower than 5 mg kg(-1). A mild (50%) matrix effect was observed for 72%, 25%, and 3% of the pesticides studied, respectively. Eighty-one percent of the pesticides showed recoveries ranging between 70% and 120%. Twelve pesticides were detected in 35 samples, all below the maximum residue levels permitted in the Brazilian legislation; 15 samples exceeded the maximum residue levels established by the EU legislation for methamidophos; and 10 exceeded limits for acephate and four for bromuconazole. Copyright © 2014 Elsevier Ltd. All rights reserved.

Validation of a liquid chromatography-electrospray ionization tandem mass spectrometric method to determine six polyether ionophores in raw, UHT, pasteurized and powdered milk.

Science.gov (United States)

Pereira, Mararlene Ulberg; Spisso, Bernardete Ferraz; Jacob, Silvana do Couto; Monteiro, Mychelle Alves; Ferreira, Rosana Gomes; Carlos, Betânia de Souza; da Nóbrega, Armi Wanderley

2016-04-01

This study aimed to validate a method developed for the determination of six antibiotics from the polyether ionophore class (lasalocid, maduramicin, monensin, narasin, salinomycin and semduramicin) at residue levels in raw, UHT, pasteurized and powdered milk using QuEChERS extraction and high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). The validation was conducted under an in-house laboratory protocol that is primarily based on 2002/657/EC Decision, but takes in account the variability of matrix sources. Overall recoveries between 93% and 113% with relative standard deviations up to 16% were obtained under intermediate precision conditions. CCα calculated values did not exceed 20% the Maximum Residue Limit for monensin and 25% the Maximum Levels for all other substances. The method showed to be simple, fast and suitable for verifying the compliance of raw and processed milk samples regarding the limits recommended by Codex Alimentarius and those adopted in European Community for polyether ionophores. Copyright © 2015 Elsevier Ltd. All rights reserved.

A Derivatization and Validation Strategy for Determining the Spatial Localization of Endogenous Amine Metabolites in Tissues using MALDI Imaging Mass Spectrometry

Science.gov (United States)

Manier, M. Lisa; Spraggins, Jeffrey M.; Reyzer, Michelle L.; Norris, Jeremy L.; Caprioli, Richard M.

2014-01-01

Imaging mass spectrometry (IMS) studies increasingly focus on endogenous small molecular weight metabolites and consequently bring special analytical challenges. Since analytical tissue blanks do not exist for endogenous metabolites, careful consideration must be given to confirm molecular identity. Here we present approaches for the improvement in detection of endogenous amine metabolites such as amino acids and neurotransmitters in tissues through chemical derivatization and matrix-assisted laser desorption/ionization (MALDI) IMS. Chemical derivatization with 4-hydroxy-3-methoxycinnamaldehyde (CA) was used to improve sensitivity and specificity. CA was applied to the tissue via MALDI sample targets precoated with a mixture of derivatization reagent and ferulic acid (FA) as a MALDI matrix. Spatial distributions of chemically derivatized endogenous metabolites in tissue were determined by high-mass resolution and MSn imaging mass spectrometry. We highlight an analytical strategy for metabolite validation whereby tissue extracts are analyzed by high-performance liquid chromatography (HPLC)-MS/MS to unambiguously identify metabolites and distinguish them from isobaric compounds. PMID:25044893

Determination of ultratrace elements in natural waters by solid-phase extraction and atomic spectrometry methods.

Science.gov (United States)

Grotti, Marco; Abelmoschi, Maria Luisa; Soggia, Francesco; Frache, Roberto

2003-01-01

A study was carried out on the preconcentration of ultratrace amounts of cadmium, lead, manganese, copper and iron from high-salinity aqueous samples and determination by atomic spectrometry methods. Sample volume, amount of resin, loading flow rate, and elution volume were optimized in order to obtain the simultaneous preconcentration of all the analytes. Quantitative recoveries were obtained by using 200 mg of iminodiacetic resin with a loading flow rate of 2 mL min(-1), elution volume of 3 mL and sample volume of 50-450 mL. Only copper in seawater samples was not completely retained by the resin (60-70% recovery), due to unfavorable competition of iminodiacetic-active groups with organically bound metal.To quantify the metals in the eluates, two atomic spectrometry techniques were compared: electrothermal atomization atomic absorption spectrometry (ETAAS) and inductively coupled plasma-optical emission spectrometry (ICP-OES) with simultaneous CCD detection system. Both techniques are suitable for sample analysis with detection limits of 1.0, 4.7, 3.3, 6.8, and 53 ng L(-1) using ETAAS and 12, 122, 3.4, 17, and 21 ng L(-1) using ICP-OES for Cd, Pb, Mn, Cu, and Fe, respectively. Relative standard deviations of the procedures ranged from 1.7 to 14% at the sub-microg L(-1) concentration level. The accuracy of both methods was verified by analyzing various certified reference materials (river water, estuarine water, coastal and off-shore seawater).

Determination of ultratrace elements in natural waters by solid-phase extraction and atomic spectrometry methods

Energy Technology Data Exchange (ETDEWEB)

Grotti, Marco; Abelmoschi, Maria Luisa; Soggia, Francesco; Frache, Roberto [Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso, 31-16146, Genoa (Italy)

2003-01-01

A study was carried out on the preconcentration of ultratrace amounts of cadmium, lead, manganese, copper and iron from high-salinity aqueous samples and determination by atomic spectrometry methods. Sample volume, amount of resin, loading flow rate, and elution volume were optimized in order to obtain the simultaneous preconcentration of all the analytes. Quantitative recoveries were obtained by using 200 mg of iminodiacetic resin with a loading flow rate of 2 mL min{sup -1}, elution volume of 3 mL and sample volume of 50-450 mL. Only copper in seawater samples was not completely retained by the resin (60-70% recovery), due to unfavorable competition of iminodiacetic-active groups with organically bound metal.To quantify the metals in the eluates, two atomic spectrometry techniques were compared: electrothermal atomization atomic absorption spectrometry (ETAAS) and inductively coupled plasma-optical emission spectrometry (ICP-OES) with simultaneous CCD detection system. Both techniques are suitable for sample analysis with detection limits of 1.0, 4.7, 3.3, 6.8, and 53 ng L{sup -1} using ETAAS and 12, 122, 3.4, 17, and 21 ng L{sup -1} using ICP-OES for Cd, Pb, Mn, Cu, and Fe, respectively. Relative standard deviations of the procedures ranged from 1.7 to 14% at the sub-{mu}g L{sup -1} concentration level. The accuracy of both methods was verified by analyzing various certified reference materials (river water, estuarine water, coastal and off-shore seawater). (orig.)

Ultra-performance liquid chromatography-tandem mass spectrometry method for the determination of febuxostat in dog plasma and its application to a pharmacokinetic study.

Science.gov (United States)

Zhang, Tianhong; Sun, Yuanpeng; Zhang, Peng; Gao, Jingmei; Wang, Shanshan; He, Zhonggui

2013-02-01

A rapid, sensitive and selective ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed and validated for the determination of febuxostat in dog plasma. Using paclitaxel as an internal standard (IS), a simple liquid-liquid extraction method with ethyl acetate was adopted for plasma sample pretreatment. Separation was carried out on an Acquity UPLC BEH C(18) column with a mobile phase consisting of acetonitrile and water (containing 0.2% formic acid). The assay was linear in the concentration ranged from 5 to 5000 ng/mL with a lower limit of quantification of 5 ng/mL for febuxostat. The single run analysis was as short as 2.0 min. Finally, the developed method was successfully applied to the pharmacokinetic study of febuxostat tablets following oral administration at a single dose of 40 mg in beagle dogs. Copyright © 2012 John Wiley & Sons, Ltd.

Simultaneous analysis by Quadrupole-Orbitrap mass spectrometry and UHPLC-MS/MS for the determination of sedative-hypnotics and sleep inducers in adulterated products.

Science.gov (United States)

Lee, Ji Hyun; Park, Han Na; Choi, Ji Yeon; Kim, Nam Sook; Park, Hyung-Joon; Park, Seong Soo; Baek, Sun Young

2017-12-01

Adulterated products are continuously detected in society and cause problems. In this study, we developed and validated a method for determining synthetic sedative-hypnotics and sleep inducers, including barbital, benzodiazepam, zolpidem, and first-generation antihistamines, in adulterated products using Quadrupole-Orbitrap mass spectrometry and ultrahigh performance liquid chromatography with tandem mass spectrometry. In Quadrupole-Orbitrap mass spectrometry analysis, target compounds were confirmed using a combination of retention time, mass tolerance, mass accuracy, and fragment ions. For quantification, several validation parameters were employed using ultrahigh performance liquid chromatography with tandem mass spectrometry. The limit of detection and limit of quantitation was 0.05-53 and 0.17-177 ng/mL, respectively. The correlation coefficient for linearity was more than 0.995. The intra- and interassay accuracies were 86-110 and 84-111%, respectively. Their precision values were evaluated as within 4.0 (intraday) and 10.7% (interday). Mean recoveries of target compounds in adulterated products ranged from 85 to 116%. The relative standard deviation of stability was less than 10.7% at 4°C for 48 h. The 144 adulterated products obtained over 3 years (2014-2016) from online and in-person vendors were tested using established methods. After rapidly screening with Quadrupole-Orbitrap mass spectrometry, the detected samples were quantified using ultrahigh performance liquid chromatography with tandem mass spectrometry. Two of them were adulterated with phenobarbital. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative analysis of drug distribution by ambient mass spectrometry imaging method with signal extinction normalization strategy and inkjet-printing technology.

Science.gov (United States)

Luo, Zhigang; He, Jingjing; He, Jiuming; Huang, Lan; Song, Xiaowei; Li, Xin; Abliz, Zeper

2018-03-01

Quantitative mass spectrometry imaging (MSI) is a robust approach that provides both quantitative and spatial information for drug candidates' research. However, because of complicated signal suppression and interference, acquiring accurate quantitative information from MSI data remains a challenge, especially for whole-body tissue sample. Ambient MSI techniques using spray-based ionization appear to be ideal for pharmaceutical quantitative MSI analysis. However, it is more challenging, as it involves almost no sample preparation and is more susceptible to ion suppression/enhancement. Herein, based on our developed air flow-assisted desorption electrospray ionization (AFADESI)-MSI technology, an ambient quantitative MSI method was introduced by integrating inkjet-printing technology with normalization of the signal extinction coefficient (SEC) using the target compound itself. The method utilized a single calibration curve to quantify multiple tissue types. Basic blue 7 and an antitumor drug candidate (S-(+)-deoxytylophorinidine, CAT) were chosen to initially validate the feasibility and reliability of the quantitative MSI method. Rat tissue sections (heart, kidney, and brain) administered with CAT was then analyzed. The quantitative MSI analysis results were cross-validated by LC-MS/MS analysis data of the same tissues. The consistency suggests that the approach is able to fast obtain the quantitative MSI data without introducing interference into the in-situ environment of the tissue sample, and is potential to provide a high-throughput, economical and reliable approach for drug discovery and development. Copyright © 2017 Elsevier B.V. All rights reserved.

Validation of a Method for Cylindrospermopsin Determination in Vegetables: Application to Real Samples Such as Lettuce (Lactuca sativa L.

Directory of Open Access Journals (Sweden)

Ana I. Prieto

2018-02-01

Full Text Available Reports on the occurrence of the cyanobacterial toxin cylindrospermopsin (CYN have increased worldwide because of CYN toxic effects in humans and animals. If contaminated waters are used for plant irrigation, these could represent a possible CYN exposure route for humans. For the first time, a method employing solid phase extraction and quantification by ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS of CYN was optimized in vegetables matrices such as lettuce (Lactuca sativa. The validated method showed a linear range, from 5 to 500 ng CYN g−1 of fresh weight (f.w., and detection and quantitation limits (LOD and LOQ of 0.22 and 0.42 ng CYN g−1 f.w., respectively. The mean recoveries ranged between 85 and 104%, and the intermediate precision from 12.7 to 14.7%. The method showed to be robust for the three different variables tested. Moreover, it was successfully applied to quantify CYN in edible lettuce leaves exposed to CYN-contaminated water (10 µg L−1, showing that the tolerable daily intake (TDI in the case of CYN could be exceeded in elderly high consumers. The validated method showed good results in terms of sensitivity, precision, accuracy, and robustness for CYN determination in leaf vegetables such as lettuce. More studies are needed in order to prevent the risks associated with the consumption of CYN-contaminated vegetables.

Validation of a Method for Cylindrospermopsin Determination in Vegetables: Application to Real Samples Such as Lettuce (Lactuca sativa L.).

Science.gov (United States)

Prieto, Ana I; Guzmán-Guillén, Remedios; Díez-Quijada, Leticia; Campos, Alexandre; Vasconcelos, Vitor; Jos, Ángeles; Cameán, Ana M

2018-02-01

Reports on the occurrence of the cyanobacterial toxin cylindrospermopsin (CYN) have increased worldwide because of CYN toxic effects in humans and animals. If contaminated waters are used for plant irrigation, these could represent a possible CYN exposure route for humans. For the first time, a method employing solid phase extraction and quantification by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) of CYN was optimized in vegetables matrices such as lettuce ( Lactuca sativa ). The validated method showed a linear range, from 5 to 500 ng CYN g -1 of fresh weight (f.w.), and detection and quantitation limits (LOD and LOQ) of 0.22 and 0.42 ng CYN g -1 f.w., respectively. The mean recoveries ranged between 85 and 104%, and the intermediate precision from 12.7 to 14.7%. The method showed to be robust for the three different variables tested. Moreover, it was successfully applied to quantify CYN in edible lettuce leaves exposed to CYN-contaminated water (10 µg L -1 ), showing that the tolerable daily intake (TDI) in the case of CYN could be exceeded in elderly high consumers. The validated method showed good results in terms of sensitivity, precision, accuracy, and robustness for CYN determination in leaf vegetables such as lettuce. More studies are needed in order to prevent the risks associated with the consumption of CYN-contaminated vegetables.

Validation of {sup 226}Ra, {sup 228}Ra and {sup 210}Pb measurements in soil and sediment samples through high resolution gamma ray spectrometry

Energy Technology Data Exchange (ETDEWEB)

Dias, Danila Carrijo da Silva; Silva, Nivaldo Carlos da; Bonifacio, Rodrigo Leandro; Guerrero, Eder Tadeu Zenun [Comissao Nacional de Energia Nuclear (LAPOC/CNEN-MG), Pocos de Caldas, MG (Brazil). Laboratorio de Pocos de Caldas

2013-07-01

Radionuclides found in ore extraction waste materials are a great source of concern regarding public health and environmental safety. One technique to determine the concentration of substances is high resolution gamma ray spectrometry using HPGe. Validating a measurement technique is essential to warrant high levels of quality to any scientific work. The Laboratory of Pocos de Caldas of the Brazilian Commission for Nuclear Energy partakes into a Quality Management System project, seeking Accreditation under ISO/IEC 17025 through the validation of techniques of chemical and radiometric analysis of environmental samples from water, soil and sediment. The focus of the Radon Laboratory at LAPOC is validation of Ra-226, Ra-228 and Pb-210 concentration determinations in soil and sediment through a gamma spectrometer system. The stages of this validation process included sample reception and preparation, detector calibration and sample analyses. Dried samples were sealed in metallic containers and analyzed after radioactive equilibrium between Ra-226 and daughters Pb-214 and Bi-214. Gamma spectrometry was performed using CANBERRA HPGe detector and gamma spectrum software Genie 2000. The photo peaks used for Ra-226 determination were 609 keV and 1020 keV of Bi-214 and 351 keV of Pb-214. For the Ra-228 determination a photopeak of 911 keV was used from its short half-life daughter Ac-228 (T1/2 = 6.12 h). For Pb-210, the photopeak of 46.5 keV was used, which, due to the low energy, self-absorption correction was needed. Parameters such as precision, bias/accuracy, linearity, detection limit and uncertainty were evaluated for that purpose. The results have pointed to satisfying results. (author)

Development and validation of an ultra-fast and sensitive microflow liquid chromatography-tandem mass spectrometry (MFLC-MS/MS) method for quantification of LSD and its metabolites in plasma and application to a controlled LSD administration study in humans.

Science.gov (United States)

Steuer, Andrea E; Poetzsch, Michael; Stock, Lorena; Eisenbeiss, Lisa; Schmid, Yasmin; Liechti, Matthias E; Kraemer, Thomas

2017-05-01

Lysergic acid diethylamide (LSD) is a semi-synthetic hallucinogen that has gained popularity as a recreational drug and has been investigated as an adjunct to psychotherapy. Analysis of LSD represents a major challenge in forensic toxicology due to its instability, low drug concentrations, and short detection windows in biological samples. A new, fast, and sensitive microflow liquid chromatography (MFLC) tandem mass spectrometry method for the validated quantification of LSD, iso-LSD, 2-oxo 3-hydroxy-LSD (oxo-HO-LSD), and N-desmethyl-LSD (nor-LSD) was developed in plasma and applied to a controlled pharmacokinetic (PK) study in humans to test whether LSD metabolites would offer for longer detection windows. Five hundred microlitres of plasma were extracted by solid phase extraction. Analysis was performed on a Sciex Eksigent MFLC system coupled to a Sciex 5500 QTrap. The method was validated according to (inter)-national guidelines. MFLC allowed for separation of the mentioned analytes within 3 minutes and limits of quantification of 0.01 ng/mL. Validation criteria were fulfilled for all analytes. PK data could be calculated for LSD, iso-LSD, and oxo-HO-LSD in all participants. Additionally, hydroxy-LSD (HO-LSD) and HO-LSD glucuronide could be qualitatively detected and PK determined in 11 and 8 subjects, respectively. Nor-LSD was only sporadically detected. Elimination half-lives of iso-LSD (median 12 h) and LSD metabolites (median 9, 7.4, 12, and 11 h for oxo-HO-LSD, HO-LSD, HO-LSD-gluc, and nor-LSD, respectively) exceeded those of LSD (median 4.2 h). However, screening for metabolites to increase detection windows in plasma seems not to be constructive due to their very low concentrations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Model-Based Method for Sensor Validation

Science.gov (United States)

Vatan, Farrokh

2012-01-01

Fault detection, diagnosis, and prognosis are essential tasks in the operation of autonomous spacecraft, instruments, and in situ platforms. One of NASA s key mission requirements is robust state estimation. Sensing, using a wide range of sensors and sensor fusion approaches, plays a central role in robust state estimation, and there is a need to diagnose sensor failure as well as component failure. Sensor validation can be considered to be part of the larger effort of improving reliability and safety. The standard methods for solving the sensor validation problem are based on probabilistic analysis of the system, from which the method based on Bayesian networks is most popular. Therefore, these methods can only predict the most probable faulty sensors, which are subject to the initial probabilities defined for the failures. The method developed in this work is based on a model-based approach and provides the faulty sensors (if any), which can be logically inferred from the model of the system and the sensor readings (observations). The method is also more suitable for the systems when it is hard, or even impossible, to find the probability functions of the system. The method starts by a new mathematical description of the problem and develops a very efficient and systematic algorithm for its solution. The method builds on the concepts of analytical redundant relations (ARRs).

In-situ spectrometry of {sup 137}Cs in the soil by unfolding method

Energy Technology Data Exchange (ETDEWEB)

Fueloep, M; Ragan, P [Inst. of Preventive and Clinical Medicine, 833301 Bratislava (Slovakia); Krnac, S [Slovak Technical Univ., Bratislava (Slovakia)

1996-12-31

This contribution is aimed to the possibility of improving the in-situ gamma spectrometry to be independent on a knowledge about a depth distribution of {sup 137}Cs in soil and sufficiently sensitive for the measurement of the post-Chernobyl {sup 137}Cs at present, as well. The depth distribution of {sup 137}Cs averaged over a large area of soil is obtained by unfolding of the detector responses to primary and in soil forward scattered photons. The proposed method employs detector with and without collimator. The {sup 137}Cs distributions obtained in-situ measurements are analysed, and comparisons are made to the results obtained with soil sampling and with standard in-situ spectrometry, as well. 5 figs., 1 tab., 4 refs.

Sensitive method for the quantitative determination of proguanil and its metabolites in rat blood and plasma by liquid chromatography-mass spectrometry.

Science.gov (United States)

Leveque, Nathalie L; Charman, William N; Chiu, Francis C K

2006-01-18

A sensitive, simple and fast liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method for the determination of proguanil (PG) and its metabolites, cycloguanil (CG) and 1-(4-chlorophenyl)biguanide (4CPB), was developed and validated over a concentration range of 1-2000 ng/mL using only 50 microL of blood or plasma. After a simple solvent precipitation procedure, the supernatant was analysed directly by HPLC-MS/MS. Separation was achieved using an ethyl-linked phenyl reverse phase column with polar endcapping with an acetonitrile-water-formic acid gradient. Mass spectrometry was performed using a triple quadrupole mass spectrometer operating in positive electrospray ionization mode. The elution of PG (254.07-->169.99), CG (252.12-->195.02) and 4CPB (212.06-->153.06) was monitored using selected reaction monitoring. The three compounds and the internal standard (chloroproguanil) were well separated by HPLC and no interfering peaks were detected at the usual concentrations found in blood and plasma. The limit of quantification of PG and CG was 1 ng/mL and 5 ng/mL for 4CPB in rat blood and plasma. The extraction efficiency of PG, CG and 4CPB from rat blood and plasma was higher than 73%. The intra- and inter-assay variability of PG, CG and 4CPB were within 12% and the accuracy within +/-5%. This new assay offers higher sensitivity and a much shorter run time over earlier methods.

Validated modified Lycopodium spore method development for ...

African Journals Online (AJOL)

Validated modified lycopodium spore method has been developed for simple and rapid quantification of herbal powdered drugs. Lycopodium spore method was performed on ingredients of Shatavaryadi churna, an ayurvedic formulation used as immunomodulator, galactagogue, aphrodisiac and rejuvenator. Estimation of ...

Sensitive, automatic method for the determination of diazepam and its five metabolites in human oral fluid by online solid-phase extraction and liquid chromatography with tandem mass spectrometry

DEFF Research Database (Denmark)

Jiang, Fengli; Rao, Yulan; Wang, Rong

2016-01-01

A novel and simple online solid-phase extraction liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous determination of diazepam and its five metabolites including nordazepam, oxazepam, temazepam, oxazepam glucuronide, and temazepam glucuronide...... in human oral fluid. Human oral fluid was obtained using the Salivette(®) collection device, and 100 μL of oral fluid samples were loaded onto HySphere Resin GP cartridge for extraction. Analytes were separated on a Waters Xterra C18 column and quantified by liquid chromatography with tandem mass...

Spectral-ratio radon background correction method in airborne γ-ray spectrometry based on compton scattering deduction

International Nuclear Information System (INIS)

Gu Yi; Xiong Shengqing; Zhou Jianxin; Fan Zhengguo; Ge Liangquan

2014-01-01

γ-ray released by the radon daughter has severe impact on airborne γ-ray spectrometry. The spectral-ratio method is one of the best mathematical methods for radon background deduction in airborne γ-ray spectrometry. In this paper, an advanced spectral-ratio method was proposed which deducts Compton scattering ray by the fast Fourier transform rather than tripping ratios, the relationship between survey height and correction coefficient of the advanced spectral-ratio radon background correction method was studied, the advanced spectral-ratio radon background correction mathematic model was established, and the ground saturation model calibrating technology for correction coefficient was proposed. As for the advanced spectral-ratio radon background correction method, its applicability and correction efficiency are improved, and the application cost is saved. Furthermore, it can prevent the physical meaning lost and avoid the possible errors caused by matrix computation and mathematical fitting based on spectrum shape which is applied in traditional correction coefficient. (authors)

Single Laboratory Validated Method for Determination of Cylindrospermopsin and Anatoxin-a in Ambient Water by Liquid Chromatography/ Tandem Mass Spectrometry (LC/MS/MS)

Science.gov (United States)

This product is an LC/MS/MS single laboratory validated method for the determination of cylindrospermopsin and anatoxin-a in ambient waters. The product contains step-by-step instructions for sample preparation, analyses, preservation, sample holding time and QC protocols to ensu...

Alternative dissolution methods for analysis of niobium containing ...

African Journals Online (AJOL)

NICO

2The South African Nuclear Energy Corporation Ltd. (Necsa), P.O. Box 582, Pretoria 0001, South Africa. ... Inductively coupled plasma optical emission spectrometry was applied for ..... Validation of the methods for niobium determination was.

Application of the bomb radiocarbon chronometer to the validation of redfish Centroberyx affinis age

International Nuclear Information System (INIS)

Kalish, J.M.

1995-01-01

Validation of methods used to estimate fish age is a critical element of the fish stock assessment process. Despite the importance of validation, few procedures are available that provide unbiased estimates of true fish age and those methods that are available are seldom used. The majority of these methods are unlikely to provide an indication of the true age of individual fish, data that are best suited to the validation process. Accelerator mass spectrometry analyses of radiocarbon in selected regions of Centroberyx affinis otoliths were used to validate the age estimation method for this species. Radiocarbon data from the otoliths of C. affinis with presumed birth dates between 1955 and 1985 described the increase in ocean radiocarbon attributable to the atmospheric detonation of nuclear weapons in the 1950s and 1960s. The results confirm the longevity of C. affinis and demonstrate the effectiveness of the bomb radiocarbon chronometer for the validation of age-estimation methods. (author). 31 refs., 2 tabs., 1 fig

A simple method for the deconvolution of 134 Cs/137 Cs peaks in gamma-ray scintillation spectrometry

International Nuclear Information System (INIS)

Darko, E.O.; Osae, E.K.; Schandorf, C.

1998-01-01

A simple method for the deconvolution of 134 Cs / 137 Cs peaks in a given mixture of 134 Cs and 137 Cs using Nal(TI) gamma-ray scintillation spectrometry is described. In this method the 795 keV energy of 134 Cs is used as a reference peak to calculate the activity of the 137 Cs directly from the measured peaks. Certified reference materials were measured using the method and compared with a high resolution gamma-ray spectrometry measurements. The results showed good agreement with the certified values. The method is very simple and does not need any complicated mathematics and computer programme to de- convolute the overlapping 604.7 keV and 661.6 keV peaks of 134 Cs and 137 Cs respectively. (author). 14 refs.; 1 tab., 2 figs

Cross-Validation of Survival Bump Hunting by Recursive Peeling Methods.

Science.gov (United States)

Dazard, Jean-Eudes; Choe, Michael; LeBlanc, Michael; Rao, J Sunil

2014-08-01

We introduce a survival/risk bump hunting framework to build a bump hunting model with a possibly censored time-to-event type of response and to validate model estimates. First, we describe the use of adequate survival peeling criteria to build a survival/risk bump hunting model based on recursive peeling methods. Our method called "Patient Recursive Survival Peeling" is a rule-induction method that makes use of specific peeling criteria such as hazard ratio or log-rank statistics. Second, to validate our model estimates and improve survival prediction accuracy, we describe a resampling-based validation technique specifically designed for the joint task of decision rule making by recursive peeling (i.e. decision-box) and survival estimation. This alternative technique, called "combined" cross-validation is done by combining test samples over the cross-validation loops, a design allowing for bump hunting by recursive peeling in a survival setting. We provide empirical results showing the importance of cross-validation and replication.

A high-performance liquid chromatography-tandem mass spectrometry method coupled with protein precipitation for determination of granisetron in human plasma and its application to a comparative pharmacokinetic study.

Science.gov (United States)

Zhou, Ying; Jiang, Ji; Hu, Pei; Wang, Hongyun

2014-12-01

A rapid, simple and validated method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) has been developed for the determination of granisetron in human plasma. Plasma samples were pre-purified by protein precipitation procedure. The chromatographic separation was achieved with Synergi Polar-RP (75 × 2 mm, 4 µm) column using a mixture of 5 mm pH4.0 ammonium formate and methanol (300:316, v/v) under isocratic conditions at a flow rate of 0.3 mL/min. The detection was performed on a triple quadrupole tandem mass spectrometer in multiple reaction monitoring mode using positive electrospray ionization. The analysis time was about 2.5 min. The method was fully validated over the concentration range 0.1-10 ng/mL. The lower limit of quantification was 0.1 ng/mL. Inter- and intra-batch precision was granisetron in Chinese healthy subjects. Copyright © 2014 John Wiley & Sons, Ltd.

Method Validation Procedure in Gamma Spectroscopy Laboratory

International Nuclear Information System (INIS)

El Samad, O.; Baydoun, R.

2008-01-01

The present work describes the methodology followed for the application of ISO 17025 standards in gamma spectroscopy laboratory at the Lebanese Atomic Energy Commission including the management and technical requirements. A set of documents, written procedures and records were prepared to achieve the management part. The technical requirements, internal method validation was applied through the estimation of trueness, repeatability , minimum detectable activity and combined uncertainty, participation in IAEA proficiency tests assure the external method validation, specially that the gamma spectroscopy lab is a member of ALMERA network (Analytical Laboratories for the Measurements of Environmental Radioactivity). Some of these results are presented in this paper. (author)

Determination of albendazole sulfoxide in human plasma by using liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Saraner, Nihal; Özkan, Güler Yağmur; Güney, Berrak; Alkan, Erkin; Burul-Bozkurt, Nihan; Sağlam, Onursal; Fikirdeşici, Ezgi; Yıldırım, Mevlüt

2016-06-01

A rapid, simple and sensitive method was developed and validated using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination of albendazole sulfoxide (ABZOX) in human plasma. The plasma samples were extracted by protein precipitation using albendazole sulfoxide-d3 as internal standard (IS). The chromatographic separation was performed on Waters Xbridge C18Column (100×4.6mm, 3.5μm) with a mobile phase consisting of ammonia solution, water and methanol at a flow rate of 0.70mL/min. ABZOX was detected and identified by mass spectrometry with electrospray ionization (ESI) in positive ion and multiple-reaction monitoring (MRM) mode. The method was linear in the range of 3-1500ng/mL for ABZOX. This method was successfully applied to the bioequivalence study in human plasma samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Method validation for strobilurin fungicides in cereals and fruit

DEFF Research Database (Denmark)

Christensen, Hanne Bjerre; Granby, Kit

2001-01-01

Strobilurins are a new class of fungicides that are active against a broad spectrum of fungi. In the present work a GC method for analysis of strobilurin fungicides was validated. The method was based on extraction with ethyl acetate/cyclohexane, clean-up by gel permeation chromatography (GPC......) and determination of the content by gas chromatography (GC) with electron capture (EC-), nitrogen/phosphorous (NP-), and mass spectrometric (MS-) detection. Three strobilurins, azoxystrobin, kresoxim-methyl and trifloxystrobin were validated on three matrices, wheat, apple and grapes. The validation was based...

The element analysis of high purity beryllium by method of laser mass-spectrometry

International Nuclear Information System (INIS)

Virich, V.D.; Kisel', O.V.; Kovtun, K.V.; Pugachev, N.S.; Yakobson, L.A.

2003-01-01

The operation is devoted to examination of a possibility of the analysis of element composition pure and high purity model of a beryllium is model by a method of laser mass spectrometry. The advantages of a method in a part of finding of a small amount of admixtures in comparison with other modes of the analysis are exhibited. The possibility of quantitative definition of a content in beryllium samples of gas-making admixtures-C,N,O surveyed

Determination of Grayanotoxins from Rhododendron brachycarpum in Dietary Supplements and Homemade Wine by Liquid Chromatography-Quadrupole Time-of-Flight-Mass Spectrometry and Liquid Chromatography-Tandem Mass Spectrometry.

Science.gov (United States)

Hwang, Taeik; Noh, Eunyoung; Jeong, Ji Hye; Park, Sung-Kwan; Shin, Dongwoo; Kang, Hoil

2018-02-28

A sensitive and specific high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (LC-QTOF-MS) method combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of grayanotoxins I and III in dietary supplements and homemade wine. Grayanotoxins I and III were successfully extracted using solid-phase extraction cartridges, characterized by LC-QTOF-MS, and quantitated by LC-MS/MS. The LC-MS/MS calibration curves were linear over concentrations of 10-100 ng/mL (grayanotoxin I) and 20-400 ng/mL (grayanotoxin III). Grayanotoxins I and III were found in 51 foodstuffs, with quantitative determinations revealing total toxin concentrations of 18.4-101 000 ng/mL (grayanotoxin I) and 15.3-56 000 ng/mL (grayanotoxin III). The potential of the validated method was demonstrated by successful quantitative analysis of grayanotoxins I and III in dietary supplements and homemade wine; the method appears suitable for the routine detection of grayanotoxins I and III from Rhododendron brachycarpum.

76 FR 28664 - Method 301-Field Validation of Pollutant Measurement Methods From Various Waste Media

Science.gov (United States)

2011-05-18

... . d m = The mean of the paired sample differences. n = Total number of paired samples. 7.4.2 t Test... being compared to a validated test method as part of the Method 301 validation and an audit sample for... tighten the acceptance criteria for the precision of candidate alternative test methods. One commenter...

Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D2O.

Science.gov (United States)

Acter, Thamina; Lee, Seulgidaun; Cho, Eunji; Jung, Maeng-Joon; Kim, Sunghwan

2018-01-01

In this study, continuous in-source hydrogen/deuterium exchange (HDX) atmospheric pressure photoionization (APPI) mass spectrometry (MS) with continuous feeding of D 2 O was developed and validated. D 2 O was continuously fed using a capillary line placed on the center of a metal plate positioned between the UV lamp and nebulizer. The proposed system overcomes the limitations of previously reported APPI HDX-MS approaches where deuterated solvents were premixed with sample solutions before ionization. This is particularly important for APPI because solvent composition can greatly influence ionization efficiency as well as the solubility of analytes. The experimental parameters for APPI HDX-MS with continuous feeding of D 2 O were optimized, and the optimized conditions were applied for the analysis of nitrogen-, oxygen-, and sulfur-containing compounds. The developed method was also applied for the analysis of the polar fraction of a petroleum sample. Thus, the data presented in this study clearly show that the proposed HDX approach can serve as an effective analytical tool for the structural analysis of complex mixtures. Graphical abstract ᅟ.

Method for detecting binding events using micro-X-ray fluorescence spectrometry

Science.gov (United States)

Warner, Benjamin P.; Havrilla, George J.; Mann, Grace

2010-12-28

Method for detecting binding events using micro-X-ray fluorescence spectrometry. Receptors are exposed to at least one potential binder and arrayed on a substrate support. Each member of the array is exposed to X-ray radiation. The magnitude of a detectable X-ray fluorescence signal for at least one element can be used to determine whether a binding event between a binder and a receptor has occurred, and can provide information related to the extent of binding between the binder and receptor.

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)

Comparison of quantification methods for the analysis of polychlorinated alkanes using electron capture negative ionization mass spectrometry.

NARCIS (Netherlands)

Rusina, T.; Korytar, P.; de Boer, J.

2011-01-01

Four quantification methods for short-chain chlorinated paraffins (SCCPs) or polychlorinated alkanes (PCAs) using gas chromatography electron capture negative ionisation low resolution mass spectrometry (GC-ECNI-LRMS) were investigated. The method based on visual comparison of congener group

Comparison of quantification methods for the analysis of polychlorinated alkanes using electron capture negative ionisation mass spectrometry

NARCIS (Netherlands)

Rusina, T.; Korytar, P.; Boer, de J.

2011-01-01

Four quantification methods for short-chain chlorinated paraffins (SCCPs) or polychlorinated alkanes (PCAs) using gas chromatography electron capture negative ionisation low resolution mass spectrometry (GC-ECNI-LRMS) were investigated. The method based on visual comparison of congener group

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

The Value of Qualitative Methods in Social Validity Research

Science.gov (United States)

Leko, Melinda M.

2014-01-01

One quality indicator of intervention research is the extent to which the intervention has a high degree of social validity, or practicality. In this study, I drew on Wolf's framework for social validity and used qualitative methods to ascertain five middle schoolteachers' perceptions of the social validity of System 44®--a phonics-based reading…

Iodate oxidation of N-Acetyl L-Cysteine: Application in drug determination and characterization of its oxidation and degradation product by mass spectrometry

International Nuclear Information System (INIS)

Siddiqui, Masom Raza; Wabaiduri, Saikh Mohammas; Alothman, Zied A; Rahman, Habibur; Alam, Sarfarah; Ali, Sajid

2014-01-01

A kinetic spectrophotometric method based on the initial rate measurement has been developed for the determination of N-acetyl L-cysteine. The developed method is based on the oxidation of N-acetyl L-cysteine with iodate. The reaction product was studied and characterized using the mass spectrometry and the structure of the product was proposed. From the mass spectrometric studies it was concluded that the oxidation of the drug resulted in the formation of a disulfide. The developed method was validated as per the guidelines of international conference on harmonization. The developed initial rate method was found to be linear in the concentration range of 1.25 - 30μg ml-1. The detection and quantitation limits were found to be 0.018 and 0.056 μG ml -1 . In the current study, the degradation product of N-acetyl L cysteine was also prepared and identified using mass spectrometry. Keywords: N- acetyl cysteine, Initial rate method, Spectrophotometry, mass spectrometry

Development of a gas chromatography-mass spectrometry method for the determination of pesticides in gaseous and particulate phases in the atmosphere.

Science.gov (United States)

Borrás, E; Sánchez, P; Muñoz, A; Tortajada-Genaro, L A

2011-08-05

A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography-mass spectrometry (GC-MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interferences. The pesticides were benfluralin, bitertanol, buprofezin, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, ethalfluralin, fenthion, lindane, malathion, methidathion, propachlor, propanil, pyriproxifen, tebuconazol and trifluralin. Comparisons of two types of sampling filters (quartz and glass fibre) and four types of solid-phase cartridges (XAD-2, XAD-4, Florisil and Orbo-49P) showed that the most suitable supports were glass fibre filter for particulate pesticides and XAD-2 and XAD-4 cartridges for gaseous pesticides (>95% recovery). Evaluations of elution solvents for ultrasonic-assisted extraction demonstrated that isooctane is better than ethylacetate, dichloromethane, methanol or a mixture of acetone:hexane (1:1). Recovery assays and the standard addition method were performed to validate the proposed methodology. Moreover, large simulator chamber experiments allowed the best study of the gas-particle partitioning of pesticides for testing the sampling efficiency for the validation of an analytical multiresidue method for pesticides in air. Satisfactory analytical parameters were obtained, with a repeatability of 5±1%, a reproducibility of 13±3% and detection limits of 0.05-0.18 pg m(-3) for the particulate phase and 26-88 pg m(-3) for the gaseous phase. Finally, the methodology was successfully applied to rural and agricultural samples in the Mediterranean area. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Validation of Land Cover Products Using Reliability Evaluation Methods

Directory of Open Access Journals (Sweden)

Wenzhong Shi

2015-06-01

Full Text Available Validation of land cover products is a fundamental task prior to data applications. Current validation schemes and methods are, however, suited only for assessing classification accuracy and disregard the reliability of land cover products. The reliability evaluation of land cover products should be undertaken to provide reliable land cover information. In addition, the lack of high-quality reference data often constrains validation and affects the reliability results of land cover products. This study proposes a validation schema to evaluate the reliability of land cover products, including two methods, namely, result reliability evaluation and process reliability evaluation. Result reliability evaluation computes the reliability of land cover products using seven reliability indicators. Process reliability evaluation analyzes the reliability propagation in the data production process to obtain the reliability of land cover products. Fuzzy fault tree analysis is introduced and improved in the reliability analysis of a data production process. Research results show that the proposed reliability evaluation scheme is reasonable and can be applied to validate land cover products. Through the analysis of the seven indicators of result reliability evaluation, more information on land cover can be obtained for strategic decision-making and planning, compared with traditional accuracy assessment methods. Process reliability evaluation without the need for reference data can facilitate the validation and reflect the change trends of reliabilities to some extent.

Integration of gas chromatography mass spectrometry methods for differentiating ricin preparation methods.

Science.gov (United States)

Wunschel, David S; Melville, Angela M; Ehrhardt, Christopher J; Colburn, Heather A; Victry, Kristin D; Antolick, Kathryn C; Wahl, Jon H; Wahl, Karen L

2012-05-07

The investigation of crimes involving chemical or biological agents is infrequent, but presents unique analytical challenges. The protein toxin ricin is encountered more frequently than other agents and is found in the seeds of Ricinus communis, commonly known as the castor plant. Typically, the toxin is extracted from castor seeds utilizing a variety of different recipes that result in varying purity of the toxin. Moreover, these various purification steps can also leave or differentially remove a variety of exogenous and endogenous residual components with the toxin that may indicate the type and number of purification steps involved. We have applied three gas chromatography-mass spectrometry (GC-MS) based analytical methods to measure the variation in seed carbohydrates and castor oil ricinoleic acid, as well as the presence of solvents used for purification. These methods were applied to the same samples prepared using four previously identified toxin preparation methods, starting from four varieties of castor seeds. The individual data sets for seed carbohydrate profiles, ricinoleic acid, or acetone amount each provided information capable of differentiating different types of toxin preparations across seed types. However, the integration of the data sets using multivariate factor analysis provided a clear distinction of all samples based on the preparation method, independent of the seed source. In particular, the abundance of mannose, arabinose, fucose, ricinoleic acid, and acetone were shown to be important differentiating factors. These complementary tools provide a more confident determination of the method of toxin preparation than would be possible using a single analytical method.

Multiresidue method for detection of pesticides in beef meat using liquid chromatography coupled to mass spectrometry detection (LC-MS) after QuEChERS extraction.

Science.gov (United States)

Oliveira, Fabiano Aurélio da Silva; Pereira, Elba Nathália Corrêa; Gobbi, Jennifer Mattedi; Soto-Blanco, Benito; Melo, Marília Martins

2018-01-01

Beef meat is an important food that can be contaminated by pesticides. This study aimed to optimize a multiresidue method for identification and quantification of pesticides in beef meat by liquid chromatography coupled to mass spectrometry detection (LC-MS). The extraction and clean-up procedures were adapted from the QuECHERS method. From the 188 analytes tested, the method was validated as qualitative method for 19 compounds and as quantitative method for 152 compounds. The results were satisfactory, yielding coefficients of variation of less than 20% and recoveries ranging from 70% to 120% and expanded uncertainty of less than 50%. The quantification limit was typically 10 µg kg -1 (but 25 µg kg -1 for 12 of the compounds) and the detection limit was 5.0 µg kg -1 . Thirty-two real samples of commercialized beef meat were analyzed without any residual pesticide being found. Thus, the results showed that the multiresidue method for detecting 171 pesticides, using adapted QuECHERS for extraction and LC-MS for detection, is suitable for analyzing beef meat.

A single-run liquid chromatography mass spectrometry method to quantify neuroactive kynurenine pathway metabolites in rat plasma.

Science.gov (United States)

Orsatti, Laura; Speziale, Roberto; Orsale, Maria Vittoria; Caretti, Fulvia; Veneziano, Maria; Zini, Matteo; Monteagudo, Edith; Lyons, Kathryn; Beconi, Maria; Chan, Kelvin; Herbst, Todd; Toledo-Sherman, Leticia; Munoz-Sanjuan, Ignacio; Bonelli, Fabio; Dominguez, Celia

2015-03-25

Neuroactive metabolites in the kynurenine pathway of tryptophan catabolism are associated with neurodegenerative disorders. Tryptophan is transported across the blood-brain barrier and converted via the kynurenine pathway to N-formyl-L-kynurenine, which is further degraded to L-kynurenine. This metabolite can then generate a group of metabolites called kynurenines, most of which have neuroactive properties. The association of tryptophan catabolic pathway alterations with various central nervous system (CNS) pathologies has raised interest in analytical methods to accurately quantify kynurenines in body fluids. We here describe a rapid and sensitive reverse-phase HPLC-MS/MS method to quantify L-kynurenine (KYN), kynurenic acid (KYNA), 3-hydroxy-L-kynurenine (3HK) and anthranilic acid (AA) in rat plasma. Our goal was to quantify these metabolites in a single run; given their different physico-chemical properties, major efforts were devoted to develop a chromatography suitable for all metabolites that involves plasma protein precipitation with acetonitrile followed by chromatographic separation by C18 RP chromatography, detected by electrospray mass spectrometry. Quantitation range was 0.098-100 ng/ml for 3HK, 9.8-20,000 ng/ml for KYN, 0.49-1000 ng/ml for KYNA and AA. The method was linear (r>0.9963) and validation parameters were within acceptance range (calibration standards and QC accuracy within ±30%). Copyright © 2015 Elsevier B.V. All rights reserved.

A new classification method for MALDI imaging mass spectrometry data acquired on formalin-fixed paraffin-embedded tissue samples.

Science.gov (United States)

Boskamp, Tobias; Lachmund, Delf; Oetjen, Janina; Cordero Hernandez, Yovany; Trede, Dennis; Maass, Peter; Casadonte, Rita; Kriegsmann, Jörg; Warth, Arne; Dienemann, Hendrik; Weichert, Wilko; Kriegsmann, Mark

2017-07-01

Matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI IMS) shows a high potential for applications in histopathological diagnosis, and in particular for supporting tumor typing and subtyping. The development of such applications requires the extraction of spectral fingerprints that are relevant for the given tissue and the identification of biomarkers associated with these spectral patterns. We propose a novel data analysis method based on the extraction of characteristic spectral patterns (CSPs) that allow automated generation of classification models for spectral data. Formalin-fixed paraffin embedded (FFPE) tissue samples from N=445 patients assembled on 12 tissue microarrays were analyzed. The method was applied to discriminate primary lung and pancreatic cancer, as well as adenocarcinoma and squamous cell carcinoma of the lung. A classification accuracy of 100% and 82.8%, resp., could be achieved on core level, assessed by cross-validation. The method outperformed the more conventional classification method based on the extraction of individual m/z values in the first application, while achieving a comparable accuracy in the second. LC-MS/MS peptide identification demonstrated that the spectral features present in selected CSPs correspond to peptides relevant for the respective classification. This article is part of a Special Issue entitled: MALDI Imaging, edited by Dr. Corinna Henkel and Prof. Peter Hoffmann. Copyright © 2016 Elsevier B.V. All rights reserved.

Development and validation of a gas chromatography/mass spectrometry procedure for confirmation of para-toluenesulfonamide in edible fish fillet tissue.

Science.gov (United States)

Idowu, Olutosin R; Kijak, Philip J; Meinertz, Jeffery R; Schmidt, Larry J

2004-01-01

Chloramine-T is a disinfectant being developed as a treatment for bacterial gill disease in cultured fish. As part of the drug approval process, a method is required for the confirmation of chloramine-T residues in edible fish tissue. The marker residue that will be used to determine the depletion of chloramine-T residues from the edible tissue of treated fish is para-toluenesulfonamide (p-TSA), a metabolite of chloramine-T. The development and validation of a procedure for the confirmation of p-TSA is described. Homogenized fish tissue is dried by mixing with anhydrous sodium sulfate, and the mixture is extracted with methylene chloride. The extract is passed through a silica gel solid-phase extraction column, from which p-TSA is subsequently eluted with acetonitrile. The acetonitrile extract is evaporated, and the oily residue is dissolved in hexane. The hexane solution is shaken with fresh acetonitrile. The acetonitrile solution is evaporated and the residue is redissolved in dilute potassium hydroxide solution. The aqueous solution is extracted with methylene chloride to further remove more of the fat co-extractive. The aqueous solution is reacted with pentafluorobenzyl bromide in presence of tetrabutylammonium hydrogensulfate. The resulting di-(pentafluorobenzyl) derivative of p-TSA is analyzed by gas chromatography/mass spectrometry. This method permits the confirmation of p-TSA in edible fish tissue at 20 ppb.

A sensitive and selective liquid chromatography/tandem mass spectrometry method for quantitative analysis of efavirenz in human plasma.

Directory of Open Access Journals (Sweden)

Praveen Srivastava

Full Text Available A selective and a highly sensitive method for the determination of the non-nucleoside reverse transcriptase inhibitor (NNRTI, efavirenz, in human plasma has been developed and fully validated based on high performance liquid chromatography tandem mass spectrometry (LC-MS/MS. Sample preparation involved protein precipitation followed by one to one dilution with water. The analyte, efavirenz was separated by high performance liquid chromatography and detected with tandem mass spectrometry in negative ionization mode with multiple reaction monitoring. Efavirenz and ¹³C₆-efavirenz (Internal Standard, respectively, were detected via the following MRM transitions: m/z 314.20243.90 and m/z 320.20249.90. A gradient program was used to elute the analytes using 0.1% formic acid in water and 0.1% formic acid in acetonitrile as mobile phase solvents, at a flow-rate of 0.3 mL/min. The total run time was 5 min and the retention times for the internal standard (¹³C₆-efavirenz and efavirenz was approximately 2.6 min. The calibration curves showed linearity (coefficient of regression, r>0.99 over the concentration range of 1.0-2,500 ng/mL. The intraday precision based on the standard deviation of replicates of lower limit of quantification (LLOQ was 9.24% and for quality control (QC samples ranged from 2.41% to 6.42% and with accuracy from 112% and 100-111% for LLOQ and QC samples. The inter day precision was 12.3% and 3.03-9.18% for LLOQ and quality controls samples, and the accuracy was 108% and 95.2-108% for LLOQ and QC samples. Stability studies showed that efavirenz was stable during the expected conditions for sample preparation and storage. The lower limit of quantification for efavirenz was 1 ng/mL. The analytical method showed excellent sensitivity, precision, and accuracy. This method is robust and is being successfully applied for therapeutic drug monitoring and pharmacokinetic studies in HIV-infected patients.

Technical note: development and validation of a method using ultra performance liquid chromatography coupled with tandem mass spectrometry for determination of vitamin B12 concentrations in milk and dairy products.

Science.gov (United States)

Zironi, E; Gazzotti, T; Barbarossa, A; Devicienti, C; Scardilli, M; Pagliuca, G

2013-05-01

A method using ultra performance liquid chromatography coupled with tandem mass spectrometry was developed to measure cobalamins in naturally enriched raw milk and to evaluate their fate during thermal treatments and along the process of cheese making. After addition of methotrexate as internal standard, samples were submitted to heat treatment in the presence of cyanide, which converts all the less-stable cobalamins into cyanocobalamin; then, purification was performed by a solid-phase extraction step. Reverse-phase ultra performance liquid chromatography separation coupled with tandem mass spectrometry provided a fast and reliable determination. Mass spectrometric analysis was carried out in multiple reaction monitoring mode. The monitored transitions were m/z 678.36 → 147.10 and 678.36 → 359.30 for vitamin B12 and m/z 455.22 → 175.13 and 455.22 → 308.22 for methotrexate (internal standard). The limit of quantification was 2 ng/g. The method showed good linearity from 2 to 20 ng/g (R(2) ≥ 0.98) and intra- and interday precisions were always less than 19%. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Validation and assessment of matrix effect and uncertainty of a gas chromatography coupled to mass spectrometry method for pesticides in papaya and avocado samples

Directory of Open Access Journals (Sweden)

Norma Susana Pano-Farias

2017-07-01

Full Text Available In this paper a method of using the “quick, easy, cheap, effective, rugged, and safe” (QuEChERS extraction and gas chromatography coupled to mass spectrometry detection (GC–MS was developed for the analysis of five frequently applied pesticides in papaya and avocado. The selected pesticides, ametryn, atrazine, carbaryl, carbofuran, and methyl parathion, represent the most commonly used classes (carbamates, organophosphorous, and triazines. Optimum separation achieved the analysis of all pesticides in 0.99. The limits of detection (LOD and quantification (LOQ in papaya ranged from 0.03 mg/kg to 0.35 mg/kg and from 0.06 mg/kg to 0.75 mg/kg, respectively. Meanwhile for avocado, LOD values varied from 0.14 mg/kg to 0.28 mg/kg and LOQ values ranged from 0.22 mg/kg to 0.40 mg/kg. Recoveries obtained for each pesticide in both matrices ranged between 60.6% and 104.3%. The expanded uncertainty of the method was < 26% for all the pesticides in both fruits. Finally, the method was applied to other fruits.

Extraction and analysis of intact glucosinolates--a validated pressurized liquid extraction/liquid chromatography-mass spectrometry protocol for Isatis tinctoria, and qualitative analysis of other cruciferous plants.

Science.gov (United States)

Mohn, Tobias; Cutting, Brian; Ernst, Beat; Hamburger, Matthias

2007-09-28

Glucosinolates have attracted significant interest due to the chemopreventive properties of some of their transformation products. Numerous protocols for the extraction and analysis of glucosinolates have been published, but limited effort has been devoted to optimize and validate crucial extraction parameters and sample preparation steps. We carried out a systematic optimization and validation of a quantitative assay for the direct analysis of intact glucosinolates in Isatis tinctoria leaves (woad, Brassicaceae). Various parameters such as solvent composition, particle size, temperature, and number of required extraction steps were optimized using pressurized liquid extraction (PLE). We observed thermal degradation of glucosinolates at temperatures above 50 degrees C, and loss of >60% within 10min at 100 degrees C, but no enzymatic degradation in the leaf samples at ambient temperature. Excellent peak shape and resolution was obtained by reversed-phase chromatography on a Phenomenex Aqua column using 10mM ammonium formate as ion-pair reagent. Detection was carried out by electrospray ionisation mass spectrometry in the negative ion mode. Analysis of cruciferous vegetables and spices such as broccoli (Brassica oleracea L. var. italica), garden cress (Lepidium sativum L.) and black mustard (Sinapis nigra L.) demonstrated the general applicability of the method.

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

A Stability-Indicating HPLC-DAD Method for Determination of Stiripentol: Development, Validation, Kinetics, Structure Elucidation and Application to Commercial Dosage Form

Directory of Open Access Journals (Sweden)

Hany W. Darwish

2014-01-01

Full Text Available A rapid, simple, sensitive, and accurate isocratic reversed-phase stability-indicating high performance liquid chromatography method has been developed and validated for the determination of stiripentol and its degradation product in its bulk form and pharmaceutical dosage form. Chromatographic separation was achieved on a Symmetry C18 column and quantification was achieved using photodiode array detector (DAD. The method was validated in accordance with the ICH requirements showing specificity, linearity (r2=0.9996, range of 1–25 μg/mL, precision (relative standard deviation lower than 2%, accuracy (mean recovery 100.08±1.73, limits of detection and quantitation (LOD = 0.024 and LOQ = 0.081 μg/mL, and robustness. Stiripentol was subjected to various stress conditions and it has shown marked stability under alkaline hydrolytic stress conditions, thermal, oxidative, and photolytic conditions. Stiripentol degraded only under acidic conditions, forming a single degradation product which was well resolved from the pure drug with significantly different retention time values. This degradation product was characterized by 1H-NMR and 13C-NMR spectroscopy as well as ion trap mass spectrometry. The results demonstrated that the method would have a great value when applied in quality control and stability studies for stiripentol.

Development of Extraction Methods for the Analysis of Perfluorinated Compounds in Leather with High Performance Liquid Chromatography Tandem Mass Spectrometry

Science.gov (United States)

Zhang, Yan; Wang, Youchao; Tang, Chuanjiang; Nie, Jingmei; Xu, Chengtao

2018-01-01

Perfluorinated compounds (PFCs), used to provide water, oil, grease, heat and stain repellency to a range of textile and other products, have been found to be persistent in the environment and are associated with adverse effects on humans and wildlife. This study presents the development and validation of an analytical method to determine the simultaneous presence of eleven PFCs in leather using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The perfluorinated compounds were primarily extracted from the samples by a liquid extraction procedure by ultrasonic, in which the parameters were optimized. Then the solid-phase extraction (SPE) is the most important advantages of the developed methodology. The sample volume and elution conditions were optimized by means of an experimental design. The proposed method was applied to determine the PFCs in leather, where the detection limits of the eleven compounds were 0.09-0.96 ng/L, and the recoveries of all compounds spiked at 5 ng/L concentration level were in the range of 65-96%, with a better RSD lower than 19% (n = 7).

Handbook on Mobile Gamma-ray Spectrometry

DEFF Research Database (Denmark)

Aage, Helle Karina; Korsbech, Uffe C C

2003-01-01

Basic physics and mathematics for Airborne and Car-borne Gamma-ray Spectrometry supplemented with practical examples and methods for advanced data processing......Basic physics and mathematics for Airborne and Car-borne Gamma-ray Spectrometry supplemented with practical examples and methods for advanced data processing...

Application of a rapid and sensitive liquid chromatography-tandem mass spectrometry method for determination of bumetanide in human plasma for a bioequivalence study.

Science.gov (United States)

Patel, Dinesh S; Sharma, Naveen; Patel, Mukesh C; Patel, Bhavin N; Shrivastav, Pranav S; Sanyal, Mallika

2012-07-01

A rapid, selective and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay has been proposed for the determination of bumetanide in human plasma using tamsulosin as internal standard (IS). The analyte and IS were extracted from 200 μL of human plasma via solid phase extraction and the chromatographic separation was achieved on Peerless Basic C18 (100 mm × 4.6 mm, 3 μm) column under isocratic conditions. Detection of bumetanide and IS was done by tandem mass spectrometry, operating in positive ionization and multiple reaction monitoring (MRM) acquisition mode. The protonated precursor to product ion transitions monitored for bumetanide and IS were m/z 365.2→240.2 and 409.2→228.2 respectively. The method was fully validated as per the US FDA guidelines. The limit of detection and lower limit of quantitation of the method were 0.03 and 0.30 ng/mL respectively with a linear dynamic range of 0.30-200.0 ng/mL for bumetanide. The intra-batch and inter-batch precision (% CV) was ≤6.9% while the mean extraction recovery was >90% across quality control levels. The method is selective in presence of four diuretic drugs and some commonly used medications by healthy volunteers. It was successfully applied to a bioequivalence study of 2mg bumetanide tablet formulation in 10 healthy Indian male subjects under fasting condition. The reproducibility in the measurement of study data was demonstrated by reanalysis of 42 incurred samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Multi-residue analysis method for analysis of pharmaceuticals using liquid chromatography-time of flight/mass spectrometry (LC-TOF/MS) in water sample

Science.gov (United States)

Al-Qaim, Fouad Fadhil; Abdullah, Md Pauzi; Othman, Mohamed Rozali

2013-11-01

In this work, a developed method using solid - phase extraction (SPE) followed by liquid chromatography - time of flight mass spectrometry (LC-ESI-TOF/MS) was developed and validated for quantification and confirmation of eleven pharmaceuticals with different therapeutic classes in water samples, Malaysia. These compounds are caffeine (CAF), prazosin (PRZ), enalapril (ENL), carbamazepine (CBZ), nifedipine (NFD), levonorgestrel (LNG), simvastatin (SMV), hydrochlorothiazide (HYD), gliclazide (GLIC), diclofenac-Na (DIC-Na) and mefenamic acid (MEF). LC was performed on a Dionex Ultimate 3000/LC 09115047 (USA) system. Chromatography was performed on a Thermo Scientific C18 (250 mm × 2.1 mm, i.d.: 5μm) column. Several parameters were optimised such as; mobile phase, gradient elution, collision energy and solvent elution for extraction of compounds from water. The recoveries obtained ranged from 30-148 % in river water. Five pharmaceutical compounds were detected in the surface water samples: caffeine, prazosin, enalpril, diclofenac-Na and mefenamic acid. The developed method is precise and accepted recoveries were got. In addition, this method is suitable to identify and quantify trace concentrations of pharmaceuticals in surface water.

High-throughput method for macrolides and lincosamides antibiotics residues analysis in milk and muscle using a simple liquid-liquid extraction technique and liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-MS/MS).

Science.gov (United States)

Jank, Louise; Martins, Magda Targa; Arsand, Juliana Bazzan; Campos Motta, Tanara Magalhães; Hoff, Rodrigo Barcellos; Barreto, Fabiano; Pizzolato, Tânia Mara

2015-11-01

A fast and simple method for residue analysis of the antibiotics classes of macrolides (erythromycin, azithromycin, tylosin, tilmicosin and spiramycin) and lincosamides (lincomycin and clindamycin) was developed and validated for cattle, swine and chicken muscle and for bovine milk. Sample preparation consists in a liquid-liquid extraction (LLE) with acetonitrile, followed by liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-ESI-MS/MS), without the need of any additional clean-up steps. Chromatographic separation was achieved using a C18 column and a mobile phase composed by acidified acetonitrile and water. The method was fully validated according the criteria of the Commission Decision 2002/657/EC. Validation parameters such as limit of detection, limit of quantification, linearity, accuracy, repeatability, specificity, reproducibility, decision limit (CCα) and detection capability (CCβ) were evaluated. All calculated values met the established criteria. Reproducibility values, expressed as coefficient of variation, were all lower than 19.1%. Recoveries range from 60% to 107%. Limits of detection were from 5 to 25 µg kg(-1).The present method is able to be applied in routine analysis, with adequate time of analysis, low cost and a simple sample preparation protocol. Copyright © 2015. Published by Elsevier B.V.

Ultra-high-performance liquid chromatography-tandem mass spectrometry measurement of climbazole deposition from hair care products onto artificial skin and human scalp

NARCIS (Netherlands)

Chen, G.; Hoptroff, M.; Fei, X.; Su, Y.; Janssen, H.-G.

2013-01-01

A sensitive and specific ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated for the measurement of climbazole deposition from hair care products onto artificial skin and human scalp. Deuterated climbazole was used as the internal

Burn-up determination of irradiated uranium oxide by means of direct gama spectrometry and by radiochemical method

International Nuclear Information System (INIS)

Cunha, I.I.L.; Nastasi, M.J.C.; Lima, F.W.

1981-09-01

The burn-up of thermal neutrons irradiated U 3 O 8 (natural uranium) samples has been determined by using both direct gamma spectrometry and radiochemical methods and the results obtained were compared. The fission products 144 Ce, 103 Ru, 106 Ru, 137 Cs and 95 Zr were chosen as burn-up monitors. In order to isolate the radioisotopes chosen as monitors, a radiochemical separation procedure has been established, in which the solvent extraction technique was used to separate cerium, cesium and ruthenium one from the other and all of them from uranium. The separation between zirconium and niobium and of both elements from the other radioisotopes and uranium was accomplished by means of adsorption on a silica-gel column, followed by selective elution of zirconium and of niobium. When use was made of the direct gamma-ray spectrometry method, the radioactivity of each nuclide of interest was measured in presence of all others. For this purpose use was made of gamma-ray spectrometry and of a Ge-Li detector. Comparison of burn-up values obtained by both methods was made by means of Student's 't' test, and this showed that results obtained in each case are statistically equal. (Author) [pt

Simultaneous quantification of acetaminophen and five acetaminophen metabolites in human plasma and urine by high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry: Method validation and application to a neonatal pharmacokinetic study.

Science.gov (United States)

Cook, Sarah F; King, Amber D; van den Anker, John N; Wilkins, Diana G

2015-12-15

Drug metabolism plays a key role in acetaminophen (paracetamol)-induced hepatotoxicity, and quantification of acetaminophen metabolites provides critical information about factors influencing susceptibility to acetaminophen-induced hepatotoxicity in clinical and experimental settings. The aims of this study were to develop, validate, and apply high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) methods for simultaneous quantification of acetaminophen, acetaminophen-glucuronide, acetaminophen-sulfate, acetaminophen-glutathione, acetaminophen-cysteine, and acetaminophen-N-acetylcysteine in small volumes of human plasma and urine. In the reported procedures, acetaminophen-d4 and acetaminophen-d3-sulfate were utilized as internal standards (IS). Analytes and IS were recovered from human plasma (10μL) by protein precipitation with acetonitrile. Human urine (10μL) was prepared by fortification with IS followed only by sample dilution. Calibration concentration ranges were tailored to literature values for each analyte in each biological matrix. Prepared samples from plasma and urine were analyzed under the same HPLC-ESI-MS/MS conditions, and chromatographic separation was achieved through use of an Agilent Poroshell 120 EC-C18 column with a 20-min run time per injected sample. The analytes could be accurately and precisely quantified over 2.0-3.5 orders of magnitude. Across both matrices, mean intra- and inter-assay accuracies ranged from 85% to 112%, and intra- and inter-assay imprecision did not exceed 15%. Validation experiments included tests for specificity, recovery and ionization efficiency, inter-individual variability in matrix effects, stock solution stability, and sample stability under a variety of storage and handling conditions (room temperature, freezer, freeze-thaw, and post-preparative). The utility and suitability of the reported procedures were illustrated by analysis of pharmacokinetic samples

SPE HG-AAS method for the determination of inorganic arsenic in rice—results from method validation studies and a survey on rice products

DEFF Research Database (Denmark)

Rasmussen, Rie Romme; Qian, Yiting; Sloth, Jens Jørgen

2013-01-01

spectrometry (HG-AAS) detection. This approach was earlier developed for seafood samples (Rasmussen et al., Anal Bioanal Chem 403:2825–2834, 2012) and has in the present work been tailored for rice products and further optimised for a higher sample throughput and a lower detection limit. Water bath heating (90...... °C, 60 min) of samples with dilute HNO3 and H2O2 solubilised and oxidised all iAs to arsenate (AsV). Loading of buffered sample extracts (pH 6 ± 1) followed by selective elution of arsenate from a strong anion exchange SPE cartridge enabled the selective iAs quantification by HG-AAS, measuring total...... arsenic (As) in the SPE eluate. The in-house validation gave mean recoveries of 101–106 % for spiked rice samples and in two reference samples. The limit of detection was 0.02 mg kg−1, and repeatability and intra-laboratory reproducibility were less than 6 and 9 %, respectively. The SPE HG-AAS method...

Volatile composition of Merlot red wine and its contribution to the aroma: optimization and validation of analytical method.

Science.gov (United States)

Arcari, Stefany Grützmann; Caliari, Vinicius; Sganzerla, Marla; Godoy, Helena Teixeira

2017-11-01

A methodology for the determination of volatile compounds in red wine using headspace solid phase microextraction (HS-SPME) combined with gas chromatography-ion trap/ mass spectrometry (GC-IT/MS) and flame ionization detector (GC -FID) was developed, validated and applied to a sample of Brazilian red wine. The optimization strategy was conducted using the Plackett-Burman design for variable selection and central composite rotational design (CCRD). The response surface methodology showed that the performance of the extraction of the volatile compounds using divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber is improved with no sample dilution, the addition of 30% NaCl, applying an extraction temperature of 56°C and extraction time of 55min. The qualitative method allowed the extraction and identification of 60 volatile compounds in the sample studied, notably the classes of esters, alcohols, and fatty acids. Furthermore, the method was successfully validated for the quantification of 55 volatile compounds of importance in wines and applied to twelve samples of Merlot red wine from South of Brazil. The calculation of the odor activity value (OAV) showed the most important components of the samples aroma. Ethyl isovalerate, ethyl hexanoate, 1-hexanol, octanoic acid and ethyl cinnamate had the greatest contribution to the aroma of the wines analyzed, which is predominantly fruity with the presence of herbal and fatty odors. Copyright © 2017 Elsevier B.V. All rights reserved.

Innovative method for carbon dioxide determination in human postmortem cardiac gas samples using headspace-gas chromatography–mass spectrometry and stable labeled isotope as internal standard

International Nuclear Information System (INIS)

Varlet, V.; Smith, F.; Froidmont, S. de; Dominguez, A.; Rinaldi, A.; Augsburger, M.; Mangin, P.; Grabherr, S.

2013-01-01

Graphical abstract: -- Highlights: •We developed a method for CO 2 analysis in cardiac samples and quantification by 13 CO 2 . •This method was fully validated by accuracy profile. •We have applied this method to perform CO 2 precise quantification for forensic applications. •Context of the death could be documented following CO 2 concentrations. -- Abstract: A novel approach to measure carbon dioxide (CO 2 ) in gaseous samples, based on a precise and accurate quantification by 13 CO 2 internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography–mass spectrometry (HS-GC–MS) method applicable in the routine determination of CO 2 . The main drawback of the GC methods discussed in the literature for CO 2 measurement is the lack of a specific internal standard necessary to perform quantification. CO 2 measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ( 13 CO 2 ) on the basis of the stoichiometric formation of CO 2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH 13 CO 3 ). This method allows a precise measurement of CO 2 concentration and was validated on various human postmortem gas samples in order to study its efficiency

A four dimensional separation method based on continuous heart-cutting gas chromatography with ion mobility and high resolution mass spectrometry.

Science.gov (United States)

Lipok, Christian; Hippler, Jörg; Schmitz, Oliver J

2018-02-09

A two-dimensional GC (2D-GC) method was developed and coupled to an ion mobility-high resolution mass spectrometer, which enables the separation of complex samples in four dimensions (2D-GC, ion mobilility spectrometry and mass spectrometry). This approach works as a continuous multiheart-cutting GC-system (GC+GC), using a long modulation time of 20s, which allows the complete transfer of most of the first dimension peaks to the second dimension column without fractionation, in comparison to comprehensive two-dimensional gas chromatography (GCxGC). Hence, each compound delivers only one peak in the second dimension, which simplifies the data handling even when ion mobility spectrometry as a third and mass spectrometry as a fourth dimension are introduced. The analysis of a plant extract from Calendula officinales shows the separation power of this four dimensional separation method. The introduction of ion mobility spectrometry provides an additional separation dimension and allows to determine collision cross sections (CCS) of the analytes as a further physicochemical constant supporting the identification. A CCS database with more than 800 standard substances including drug-like compounds and pesticides was used for CCS data base search in this work. Copyright © 2017 Elsevier B.V. All rights reserved.

Liquid chromatography/tandem mass spectrometry method for quantitative estimation of solutol HS15 and its applications

Directory of Open Access Journals (Sweden)

V. Vijaya Bhaskar

2015-04-01

Full Text Available A rapid, sensitive and selective pseudoMRM (pMRM-based method for the determination of solutol HS15 (SHS15 in rat plasma was developed using liquid chromatography/tandem mass spectrometry (LC–MS/MS. The most abundant ions corresponding to SHS15 free polyethyleneglycol (PEG oligomers at m/z 481, 525, 569, 613, 657, 701, 745, 789, 833, 877, 921 and 965 were selected for pMRM in electrospray mode of ionization. Purity of the lipophilic and hydrophilic components of SHS15 was estimated using evaporative light scattering detector (ELSD. Plasma concentrations of SHS15 were measured after oral administration at 2.50 g/kg dose and intravenous administration at 1.00 g/kg dose in male Sprague Dawley rats. SHS15 has poor oral bioavailability of 13.74% in rats. Differences in pharmacokinetics of oligomers were studied. A novel proposal was conveyed to the scientific community, where formulation excipient could be analyzed as a qualifier in the analysis of new chemical entities (NCEs to address the spiky plasma concentration profiles. Keywords: SHS15, LC–MS/MS, Spiky profiles, Validation

A rapid liquid chromatography tandem mass spectrometry-based method for measuring propranolol on dried blood spots.

Science.gov (United States)

Della Bona, Maria Luisa; Malvagia, Sabrina; Villanelli, Fabio; Giocaliere, Elisa; Ombrone, Daniela; Funghini, Silvia; Filippi, Luca; Cavallaro, Giacomo; Bagnoli, Paola; Guerrini, Renzo; la Marca, Giancarlo

2013-05-05

Propranolol, a non-selective beta blocker drug, is used in young infants and newborns for treating several heart diseases; its pharmacokinetics has been extensively evaluated in adult patients using extrapolation to treat pediatric population. The purpose of the present study was to develop and validate a method to measure propranolol levels in dried blood spots. The analysis was performed by using liquid chromatography/tandem mass spectrometry operating in multiple reaction monitoring mode. The calibration curve in matrix was linear in the concentration range of 2.5-200 μg/L with correlation coefficient r=0.9996. Intra-day and inter-day precisions and biases were less than 8.0% (n=10) and 11.5% (n=10) respectively. The recoveries ranged from 94 to 100% and the matrix effect did not result in a severe signal suppression. Propranolol on dried blood spot showed a good stability at three different temperatures for one month. This paper describes a micromethod for measuring propranolol levels on dried blood spot, which determines a great advantage in neonates or young infants during pharmacokinetic studies because of less invasive sampling and small blood volume required. Copyright © 2013 Elsevier B.V. All rights reserved.

New developments in radiometrics and mass spectrometry methods for radionuclide analysis of environmental samples

International Nuclear Information System (INIS)

Povinec, P.P.; LaRosa, J.J.; Lee, S.H.; Wyse, E.

2002-01-01

The radionuclide levels observed at present in the environment are very low, therefore high sensitive analytical systems are required for carrying out environmental investigations. One very important recent development in analytical techniques for low-level activity measurements is the production of large volume HPGe detectors (up to 200% relative efficiency to 75 mm diameter x 75 mm long NaI (Tl) crystals). Their high efficiency and excellent energy resolution permit the analyses of various gamma-emitters in composite samples selectively and very often non-destructively (e.g. in sea sediments). However, this technique is restricted to gamma-emitters only (e.g. for 7 Be, 40 K, 54 Mn, 60 Co, 137 Cs, 210 Pb, etc.). Other radionuclides frequently found in the marine environment are the pure beta-emitters, like 3 H, 14 C, 32 Si, 32 P, 90 Sr, 241 Pu, etc., where mainly liquid scintillation counting has made great improvements in recent years. However, for some of these radionuclides mass spectrometry methods represent a real breakthrough in low-level counting, e.g. 3 He in-growth mass spectrometry for 3 H, or accelerator mass spectrometry (AMS) for 14 C

International Harmonization and Cooperation in the Validation of Alternative Methods.

Science.gov (United States)

Barroso, João; Ahn, Il Young; Caldeira, Cristiane; Carmichael, Paul L; Casey, Warren; Coecke, Sandra; Curren, Rodger; Desprez, Bertrand; Eskes, Chantra; Griesinger, Claudius; Guo, Jiabin; Hill, Erin; Roi, Annett Janusch; Kojima, Hajime; Li, Jin; Lim, Chae Hyung; Moura, Wlamir; Nishikawa, Akiyoshi; Park, HyeKyung; Peng, Shuangqing; Presgrave, Octavio; Singer, Tim; Sohn, Soo Jung; Westmoreland, Carl; Whelan, Maurice; Yang, Xingfen; Yang, Ying; Zuang, Valérie

The development and validation of scientific alternatives to animal testing is important not only from an ethical perspective (implementation of 3Rs), but also to improve safety assessment decision making with the use of mechanistic information of higher relevance to humans. To be effective in these efforts, it is however imperative that validation centres, industry, regulatory bodies, academia and other interested parties ensure a strong international cooperation, cross-sector collaboration and intense communication in the design, execution, and peer review of validation studies. Such an approach is critical to achieve harmonized and more transparent approaches to method validation, peer-review and recommendation, which will ultimately expedite the international acceptance of valid alternative methods or strategies by regulatory authorities and their implementation and use by stakeholders. It also allows achieving greater efficiency and effectiveness by avoiding duplication of effort and leveraging limited resources. In view of achieving these goals, the International Cooperation on Alternative Test Methods (ICATM) was established in 2009 by validation centres from Europe, USA, Canada and Japan. ICATM was later joined by Korea in 2011 and currently also counts with Brazil and China as observers. This chapter describes the existing differences across world regions and major efforts carried out for achieving consistent international cooperation and harmonization in the validation and adoption of alternative approaches to animal testing.

Development and validation of mass spectrometry-based methods for food quality and food safety assessment

OpenAIRE

Bignardi, Chiara

2014-01-01

In this PhD thesis, analytical chemistry plays a significant role in the assessment of food quality and safety; in particular, three different topics have been addressed to and they are presented into three chapters in which different analytical methodologies have been developed, validated and applied successfully in different topics of food chemistry research. The first chapter is focused on an innovative analytical technique, capillary zone electrophoresis coupled to tandem mass spectrom...

Development and validation of an LC-MS/MS method for the determination of adapalene in pharmaceutical forms for skin application

Directory of Open Access Journals (Sweden)

Dobričić Vladimir

2016-01-01

Full Text Available Development and validation of a liquid chromatography - tandem mass spectrometry (LC-MS/MS method for the determination of adapalene in pharmaceutical forms for skin application were presented. The MS/MS analysis of adapalene was performed by use of three mobile phases, consisted of acetonitrile and (a 0.1 % formic acid, (b 0.1 % trifluoroacetic acid and (c 20 mM ammonium acetate. The strongest signals of parent ion and dominant product ion were obtained in negative mode by use of the mobile phase (c. Validation of this method was performed according to the ICH guidelines. Small variations of selected chromatographic parameters (concentration of ammonium acetate, mobile phase composition, column temperature and flow rate did not affect qualitative and quantitative system responses significantly, which proved method’s robustness. The method is specific for the determination of adapalene. Linearity was proved in the concentration range 6.7 - 700.0 ng mL-1 (r = 0.9990, with limits of detection and quantification 2.0 ng mL-1 and 6.7 ng mL-1, respectively. Accuracy was confirmed by calculated recoveries (98.4 % - 101.5 %. Precision was tested at three levels: injection repeatability, analysis repeatability and intermediate precision. Calculated relative standard deviations were less than 1, 2 and 3 %, respectively. [Projekat Ministartsva nauke Republike Srbije, br. OI172041 i br. TR34031

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--part 1: instrument validation of the DELTAplusXP IRMS for bulk nitrogen isotope ratio measurements.

Science.gov (United States)

Benson, Sarah J; Lennard, Christopher J; Hill, David M; Maynard, Philip; Roux, Claude

2010-01-01

A significant amount of research has been conducted into the use of stable isotopes to assist in determining the origin of various materials. The research conducted in the forensic field shows the potential of isotope ratio mass spectrometry (IRMS) to provide a level of discrimination not achievable utilizing traditional forensic techniques. Despite the research there have been few, if any, publications addressing the validation and measurement uncertainty of the technique for forensic applications. This study, the first in a planned series, presents validation data for the measurement of bulk nitrogen isotope ratios in ammonium nitrate (AN) using the DELTA(plus)XP (Thermo Finnigan) IRMS instrument equipped with a ConFlo III interface and FlashEA 1112 elemental analyzer (EA). Appropriate laboratory standards, analytical methods and correction calculations were developed and evaluated. A validation protocol was developed in line with the guidelines provided by the National Association of Testing Authorities, Australia (NATA). Performance characteristics including: accuracy, precision/repeatability, reproducibility/ruggedness, robustness, linear range, and measurement uncertainty were evaluated for the measurement of nitrogen isotope ratios in AN. AN (99.5%) and ammonium thiocyanate (99.99+%) were determined to be the most suitable laboratory standards and were calibrated against international standards (certified reference materials). All performance characteristics were within an acceptable range when potential uncertainties, including the manufacturer's uncertainty of the technique and standards, were taken into account. The experiments described in this article could be used as a model for validation of other instruments for similar purposes. Later studies in this series will address the more general issue of demonstrating that the IRMS technique is scientifically sound and fit-for-purpose in the forensic explosives analysis field.

The Method of Manufactured Universes for validating uncertainty quantification methods

KAUST Repository

Stripling, H.F.

2011-09-01

The Method of Manufactured Universes is presented as a validation framework for uncertainty quantification (UQ) methodologies and as a tool for exploring the effects of statistical and modeling assumptions embedded in these methods. The framework calls for a manufactured reality from which experimental data are created (possibly with experimental error), an imperfect model (with uncertain inputs) from which simulation results are created (possibly with numerical error), the application of a system for quantifying uncertainties in model predictions, and an assessment of how accurately those uncertainties are quantified. The application presented in this paper manufactures a particle-transport universe, models it using diffusion theory with uncertain material parameters, and applies both Gaussian process and Bayesian MARS algorithms to make quantitative predictions about new experiments within the manufactured reality. The results of this preliminary study indicate that, even in a simple problem, the improper application of a specific UQ method or unrealized effects of a modeling assumption may produce inaccurate predictions. We conclude that the validation framework presented in this paper is a powerful and flexible tool for the investigation and understanding of UQ methodologies. © 2011 Elsevier Ltd. All rights reserved.

Development and Validation of Analytical Method for Losartan ...

African Journals Online (AJOL)

Development and Validation of Analytical Method for Losartan-Copper Complex Using UV-Vis Spectrophotometry. ... Tropical Journal of Pharmaceutical Research ... Purpose: To develop a new spectrophotometric method for the analysis of losartan potassium in pharmaceutical formulations by making its complex with ...

A novel liquid chromatography/tandem mass spectrometry (LC-MS/MS) based bioanalytical method for quantification of ethyl esters of Eicosapentaenoic acid (EPA) and Docosahexaenoic acid (DHA) and its application in pharmacokinetic study.

Science.gov (United States)

Viswanathan, Sekarbabu; Verma, P R P; Ganesan, Muniyandithevar; Manivannan, Jeganathan

2017-07-15

Omega-3 fatty acids are clinically useful and the two marine omega-3 fatty acids eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are prevalent in fish and fish oils. Omega-3 fatty acid formulations should undergo a rigorous regulatory step in order to obtain United States Food and Drug Administration (USFDA) approval as prescription drug. In connection with that, despite quantifying EPA and DHA fatty acids, there is a need for quantifying the level of ethyl esters of them in biological samples. In this study, we make use of reverse phase high performance liquid chromatography coupled with mass spectrometry (RP-HPLC-MS)technique for the method development. Here, we have developed a novel multiple reaction monitoring method along with optimized parameters for quantification of EPA and DHA as ethyl esters. Additionally, we attempted to validate the bio-analytical method by conducting the sensitivity, selectivity, precision accuracy batch, carryover test and matrix stability experiments. Furthermore, we also implemented our validated method for evaluation of pharmacokinetics of omega fatty acid ethyl ester formulations. Copyright © 2017 Elsevier B.V. All rights reserved.

OWL-based reasoning methods for validating archetypes.

Science.gov (United States)

Menárguez-Tortosa, Marcos; Fernández-Breis, Jesualdo Tomás

2013-04-01

Some modern Electronic Healthcare Record (EHR) architectures and standards are based on the dual model-based architecture, which defines two conceptual levels: reference model and archetype model. Such architectures represent EHR domain knowledge by means of archetypes, which are considered by many researchers to play a fundamental role for the achievement of semantic interoperability in healthcare. Consequently, formal methods for validating archetypes are necessary. In recent years, there has been an increasing interest in exploring how semantic web technologies in general, and ontologies in particular, can facilitate the representation and management of archetypes, including binding to terminologies, but no solution based on such technologies has been provided to date to validate archetypes. Our approach represents archetypes by means of OWL ontologies. This permits to combine the two levels of the dual model-based architecture in one modeling framework which can also integrate terminologies available in OWL format. The validation method consists of reasoning on those ontologies to find modeling errors in archetypes: incorrect restrictions over the reference model, non-conformant archetype specializations and inconsistent terminological bindings. The archetypes available in the repositories supported by the openEHR Foundation and the NHS Connecting for Health Program, which are the two largest publicly available ones, have been analyzed with our validation method. For such purpose, we have implemented a software tool called Archeck. Our results show that around 1/5 of archetype specializations contain modeling errors, the most common mistakes being related to coded terms and terminological bindings. The analysis of each repository reveals that different patterns of errors are found in both repositories. This result reinforces the need for making serious efforts in improving archetype design processes. Copyright © 2012 Elsevier Inc. All rights reserved.

Development of a validated HPLC method for the quantitative determination of trelagliptin succinate and its related substances in pharmaceutical dosage forms.

Science.gov (United States)

Luo, Zhiqiang; Chen, Xinjing; Wang, Guopeng; Du, Zhibo; Ma, Xiaoyun; Wang, Hao; Yu, Guohua; Liu, Aoxue; Li, Mengwei; Peng, Wei; Liu, Yang

2018-01-01

Trelagliptin succinate is a dipeptidyl peptidase IV (DPP-4) inhibitor which is used as a new long-acting drug for once-weekly treatment of type 2 diabetes mellitus (DM). In the present study, a rapid, sensitive and accurate high-performance liquid chromatography (HPLC) method was developed and validated for separation and determination of trelagliptin succinate and its eight potential process-related impurities. The chromatographic separation was achieved on a Waters Xselect CSH™ C 18 (250mm×4.6mm, 5.0μm) column. The mobile phases comprised of 0.05% trifluoroacetic acid in water as well as acetonitrile containing 0.05% trifluoroacetic acid. The compounds of interest were monitored at 224nm and 275nm. The stability-indicating capability of this method was evaluated by performing stress test studies. Trelagliptin succinate was found to degrade significantly in acid, base, oxidative and thermal stress conditions and only stable in photolytic degradation condition. The degradation products were well resolved from the main peak and its impurities. In addition, the major degradation impurities formed under acid, base, oxidative and thermal stress conditions were characterized by ultra-high-performance liquid chromatography coupled with linear ion trap-Orbitrap tandem mass spectrometry (UHPLC-LTQ-Orbitrap). The method was validated to fulfill International Conference on Harmonisation (ICH) requirements and this validation included specificity, linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, precision and robustness. The developed method in this study could be applied for routine quality control analysis of trelagliptin succinate tablets, since there is no official monograph. Copyright © 2017 Elsevier B.V. All rights reserved.

Development and validation of a gas chromatography-mass spectrometry assay for opiates and cocaine in human teeth.

Science.gov (United States)

Pellegrini, Manuela; Casá, Adriana; Marchei, Emilia; Pacifici, Roberta; Mayné, Ruth; Barbero, Vanessa; Garcia-Algar, Oscar; Pichini, Simona

2006-02-24

A procedure based on gas chromatography-mass spectrometry (GC-MS) is described for determination of opiates (6-monoacetylmorphine, morphine and codeine) and cocaine and metabolites (cocaine, benzoylecgonine and cocaethylene) in human teeth. After addition of nalorphine as internal standard, pulverized samples were incubated in HCl at 37 degrees C for 18 h. Then, after pH adjustment to 6, and the analytes were extracted with two volumes of 3 ml of chloroform/isopropanol (9:1). Chromatography was performed on a fused silica capillary column and analytes were determined in the selected-ion-monitoring (SIM) mode. The assay was validated in the range 7.5 (6.0 in case of codeine) to 500 ng/g with mean absolute recoveries ranged between 74.1 and 92.1% for the different analytes and precision and accuracy always better than 15%. The method was applied to the analysis of teeth from drug-addicts to assess past chronic consumption and verify self-reported declarations. In case of opiates, concentration range was 36.5-570.0 ng/g for 6-monoacetylmorphine, 8.7-154.8 ng/g for morphine and 7.9-127.9 ng/g for codeine. Cocaine concentration ranged between 5.6 and 57.2 ng/g with its principal metabolite benzoylecgonine varying from 12.6 to 81.7 ng/g and cocaethylene present in only one sample at 10 ng/g value. Teeth can be a promising non-invasive biological matrix in biomedical analysis for both clinical and forensic purposes.

Development and Validation of Improved Method for Fingerprint ...

African Journals Online (AJOL)

Purpose: To develop and validate an improved method by capillary zone electrophoresis with photodiode array detection for the fingerprint analysis of Ligusticum chuanxiong Hort. (Rhizoma Chuanxiong). Methods: The optimum high performance capillary electrophoresis (HPCE) conditions were 30 mM borax containing 5 ...

Multilaboratory Validation of First Action Method 2016.04 for Determination of Four Arsenic Species in Fruit Juice by High-Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry.

Science.gov (United States)

Kubachka, Kevin; Heitkemper, Douglas T; Conklin, Sean

2017-07-01

Before being designated AOAC First Action Official MethodSM 2016.04, the U.S. Food and Drug Administration's method, EAM 4.10 High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometric Determination of Four Arsenic Species in Fruit Juice, underwent both a single-laboratory validation and a multilaboratory validation (MLV) study. Three federal and five state regulatory laboratories participated in the MLV study, which is the primary focus of this manuscript. The method was validated for inorganic arsenic (iAs) measured as the sum of the two iAs species arsenite [As(III)] and arsenate [As(V)], dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) by analyses of 13 juice samples, including three apple juice, three apple juice concentrate, four grape juice, and three pear juice samples. In addition, two water Standard Reference Materials (SRMs) were analyzed. The method LODs and LOQs obtained among the eight laboratories were approximately 0.3 and 2 ng/g, respectively, for each of the analytes and were adequate for the intended purpose of the method. Each laboratory analyzed method blanks, fortified method blanks, reference materials, triplicate portions of each juice sample, and duplicate fortified juice samples (one for each matrix type) at three fortification levels. In general, repeatability and reproducibility of the method was ≤15% RSD for each species present at a concentration >LOQ. The average recovery of fortified analytes for all laboratories ranged from 98 to 104% iAs, DMA, and MMA for all four juice sample matrixes. The average iAs results for SRMs 1640a and 1643e agreed within the range of 96-98% of certified values for total arsenic.

Method validation for chemical composition determination by electron microprobe with wavelength dispersive spectrometer

Science.gov (United States)

Herrera-Basurto, R.; Mercader-Trejo, F.; Muñoz-Madrigal, N.; Juárez-García, J. M.; Rodriguez-López, A.; Manzano-Ramírez, A.

2016-07-01

The main goal of method validation is to demonstrate that the method is suitable for its intended purpose. One of the advantages of analytical method validation is translated into a level of confidence about the measurement results reported to satisfy a specific objective. Elemental composition determination by wavelength dispersive spectrometer (WDS) microanalysis has been used over extremely wide areas, mainly in the field of materials science, impurity determinations in geological, biological and food samples. However, little information is reported about the validation of the applied methods. Herein, results of the in-house method validation for elemental composition determination by WDS are shown. SRM 482, a binary alloy Cu-Au of different compositions, was used during the validation protocol following the recommendations for method validation proposed by Eurachem. This paper can be taken as a reference for the evaluation of the validation parameters more frequently requested to get the accreditation under the requirements of the ISO/IEC 17025 standard: selectivity, limit of detection, linear interval, sensitivity, precision, trueness and uncertainty. A model for uncertainty estimation was proposed including systematic and random errors. In addition, parameters evaluated during the validation process were also considered as part of the uncertainty model.

Development and validation of an SPE HG-AAS method for determination of inorganic arsenic in samples of marine origin

Energy Technology Data Exchange (ETDEWEB)

Rasmussen, Rie R.; Larsen, Erik H.; Sloth, Jens J. [Technical University of Denmark, National Food Institute, Division of Food Chemistry, Soeborg (Denmark); Hedegaard, Rikke V. [Technical University of Denmark, National Food Institute, Division of Food Chemistry, Soeborg (Denmark); University of Copenhagen, Faculty of Life Sciences, Department of Food Science, Frederiksberg (Denmark)

2012-07-15

The present paper describes a novel method for the quantitative determination of inorganic arsenic (iAs) in food and feed of marine origin. The samples were subjected to microwave-assisted extraction using diluted hydrochloric acid and hydrogen peroxide, which solubilised the analytes and oxidised arsenite (As{sup III}) to arsenate (As{sup V}). Subsequently, a pH buffering of the sample extract at pH 6 enabled selective elution of As{sup V} from a strong anion exchange solid-phase extraction (SPE) cartridge. Hydride generation atomic absorption spectrometry (HG-AAS) was applied to quantify the concentration of iAs (sum of As{sup III} and As{sup V}) as the total arsenic (As) in the SPE eluate. The results of the in-house validation showed that mean recoveries of 101-104% were achieved for samples spiked with iAs at 0.5, 1.0 and 1.5 mg.kg{sup -1}, respectively. The limit of detection was 0.08 mg kg{sup -1}, and the repeatability (RSD{sub r}) and intra-laboratory reproducibility (RSD{sub IR}) were less than 8% and 13%, respectively, for samples containing 0.2 to 1.5 mg kg{sup -1} iAs. The trueness of the SPE HG-AAS method was verified by confirming results obtained by parallel analysis using high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry. It was demonstrated that the two sets of results were not significantly different (P < 0.05). The SPE HG-AAS method was applied to 20 marine food and feed samples, and concentrations of up to 0.14 mg kg{sup -1} of iAs were detected. (orig.)

Development and validation of a spectroscopic method for the ...

African Journals Online (AJOL)

Development and validation of a spectroscopic method for the simultaneous analysis of ... advanced analytical methods such as high pressure liquid ..... equipment. DECLARATIONS ... high-performance liquid chromatography. J Chromatogr.

Method Comparison of Neutron Activation Analysis and Atomic Absorption Spectrometry for Determination of Zinc in Food Samples

International Nuclear Information System (INIS)

Endah Damastuti; Syukria Kurniawati; Natalia Adventini

2009-01-01

Zinc as a micro nutrient, has important roles in human metabolism system. It is required by the body in appropriate amount from food intake. Due to the very low concentration of Zinc in food, high selectivity and sensitivity analysis technique is required for the determination, such as Neutron Activation Analysis (NAA) and Atomic Absorption Spectrometry (AAS). In this experiment, both methods were compared in zinc analysis of food samples. The subject of this experiment is to examine of those methods conformity and improving the technique capability in zinc analysis in food sample. Those methods were validated by analyzing zinc in SRM NIST 1548a Typical Diet and were tested its accuracy and precision. The results of Zn concentration were 25.1 ± 2.14 mg/kg by NAA and 24.1 ± 1.40 mg/kg by AAS while the certificate value was 24.6 ± 1.80 mg/kg. Percentage of relative bias, %CV, μ-test score and HORRAT(Horwitz ratio) value given by NAA were 2%, 8.5%, 0.18 and 0.9 respectively, while %relative bias, %CV, μ-test score and HORRAT value given by AAS were 2%, 5.8 %, 0.20 and 0.6 respectively. The result obtained for Zn concentration in various food samples by NAA and AAS were varied from 13.7 – 29.3 mg/kg with mean value 19.8 mg/kg and 11.2 – 26.0 mg/kg with mean value 17.3 mg/kg (author)

Chiral liquid chromatography-mass spectrometry (LC-MS/MS) method development for the detection of salbutamol in urine samples.

Science.gov (United States)

Chan, Sue Hay; Lee, Warren; Asmawi, Mohd Zaini; Tan, Soo Choon

2016-07-01

A sequential solid-phase extraction (SPE) method was developed and validated using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for the detection and quantification of salbutamol enantiomers in porcine urine. Porcine urine samples were hydrolysed with β-glucuronidase/arylsulfatase from Helix pomatia and then subjected to a double solid-phase extraction (SPE) first using the Abs-Elut Nexus SPE and then followed by the Bond Elut Phenylboronic Acid (PBA) SPE. The salbutamol enantiomers were separated using the Astec CHIROBIOTIC™ T HPLC column (3.0mm×100mm; 5μm) maintained at 15°C with a 15min isocratic run at a flow rate of 0.4mL/min. The mobile phase constituted of 5mM ammonium formate in methanol. Salbutamol and salbutamol-tert-butyl-d9 (internal standard, IS) was monitored and quantified with the multiple reaction monitoring (MRM) mode. The method showed good linearity for the range of 0.1-10ng/mL with limit of quantification at 0.3ng/mL. Analysis of the QC samples showed intra- and inter-assay precisions to be less than 5.04%, and recovery ranging from 83.82 to 102.33%. Copyright © 2016 Elsevier B.V. All rights reserved.

Rapid determination of quetiapine in blood by gas chromatography-mass spectrometry. Application to post-mortem cases.

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López-Guarnido, Olga; Tabernero, María Jesús; Hernández, Antonio F; Rodrigo, Lourdes; Bermejo, Ana M

2014-10-01

A simple, fast and sensitive method for the determination of quetiapine in human blood has been developed and validated. The method involved a basic liquid-liquid extraction procedure and subsequent analysis by gas chromatography-mass spectrometry, previous derivatization with bis(trimethylsilyl)-trifluoro-acetamide and chorotrimethylsilane (99 : 1). The methods of validation included linearity with a correlation coefficient > 0.99 over the range 0.02-1 µg ml(-1), intra- and interday precision (always < 12%) and accuracy (mean relative error always < 12%) to meet the bioanalytical acceptance criteria. The limit of detection was 0.005 µg ml(-1). The procedure was further applied to post mortems from the Institute of Legal Medicine, University of Santiago de Compostela. Copyright © 2013 John Wiley & Sons, Ltd.

Bayesian risk-based decision method for model validation under uncertainty

International Nuclear Information System (INIS)

Jiang Xiaomo; Mahadevan, Sankaran

2007-01-01

This paper develops a decision-making methodology for computational model validation, considering the risk of using the current model, data support for the current model, and cost of acquiring new information to improve the model. A Bayesian decision theory-based method is developed for this purpose, using a likelihood ratio as the validation metric for model assessment. An expected risk or cost function is defined as a function of the decision costs, and the likelihood and prior of each hypothesis. The risk is minimized through correctly assigning experimental data to two decision regions based on the comparison of the likelihood ratio with a decision threshold. A Bayesian validation metric is derived based on the risk minimization criterion. Two types of validation tests are considered: pass/fail tests and system response value measurement tests. The methodology is illustrated for the validation of reliability prediction models in a tension bar and an engine blade subjected to high cycle fatigue. The proposed method can effectively integrate optimal experimental design into model validation to simultaneously reduce the cost and improve the accuracy of reliability model assessment

Comparison of the analytical methods used to determine natural and artificial radionuclides from environmental samples by gamma, alpha and beta spectrometry

DEFF Research Database (Denmark)

Pöllänen, Roy; Virtanen, Sinikka; Kämäräinen, Meerit

In CAMNAR, an extensive interlaboratory exercise on the analytical methods used to determine several radionuclides present in the environmental samples was organized. Activity concentration of different natural radionuclides, such as Rn-222, Pb-210, Po-210, K-40, Ra-226, Ra-228 and isotopes...... of uranium, in addition to artificial Cs-137 and Am-241 were analysed from lake sediment samples and drinking water. The measurement techniques were gamma-ray spectrometry, alpha spectrometry, liquid scintillation counting and inductively coupled plasma mass spectrometry. Twenty six laboratories from nine...

Spacecraft early design validation using formal methods

International Nuclear Information System (INIS)

Bozzano, Marco; Cimatti, Alessandro; Katoen, Joost-Pieter; Katsaros, Panagiotis; Mokos, Konstantinos; Nguyen, Viet Yen; Noll, Thomas; Postma, Bart; Roveri, Marco

2014-01-01

The size and complexity of software in spacecraft is increasing exponentially, and this trend complicates its validation within the context of the overall spacecraft system. Current validation methods are labor-intensive as they rely on manual analysis, review and inspection. For future space missions, we developed – with challenging requirements from the European space industry – a novel modeling language and toolset for a (semi-)automated validation approach. Our modeling language is a dialect of AADL and enables engineers to express the system, the software, and their reliability aspects. The COMPASS toolset utilizes state-of-the-art model checking techniques, both qualitative and probabilistic, for the analysis of requirements related to functional correctness, safety, dependability and performance. Several pilot projects have been performed by industry, with two of them having focused on the system-level of a satellite platform in development. Our efforts resulted in a significant advancement of validating spacecraft designs from several perspectives, using a single integrated system model. The associated technology readiness level increased from level 1 (basic concepts and ideas) to early level 4 (laboratory-tested)

Quantification of plasma myo-inositol using gas chromatography-mass spectrometry.

Science.gov (United States)

Guo, Jin; Shi, Yingfei; Xu, Chengbao; Zhong, Rugang; Zhang, Feng; Zhang, Ting; Niu, Bo; Wang, Jianhua

2016-09-01

Myo-inositol (MI) deficiency is associated with an increased risk for neural tube defects (NTDs), mental disorders and metabolic diseases. We developed a gas chromatography-mass spectrometry (GC-MS) method to detect MI in human plasma, which was accurate, relatively efficient and convenient for clinical application. An external standard method was used for determination of plasma MI. Samples were analyzed by GC-MS after derivatization. The stable-isotope labeled internal standard approach was used to validate the method's accuracy. Alpha fetal protein (AFP) was detected by chemiluminescence immunoassay. The method was validated by determining the linearity, sensitivity and recovery rate. There was a good agreement between the internal standard approach and the present method. The NTD-affected pregnancies showed lower plasma MI (P=0.024) and higher AFP levels (P=0.001) than control. Maternal MI level showed a better discrimination in spina bifida subgroup, while AFP level showed a better discrimination in anencephaly subgroup after stratification analysis. We developed a sensitive and reliable method for the detection of clinical plasma MI, which might be a marker for NTDs screening, and established fundamental knowledge for clinical diagnosis and prevention for the diseases related to disturbed MI metabolism. Copyright © 2016 Elsevier B.V. All rights reserved.

Method validation for uranium content analysis using a potentiometer T-90

International Nuclear Information System (INIS)

Torowati; Ngatijo; Rahmiati

2016-01-01

An experimental method validation has been conducted for uranium content analysis using Potentiometer T-90. The method validation experiment was performed in the quality control laboratory of Experiment Fuel Element Installation, PTBBN - BATAN. The objective is to determine the level of precision and accuracy of analytical results for uranium analysis referring to the latest American Standard Test Method (ASTM) of ASTM C1267-11, which is a modified reference method by reducing of reagent consumption by 10% of the amount used by the original method. The ASTM C 1267-11 reference is a new ASTM as a substitute for the older ASTM namely ASTM C799, Vol.12.01, 2003. It is, therefore, necessary to validate the renewed method. The tool used for the analysis of uranium was potentiometer T-90 and the material used was standard uranium oxide powder CRM (Certificate Reference Material). Validation of the method was done by analyzing standard uranium powder by 7 times weighing and 7 times analysis. Analysis results were used to determine the level of accuracy, precision, Relative Standard Deviation (RSD) and Horwitz coefficient Variation and limit detection and quantitation. The average uranium obtained for this method validation is 84.36% with Standard Deviation (SD) of 0.12%, Relative Standard Deviation (RSD) 0.14% and 2/3 Horwitz coefficient Variation (CV Horwitz) 2.05%. The results show that RSD value is smaller than the value of (2/3) CV Horwitz, which means that this method has a high precision. The accuracy value obtained is 0.48%, and since the acceptance limit of high level of accuracy is when the accuracy value is <2.00%, this method is regarded as having a high degree of accuracy [1]. The limit of detection (LOD) and and the limit of quantitation (LOQ) are 0.0145 g/L and 0.0446 g/L respectively. It is concluded that the ASTM C 1267-11 reference method is valid for use. (author)

Likelihood ratio data to report the validation of a forensic fingerprint evaluation method

Directory of Open Access Journals (Sweden)

Daniel Ramos

2017-02-01

Full Text Available Data to which the authors refer to throughout this article are likelihood ratios (LR computed from the comparison of 5–12 minutiae fingermarks with fingerprints. These LRs data are used for the validation of a likelihood ratio (LR method in forensic evidence evaluation. These data present a necessary asset for conducting validation experiments when validating LR methods used in forensic evidence evaluation and set up validation reports. These data can be also used as a baseline for comparing the fingermark evidence in the same minutiae configuration as presented in (D. Meuwly, D. Ramos, R. Haraksim, [1], although the reader should keep in mind that different feature extraction algorithms and different AFIS systems used may produce different LRs values. Moreover, these data may serve as a reproducibility exercise, in order to train the generation of validation reports of forensic methods, according to [1]. Alongside the data, a justification and motivation for the use of methods is given. These methods calculate LRs from the fingerprint/mark data and are subject to a validation procedure. The choice of using real forensic fingerprint in the validation and simulated data in the development is described and justified. Validation criteria are set for the purpose of validation of the LR methods, which are used to calculate the LR values from the data and the validation report. For privacy and data protection reasons, the original fingerprint/mark images cannot be shared. But these images do not constitute the core data for the validation, contrarily to the LRs that are shared.

Evaluation of a method for the determination of chromium in urine by atomic absorption spectrometry

International Nuclear Information System (INIS)

Garcia, M.; Sardinas, O.; Castaneda, I.; Sanchez, R.

1990-01-01

A method for the determination of chromium in urine by atomic absorption spectrometry, using electrothermic atomization with pyrolytic graphite tubes, is proposed. The determinations are performed by standard addition. The method is applicable to biologic monitoring of populations with different degrees of exposition. It is also used in the analysis of chromium in sediments. Results of chromium in urine of a population group non-exposed to the metal are presented. 11 refs

Multiresidue Method for Quantification of Sulfonamides and Trimethoprim in Tilapia Fillet by Liquid Chromatography Coupled to Quadrupole Time-of-Flight Mass Spectrometry Using QuEChERS for Sample Preparation.

Science.gov (United States)

Nunes, Kátia S D; Assalin, Márcia R; Vallim, José H; Jonsson, Claudio M; Queiroz, Sonia C N; Reyes, Felix G R

2018-01-01

A multiresidue method for detecting and quantifying sulfonamides (sulfapyridine, sulfamerazine, sulfathiazole, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfamethoxypyridazine) and trimethoprim in tilapia fillet ( Oreochromis niloticus ) using liquid chromatography coupled to mass spectrometry was developed and validated. The sample preparation was optimized using the QuEChERS approach. The chromatographic separation was performed using a C18 column and 0.1% formic acid in water and acetonitrile as the mobile phase in the isocratic elution mode. Method validation was performed based on the Commission Decision 2002/657/EC and Brazilian guideline. The validation parameters evaluated were linearity ( r  ≥ 0.99); limits of detection (LOD) and quantification (LOQ), 1 ng·g -1 and 5 ng·g -1 , respectively; intraday and interdays precision (CV lower than 19.4%). The decision limit (CC α 102.6-120.0 ng·g -1 and 70 ng·g -1 for sulfonamides and trimethoprim, respectively) and detection capability (CC β 111.7-140.1 ng·g -1 and 89.9 ng·g -1 for sulfonamides and trimethoprim, respectively) were determined. Analyses of tilapia fillet samples from fish exposed to sulfamethazine through feed (incurred samples) were conducted in order to evaluate the method. This new method was demonstrated to be fast, sensitive, and suitable for monitoring sulfonamides and trimethoprim in tilapia fillet in health surveillance programs, as well as to be used in pharmacokinetics and residue depletion studies.

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.)

A simple and fast method for the inspection of preservatives in cheeses and cream by liquid chromatography- electrospray tandem mass spectrometry.

Science.gov (United States)

Molognoni, Luciano; de Sá Ploêncio, Leandro Antunes; Valese, Andressa Camargo; De Dea Lindner, Juliano; Daguer, Heitor

2016-01-15

In this work, a simplified extraction and short time of analysis method for the simultaneous determination of natamycin, nisin and sorbic acid in cheeses and cream by reverse phase liquid chromatography-electrospray-tandem mass spectrometry was developed. Full validation was performed according to the Commission Decision 2002/657/EC criteria and method applicability was checked on several samples, aiming to inspect their compliance with regulatory limits. The method was linear in the concentration ranges of 0-10mg kg(-1) (natamycin), 0-25mg kg(-1) (nisin) and 0 20mg kg(-1) (sorbic acid). Samples of the three most consumed types of cheese (fresh, pasta filata and ripened) in Brazil and cream (ultra high temperature and pasteurized, 20-30% fat content) were assessed. A surprising rate of non-compliance was observed, especially among ripened grated cheeses, since 80% of samples were above the maximum limit for sorbic acid with an average concentration of 2766.3±10.8mg kg(-1). Moreover, a major non-compliance for the cream samples was observed. The proposed method can be applied as an efficient tool for the inspection of preservatives in cheeses and cream. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparison of photoacoustic radiometry to gas chromatography/mass spectrometry methods for monitoring chlorinated hydrocarbons

International Nuclear Information System (INIS)

Sollid, J.E.; Trujillo, V.L.; Limback, S.P.; Woloshun, K.A.

1996-01-01

A comparison of two methods of gas chromatography mass spectrometry (GCMS) and a nondispersive infrared technique, photoacoustic radiometry (PAR), is presented in the context of field monitoring a disposal site. First is presented an historical account describing the site and early monitoring to provide an overview. The intent and nature of the monitoring program changed when it was proposed to expand the Radiological Waste Site close to the Hazardous Waste Site. Both the sampling methods and analysis techniques were refined in the course of this exercise

Development and Validation of an ICP-MS Method for Simultaneous Determination of Selected Metals in Electronic Cigarette Aerosol

Directory of Open Access Journals (Sweden)

Ohashi Shintaro

2018-04-01

Full Text Available Safety and quality standards for electronic cigarettes (e-cigarettes have been introduced regionally. In 2016, the U.S. Food and Drug Administration (FDA issued a rule to regulate e-cigarettes, requiring to report harmful and potentially harmful constituents (HPHCs. In the United Kingdom, the British Standards Institution (BSI specified the metals to be monitored for e-cigarettes. In this study, a method was developed and validated for the simultaneous determination of 13 metals (Be, Al, Cr, Fe, Co, Ni, Cu, As, Se, Ag, Cd, Sn and Pb in e-cigarette aerosol. Furthermore, matrix effects of major constituents in the aerosol were investigated using glycerol or 1,2-propylene glycol solutions. E-cigarette aerosol was generated by a rotary smoking machine according to CORESTA Recommended Method N° 81 and collected by an electrostatic precipitator coupled to an impinger containing nitric acid. The collected aerosol was dissolved in nitric acid and an aliquot of this solution was analyzed by inductively coupled plasma mass spectrometry (ICP-MS equipped with a collision/reaction cell.

Human Factors methods concerning integrated validation of nuclear power plant control rooms

International Nuclear Information System (INIS)

Oskarsson, Per-Anders; Johansson, Bjoern J.E.; Gonzalez, Natalia

2010-02-01

The frame of reference for this work was existing recommendations and instructions from the NPP area, experiences from the review of the Turbic Validation and experiences from system validations performed at the Swedish Armed Forces, e.g. concerning military control rooms and fighter pilots. These enterprises are characterized by complex systems in extreme environments, often with high risks, where human error can lead to serious consequences. A focus group has been performed with representatives responsible for Human Factors issues from all Swedish NPP:s. The questions that were discussed were, among other things, for whom an integrated validation (IV) is performed and its purpose, what should be included in an IV, the comparison with baseline measures, the design process, the role of SSM, which methods of measurement should be used, and how the methods are affected of changes in the control room. The report brings different questions to discussion concerning the validation process. Supplementary methods of measurement for integrated validation are discussed, e.g. dynamic, psychophysiological, and qualitative methods for identification of problems. Supplementary methods for statistical analysis are presented. The study points out a number of deficiencies in the validation process, e.g. the need of common guidelines for validation and design, criteria for different types of measurements, clarification of the role of SSM, and recommendations for the responsibility of external participants in the validation process. The authors propose 12 measures for taking care of the identified problems

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

Science.gov (United States)

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

2015-09-02

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

Spectrometry techniques for radioactivity measurements

International Nuclear Information System (INIS)

Anilkumar, S.

2016-01-01

The energy of the radiation emission following the nuclear decay is unique and the characteristic of the radio nuclide which undergoes decay. Thus measurement of the energy of the radiation offers a method of identifying the radio nuclides. The prime requirement of the energy measurement is a suitable detector which shows response proportional to the energy of the radiation rather than the presence of the radiation. The response from such detectors are suitably processed and distributed with respect to the signal strength which is proportional to incident energy. This distribution is normally referred as energy spectrum and is recorded in the multichannel analyser. The measurement of energy and intensity of radiation from the spectrum is called radiation spectrometry. Thus the radiation spectrometry allows the identification and quantification of radioactive isotopes in variety of matrices. The radiation spectrometry has now become a popular radioanalytical technique in wide area of nuclear fuel cycle programs. The popular spectrometry techniques commonly used for the radioactivity measurement and analysis are Alpha spectrometry, Gamma ray spectrometry and Beta spectrometry

Comprehension of complex biological processes by analytical methods: how far can we go using mass spectrometry?

International Nuclear Information System (INIS)

Gerner, C.

2013-01-01

Comprehensive understanding of complex biological processes is the basis for many biomedical issues of great relevance for modern society including risk assessment, drug development, quality control of industrial products and many more. Screening methods provide means for investigating biological samples without research hypothesis. However, the first boom of analytical screening efforts has passed and we again need to ask whether and how to apply screening methods. Mass spectrometry is a modern tool with unrivalled analytical capacities. This applies to all relevant characteristics of analytical methods such as specificity, sensitivity, accuracy, multiplicity and diversity of applications. Indeed, mass spectrometry qualifies to deal with complexity. Chronic inflammation is a common feature of almost all relevant diseases challenging our modern society; these diseases are apparently highly diverse and include arteriosclerosis, cancer, back pain, neurodegenerative diseases, depression and other. The complexity of mechanisms regulating chronic inflammation is the reason for the practical challenge to deal with it. The presentation shall give an overview of capabilities and limitations of the application of this analytical tool to solve critical questions with great relevance for our society. (author)

Quantitative determination of total cesium in highly active liquid waste by using liquid electrode plasma optical emission spectrometry.

Science.gov (United States)

Do, Van-Khoai; Yamamoto, Masahiko; Taguchi, Shigeo; Takamura, Yuzuru; Surugaya, Naoki; Kuno, Takehiko

2018-06-01

A sensitive analytical method for determination of total cesium (Cs) in highly active liquid waste (HALW) by using modified liquid electrode plasma optical emission spectrometry (LEP-OES) is developed in this study. The instrument is modified to measure radioactive samples in a glove box. The effects of important factors, including pulsed voltage sequence and nitric acid concentration, on the emission of Cs are investigated. The limit of detection (LOD) and limit of quantification (LOQ) are 0.005 mg/L and 0.02 mg/L, respectively. The achieved LOD is one order lower than that of recently developed spectroscopic methods using liquid discharge plasma. The developed method is validated by subjecting a simulated HALW sample to inductively coupled plasma mass spectrometry (ICP-MS). The recoveries obtained from a spike-and-recovery test are 96-102%, implying good accuracy. The method is successfully applied to the quantification of Cs in a real HALW sample at the Tokai reprocessing plant in Japan. Apart from dilution and filtration of the HALW sample, no other pre-treatment process is required. The results agree well with the values obtained using gamma spectrometry. The developed method offers a reliable technique for rapid analysis of total Cs in HALW samples. Copyright © 2018 Elsevier B.V. All rights reserved.

A liquid chromatography with tandem mass spectrometry method for quantitating total and unbound ceritinib in patient plasma and brain tumor

Directory of Open Access Journals (Sweden)

Xun Bao

2018-02-01

Full Text Available A rapid, sensitive, and robust reversed-phase liquid chromatography with tandem mass spectrometry method was developed and validated for the determination of total and unbound ceritinib, a second-generation ALK inhibitor, in patient plasma and brain tumor tissue samples. Sample preparation involved simple protein precipitation with acetonitrile. Chromatographic separation was achieved on a Waters ACQUITY UPLC BEH C18 column using a 4-min gradient elution consisting of mobile phase A (0.1% formic acid in water and mobile phase B (0.1% formic acid in acetonitrile, at a flow rate of 0.4 mL/min. Ceritinib and the internal standard ([13C6]ceritinib were monitored using multiple reaction monitoring mode under positive electrospray ionization. The lower limit of quantitation (LLOQ was 1 nM of ceritinib in plasma. The calibration curve was linear over ceritinib concentration range of 1–2000 nM in plasma. The intra- and inter-day precision and accuracy were within the generally accepted criteria for bioanalytical method (<15%. The method was successfully applied to assess ceritinib brain tumor penetration, as assessed by the unbound drug brain concentration to unbound drug plasma concentration ratio, in patients with brain tumors.

Validation of calculational methods for nuclear criticality safety - approved 1975

International Nuclear Information System (INIS)

Anon.

1977-01-01

The American National Standard for Nuclear Criticality Safety in Operations with Fissionable Materials Outside Reactors, N16.1-1975, states in 4.2.5: In the absence of directly applicable experimental measurements, the limits may be derived from calculations made by a method shown to be valid by comparison with experimental data, provided sufficient allowances are made for uncertainties in the data and in the calculations. There are many methods of calculation which vary widely in basis and form. Each has its place in the broad spectrum of problems encountered in the nuclear criticality safety field; however, the general procedure to be followed in establishing validity is common to all. The standard states the requirements for establishing the validity and area(s) of applicability of any calculational method used in assessing nuclear criticality safety

Fatty acid ethyl esters (FAEEs) as markers for alcohol in meconium: method validation and implementation of a screening program for prenatal drug exposure.

Science.gov (United States)

Hastedt, Martin; Krumbiegel, Franziska; Gapert, René; Tsokos, Michael; Hartwig, Sven

2013-09-01

Alcohol consumption during pregnancy is a widespread problem and can cause severe fetal damage. As the diagnosis of fetal alcohol syndrome is difficult, the implementation of a reliable marker for alcohol consumption during pregnancy into meconium drug screening programs would be invaluable. A previously published gas chromatography mass spectrometry method for the detection of fatty acid ethyl esters (FAEEs) as alcohol markers in meconium was optimized and newly validated for a sample size of 50 mg. This method was applied to 122 cases from a drug-using population. The meconium samples were also tested for common drugs of abuse. In 73 % of the cases, one or more drugs were found. Twenty percent of the samples tested positive for FAEEs at levels indicating significant alcohol exposure. Consequently, alcohol was found to be the third most frequently abused substance within the study group. This re-validated method provides an increase in testing sensitivity, is reliable and easily applicable as part of a drug screening program. It can be used as a non-invasive tool to detect high alcohol consumption in the last trimester of pregnancy. The introduction of FAEEs testing in meconium screening was found to be of particular use in a drug-using population.

Innovative method for carbon dioxide determination in human postmortem cardiac gas samples using headspace-gas chromatography–mass spectrometry and stable labeled isotope as internal standard

Energy Technology Data Exchange (ETDEWEB)

Varlet, V., E-mail: vincent.varlet@chuv.ch [Toxicology and Forensic Chemistry Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Smith, F. [Toxicology and Forensic Chemistry Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Froidmont, S. de; Dominguez, A.; Rinaldi, A. [Forensic Medicine Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Augsburger, M. [Toxicology and Forensic Chemistry Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Mangin, P.; Grabherr, S. [Forensic Medicine Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland)

2013-06-19

Graphical abstract: -- Highlights: •We developed a method for CO{sub 2} analysis in cardiac samples and quantification by {sup 13}CO{sub 2}. •This method was fully validated by accuracy profile. •We have applied this method to perform CO{sub 2} precise quantification for forensic applications. •Context of the death could be documented following CO{sub 2} concentrations. -- Abstract: A novel approach to measure carbon dioxide (CO{sub 2}) in gaseous samples, based on a precise and accurate quantification by {sup 13}CO{sub 2} internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography–mass spectrometry (HS-GC–MS) method applicable in the routine determination of CO{sub 2}. The main drawback of the GC methods discussed in the literature for CO{sub 2} measurement is the lack of a specific internal standard necessary to perform quantification. CO{sub 2} measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ({sup 13}CO{sub 2}) on the basis of the stoichiometric formation of CO{sub 2} by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH{sup 13}CO{sub 3}). This method allows a precise measurement of CO{sub 2} concentration and was validated on various human postmortem gas samples in order to study its efficiency.

Development and Validation of a Novel LC-MS/MS Opioid Confirmation Assay: Evaluation of β-glucuronidase Enzymes and Sample Cleanup Methods.

Science.gov (United States)

Yang, He S; Wu, Alan H B; Lynch, Kara L

2016-06-01

With the rise in the use and misuse of prescription opioids, there is an increasing need for the confirmed identification of opioid analgesics in toxicology laboratories. The goals of this study were to (i) systematically evaluate the hydrolysis efficiency of four β-glucuronidase enzymes under optimized condition; (ii) evaluate compound recovery, matrix effects and precision of three protein precipitation plates and (iii) develop and validate a qualitative liquid-chromatography mass spectrometry (LC-MS/MS) assay to identify 13 opioids in urine. A recombinant β-glucuronidase exhibited the best overall hydrolysis efficiency for seven opioid glucuronide conjugates compared with β-glucuronidase from red abalone, Escherichia coli and Patella vulgata One of the protein precipitation plates tested exhibited overall better recovery of the opioids and lower ion suppression compared with the other two plates. An ESI positive mode LC-MS/MS assay for qualitative opioid analysis was developed and validated. Linearity, LOD, precision, matrix effect, recovery, carryover and interference of the method were evaluated. Sixty-two patient samples were analyzed by both a legacy GC-MS opioid method and the LC-MS/MS method, and 22 samples were analyzed by the LC-MS/MS and an LC-MS/MS reference method. The results of the comparisons showed good concordance. Overall, we described an efficient sample preparation procedure for a sensitive qualitative opioid confirmation assay in urine. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Development, validation and accreditation of a method for the determination of Pb, Cd, Cu and As in seafood and fish feed samples.

Science.gov (United States)

Psoma, A K; Pasias, I N; Rousis, N I; Barkonikos, K A; Thomaidis, N S

2014-05-15

A rapid, sensitive, accurate and precise method for the determination of Pb, Cd, As and Cu in seafood and fish feed samples by Simultaneous Electrothermal Atomic Absorption Spectrometry was developed in regard to Council Directive 333/2007EC and ISO/IEC 17025 (2005). Different approaches were investigated in order to shorten the analysis time, always taking into account the sensitivity. For method validation, precision (repeatability and reproducibility) and accuracy by addition recovery tests have been assessed as performance criteria. The expanded uncertainties based on the Eurachem/Citac Guidelines were calculated. The method was accredited by the Hellenic Accreditation System and it was applied for an 8 years study in seafood (n=202) and fish feeds (n=275) from the Greek market. The annual and seasonal variation of the elemental content and correlation among the elemental content in fish feeds and the respective fish samples were also accomplished. Copyright © 2013 Elsevier Ltd. All rights reserved.

Development and validation of LC-MS/MS method with multiple reactions monitoring mode for quantification of vanillin and syringaldehyde in plum brandies

Directory of Open Access Journals (Sweden)

Tešević Vele

2014-01-01

Full Text Available An ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-QqQ-MS/MS method with multiple reactions monitoring mode (MRM has been developed and validated for quantification of vanillin and syringaldehyde in plum brandy. The method showed good linearity (0.05 to 10 mgL−1 and low limits of detection and quantification (LOD and LOQ were 11.6 µgL−1 and 38.2 µgL−1 for vanillin, and 12.7 µgL−1 and 42.0 µgL−1 for syringaldehyde, respectively. The overall intra-day and inter-day variations were less than 4.21%, and the overall recovery over 93.0%. The correlation coefficients (R2 of the calibration curves were higher than 0.9999. In order to evaluate if the method is suitable for use as a routine analytical tool, in 31 Serbian plum brandy samples vanillin and syringaldehide were determined. [Projekat Ministarstva nauke Republike Srbije, br. 172053

A liquid chromatography – tandem mass spectrometry method to measure a selected panel of uremic retention solutes derived from endogenous and colonic microbial metabolism

Energy Technology Data Exchange (ETDEWEB)

Loor, Henriette de; Poesen, Ruben [KU Leuven – University of Leuven, Department of Microbiology and Immunology, Laboratory of Nephrology, B-3000 Leuven (Belgium); De Leger, Wout; Dehaen, Wim [KU Leuven – University of Leuven, Department of Chemistry, Division of Molecular Design and Synthesis, B-3000 Leuven (Belgium); Augustijns, Patrick [KU Leuven – University of Leuven, Department of Pharmaceutical and Pharmacological Sciences, Drug Delivery and Disposition, B-3000 Leuven (Belgium); Evenepoel, Pieter [KU Leuven – University of Leuven, Department of Microbiology and Immunology, Laboratory of Nephrology, B-3000 Leuven (Belgium); University Hospitals Leuven, Department of Nephrology and Renal Transplantation, B-3000 Leuven (Belgium); Meijers, Björn, E-mail: bjorn.meijers@uzleuven.be [KU Leuven – University of Leuven, Department of Microbiology and Immunology, Laboratory of Nephrology, B-3000 Leuven (Belgium); University Hospitals Leuven, Department of Nephrology and Renal Transplantation, B-3000 Leuven (Belgium)

2016-09-14

Chronic kidney disease (CKD) is associated with an increased risk of mortality and cardiovascular disease, which is, at least partly, mediated by the accumulation of so-called uremic retention solutes. Although there has been an increasing interest in the behavior of these solutes, derived from both the endogenous and colonic microbial metabolism, methods to simultaneously and accurately measure a broad panel of relevant uremic retention solutes remain scarce. We developed a highly sensitive ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. A high throughput sample preparation was used with extraction of analytes from 50 μl serum using Ostro plate technology. For most solutes, stable isotopes labelled metabolites were used as internal standards. Chromatography was achieved using an Acquity UPLC CSH Fluoro Phenyl column. The total run time was 8 min, the mobile phase was a gradient of 0.1% formic acid in Milli-Q water and pure methanol at a flow rate of 0.5 ml min{sup −1}. Detection was performed using a tandem mass spectrometer with alternated positive and negative electrospray ionization. Calibration curves were linear for all solutes. Precision was assessed according to the NCCLS EP5-T guideline, being below 15% for all metabolites. Mean recoveries were between 83 and 104% for all metabolites. The validated method was successfully applied in a cohort of 488 patients with CKD. We developed and validated a sensitive and robust UPLC-MS/MS method for quantification of 15 uremic retention solutes derived from endogenous and colonic microbial metabolism. This method allows for studying the behavior and relevance of these solutes in patients with CKD. - Highlights: • Simultaneous quantification of fifteen relevant uremic retention solutes. • Comprehensive validation, highly sensitive and high through-put LC-MSMS method. • Comparison of different blood tubes. • Freeze-thaw stability. • Successful implementation in a

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

Determination of four forms of vitamin B12 and other B vitamins in seawater by liquid chromatography/tandem mass spectrometry.

Science.gov (United States)

Heal, Katherine R; Carlson, Laura Truxal; Devol, Allan H; Armbrust, E Virginia; Moffett, James W; Stahl, David A; Ingalls, Anitra E

2014-11-30

Vitamin B(12) is an essential nutrient for more than half of surveyed marine algae species, but methods for directly measuring this important cofactor in seawater are limited. Current mass spectrometry methods do not quantify all forms of B(12), potentially missing a significant portion of the B(12) pool. We present a method to measure vitamins B(1), B(2), B(6), B(7) and four forms of B(12) dissolved in seawater. The method entails solid-phase extraction, separation by ultra-performance liquid chromatography, and detection by triple-quadrupole tandem mass spectrometry using stable-isotope-labeled internal standards. We demonstrated the use of this method in the environment by analyzing B(12) concentrations at different depths in the Hood Canal, part of the Puget Sound estuarine system in Washington State. Recovery of vitamin B(12) forms during the preconcentration steps was >71% and the limits of detection were B(12) in seawater at our field site. We developed a method for quantifying four forms of B(12) in seawater by liquid chromatography/mass spectrometry with the option of simultaneous analysis of vitamins B(1), B(2), B(6), and B(7). We validated the method and demonstrated its application in the field. Copyright © 2014 John Wiley & Sons, Ltd.

Fast Atom Bombardment Spectrometry - a novel analytical method for biologically interesting, non-volatile substances

International Nuclear Information System (INIS)

Schmid, E.

1987-03-01

Today important chemical substances like proteins can be produced easily and in large amounts. The primary structure of proteins can be analysed automatically, however the procedure can take some months of time. A novel method, fast atom bombardment mass spectrometry (FAB-MS) in combination with enzymatic degradation not only decreases the analysis time, but gives also additional information about the primary structure. Especially for the verification of protein structures - which is important for recombinant proteins - FAB-MS is a very useful method. 40 refs., 56 figs. (P.W.)

Urban gamma spectrometry. Report 2

Energy Technology Data Exchange (ETDEWEB)

Aage, H.K. (Technical Univ. of Denmark, Kgs. Lyngby (Denmark)); Kuukankorpi, S.; Moring, M.; Smolander, P.; Toivonen, H. (Radiation and Nuclear Safety Authority, Helsinki (Finland))

2009-06-15

Urban gamma spectrometry has been given only minor attention with the focus being on rural gamma spectrometry. However, in recent years the Nordic emergency management authorities have turned focus towards border control and lost or stolen sources. Gamma spectra measured in urban areas are characterized by a wide variety of spectrum shapes and very fast changes in environmental background. In 2004 a Danish CGS (Carborne Gamma Spectrometry) survey took place in Copenhagen. It was found that gamma spectrometry in urban areas is far more complicated to interpret than had previously been thought and a new method 'Fitting with Spectral Components', FSC, based on NASVD, was tested with some success. In Finland, a database 'LINSSI' has been developed for spectral data management. In CGS search mode a 'peak hypothesis test' is applied to the measured spectra. This system was tested during the Helsinki 2005 Athletics World Championship and it provides fast and reliable automated alarms for intermediate and high level signals. In Sweden mobile detector systems are used for border controls and problems are encountered when making measurement in harbour, container areas. The methods for handling data and for interpretation of urban gamma spectrometry measurements were compared and tested on the same data sets from Copenhagen and Helsinki. Software tools were developed for converting data between the Finnish LINSSI database and the binary file formats used in Denmark and Sweden. The Processing methods used at DTU and STUK have different goals. The ASSS and FSC methods are designed to optimize the overall detection capability of the system, while sacrificing speed, usability and to a certain level robustness. These methods cannot always be used for real time analysis. The Peak Significance method is designed to give robust alarms in real time, while sacrificing some of the detection capability. Thus these methods are not interchangeable, but rather

Urban gamma spectrometry. Report 2

International Nuclear Information System (INIS)

Aage, H.K.; Kuukankorpi, S.; Moring, M.; Smolander, P.; Toivonen, H.

2009-06-01

Urban gamma spectrometry has been given only minor attention with the focus being on rural gamma spectrometry. However, in recent years the Nordic emergency management authorities have turned focus towards border control and lost or stolen sources. Gamma spectra measured in urban areas are characterized by a wide variety of spectrum shapes and very fast changes in environmental background. In 2004 a Danish CGS (Carborne Gamma Spectrometry) survey took place in Copenhagen. It was found that gamma spectrometry in urban areas is far more complicated to interpret than had previously been thought and a new method 'Fitting with Spectral Components', FSC, based on NASVD, was tested with some success. In Finland, a database 'LINSSI' has been developed for spectral data management. In CGS search mode a 'peak hypothesis test' is applied to the measured spectra. This system was tested during the Helsinki 2005 Athletics World Championship and it provides fast and reliable automated alarms for intermediate and high level signals. In Sweden mobile detector systems are used for border controls and problems are encountered when making measurement in harbour, container areas. The methods for handling data and for interpretation of urban gamma spectrometry measurements were compared and tested on the same data sets from Copenhagen and Helsinki. Software tools were developed for converting data between the Finnish LINSSI database and the binary file formats used in Denmark and Sweden. The Processing methods used at DTU and STUK have different goals. The ASSS and FSC methods are designed to optimize the overall detection capability of the system, while sacrificing speed, usability and to a certain level robustness. These methods cannot always be used for real time analysis. The Peak Significance method is designed to give robust alarms in real time, while sacrificing some of the detection capability. Thus these methods are not interchangeable, but rather complementary. An ideal system

A novel liquid chromatography/mass spectrometry method for determination of neurotransmitters in brain tissue: Application to human tauopathies.

Science.gov (United States)

Forgacsova, Andrea; Galba, Jaroslav; Garruto, Ralph M; Majerova, Petra; Katina, Stanislav; Kovac, Andrej

2018-01-15

Neurotransmitters, small molecules widely distributed in the central nervous system are essential in transmitting electrical signals across neurons via chemical communication. Dysregulation of these chemical signaling molecules is linked to numerous neurological diseases including tauopathies. In this study, a precise and reliable liquid chromatography method was established with tandem mass spectrometry detection for the simultaneous determination of aspartic acid, asparagine, glutamic acid, glutamine, γ-aminobutyric acid, N-acetyl-l-aspartic acid, pyroglutamic acid, acetylcholine and choline in human brain tissue. The method was successfully applied to the analysis of human brain tissues from three different tauopathies; corticobasal degeneration, progressive supranuclear palsy and parkinsonism-dementia complex of Guam. Neurotransmitters were analyzed on ultra-high performance chromatography (UHPLC) using an ethylene bridged hybrid amide column coupled with tandem mass spectrometry (MS/MS). Identification and quantification of neurotransmitters was carried out by ESI+ mass spectrometry detection. We optimized sample preparation to achieve simple and fast extraction of all nine analytes. Our method exhibited an excellent linearity for all analytes (all coefficients of determination >0.99), with inter-day and intra-day precision yielding relative standard deviations 3.2%-11.2% and an accuracy was in range of 92.6%-104.3%. The present study, using the above method, is the first to demonstrate significant alterations of brain neurotransmitters caused by pathological processes in the brain tissues of patient with three different tauopathies. Copyright © 2017 Elsevier B.V. All rights reserved.

Moving beyond Traditional Methods of Survey Validation

Science.gov (United States)

Maul, Andrew

2017-01-01

In his focus article, "Rethinking Traditional Methods of Survey Validation," published in this issue of "Measurement: Interdisciplinary Research and Perspectives," Andrew Maul wrote that it is commonly believed that self-report, survey-based instruments can be used to measure a wide range of psychological attributes, such as…

Single laboratory validation of the determination of yohimbine in yohimbe bark and related dietary supplements using UHPLC/UV/MS

Science.gov (United States)

A single laboratory validation has been performed on a practical ultra high-performance liquid chromatography (UHPLC), diode array detection (DAD), and tandem mass spectrometry (MS) method for determination of yohimbine in yohimbe barks and related dietary supplements. Good separation was achieved u...

Validation and application of a GC-MS method for the determination of haloacetic acids in drinking water

Directory of Open Access Journals (Sweden)

Chiavelli Lucas U.R.

2016-01-01

Full Text Available Usually, water treatment plants employ chlorine or sodium hypochlorite during the disinfection process, ensuring that there are not any pathogenic microorganisms in water. However, chlorine might react with natural organic matter and lead to formation of potentially carcinogenic by-products regarding human health, such as haloacetic acids (HAAs. Several countries regulate the levels of these acids in drinking water. Therefore, their concentrations must be monitored with the greatest accuracy as possible. In order to achieve this goal, a method through gas chromatography coupled with mass spectrometry (GC-MS was validated and applied to the determination of HAAs in samples of water destined to the public water service provision from the city of Maringá, Paraná State, Brazil. Measurements between two periods have close recovery values, indicating that the method has good accuracy during the same day. The limits of detection (LOD and quantification (LOQ were satisfactory, with LOD 0.42 μg L-1 and LOQ 1.40 μg L-1 for dichloro-acetic acid (DCAA analysis. Recovery values obtained for the nine haloace-tics acids (HAA9 corresponded to 69.9-107.3 % for samples. The repeatability performed for two periods presented close relative standard deviation (RSD values, indicating that the method has good accuracy during the same day.

Hydrophilic interaction liquid chromatography-tandem mass spectrometry quantitative method for the cellular analysis of varying structures of gemini surfactants designed as nanomaterial drug carriers.

Science.gov (United States)

Donkuru, McDonald; Michel, Deborah; Awad, Hanan; Katselis, George; El-Aneed, Anas

2016-05-13

Diquaternary gemini surfactants have successfully been used to form lipid-based nanoparticles that are able to compact, protect, and deliver genetic materials into cells. However, what happens to the gemini surfactants after they have released their therapeutic cargo is unknown. Such knowledge is critical to assess the quality, safety, and efficacy of gemini surfactant nanoparticles. We have developed a simple and rapid liquid chromatography electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) method for the quantitative determination of various structures of gemini surfactants in cells. Hydrophilic interaction liquid chromatography (HILIC) was employed allowing for a short simple isocratic run of only 4min. The lower limit of detection (LLOD) was 3ng/mL. The method was valid to 18 structures of gemini surfactants belonging to two different structural families. A full method validation was performed for two lead compounds according to USFDA guidelines. The HILIC-MS/MS method was compatible with the physicochemical properties of gemini surfactants that bear a permanent positive charge with both hydrophilic and hydrophobic elements within their molecular structure. In addition, an effective liquid-liquid extraction method (98% recovery) was employed surpassing previously used extraction methods. The analysis of nanoparticle-treated cells showed an initial rise in the analyte intracellular concentration followed by a maximum and a somewhat more gradual decrease of the intracellular concentration. The observed intracellular depletion of the gemini surfactants may be attributable to their bio-transformation into metabolites and exocytosis from the host cells. Obtained cellular data showed a pattern that grants additional investigations, evaluating metabolite formation and assessing the subcellular distribution of tested compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Validation Process Methods

Energy Technology Data Exchange (ETDEWEB)

Lewis, John E. [National Renewable Energy Lab. (NREL), Golden, CO (United States); English, Christine M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Gesick, Joshua C. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukkamala, Saikrishna [National Renewable Energy Lab. (NREL), Golden, CO (United States)

2018-01-04

This report documents the validation process as applied to projects awarded through Funding Opportunity Announcements (FOAs) within the U.S. Department of Energy Bioenergy Technologies Office (DOE-BETO). It describes the procedures used to protect and verify project data, as well as the systematic framework used to evaluate and track performance metrics throughout the life of the project. This report also describes the procedures used to validate the proposed process design, cost data, analysis methodologies, and supporting documentation provided by the recipients.

Screening and quantitative determination of twelve acidic and neutral pharmaceuticals in whole blood by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry

DEFF Research Database (Denmark)

Simonsen, Kirsten Wiese; Steentoft, Anni; Buck, Maike

2010-01-01

. The method was fully validated for salicylic acid, paracetamol, phenobarbital, carisoprodol, meprobamate, topiramate, etodolac, chlorzoxazone, furosemide, ibuprofen, warfarin, and salicylamide. The method also tentatively includes thiopental, theophylline, piroxicam, naproxen, diclophenac, and modafinil......We describe a multi-method for simultaneous identification and quantification of 12 acidic and neutral compounds in whole blood. The method involves a simple liquid-liquid extraction, and the identification and quantification are performed using liquid chromatography-tandem mass spectrometry...

A comprehensive high-resolution mass spectrometry approach for characterization of metabolites by combination of ambient ionization, chromatography and imaging methods.

Science.gov (United States)

Berisha, Arton; Dold, Sebastian; Guenther, Sabine; Desbenoit, Nicolas; Takats, Zoltan; Spengler, Bernhard; Römpp, Andreas

2014-08-30

An ideal method for bioanalytical applications would deliver spatially resolved quantitative information in real time and without sample preparation. In reality these requirements can typically not be met by a single analytical technique. Therefore, we combine different mass spectrometry approaches: chromatographic separation, ambient ionization and imaging techniques, in order to obtain comprehensive information about metabolites in complex biological samples. Samples were analyzed by laser desorption followed by electrospray ionization (LD-ESI) as an ambient ionization technique, by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging for spatial distribution analysis and by high-performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS) for quantitation and validation of compound identification. All MS data were acquired with high mass resolution and accurate mass (using orbital trapping and ion cyclotron resonance mass spectrometers). Grape berries were analyzed and evaluated in detail, whereas wheat seeds and mouse brain tissue were analyzed in proof-of-concept experiments. In situ measurements by LD-ESI without any sample preparation allowed for fast screening of plant metabolites on the grape surface. MALDI imaging of grape cross sections at 20 µm pixel size revealed the detailed distribution of metabolites which were in accordance with their biological function. HPLC/ESI-MS was used to quantify 13 anthocyanin species as well as to separate and identify isomeric compounds. A total of 41 metabolites (amino acids, carbohydrates, anthocyanins) were identified with all three approaches. Mass accuracy for all MS measurements was better than 2 ppm (root mean square error). The combined approach provides fast screening capabilities, spatial distribution information and the possibility to quantify metabolites. Accurate mass measurements proved to be critical in order to reliably combine data from different MS

An intelligent detection method for high-field asymmetric waveform ion mobility spectrometry.

Science.gov (United States)

Li, Yue; Yu, Jianwen; Ruan, Zhiming; Chen, Chilai; Chen, Ran; Wang, Han; Liu, Youjiang; Wang, Xiaozhi; Li, Shan

2018-04-01

In conventional high-field asymmetric waveform ion mobility spectrometry signal acquisition, multi-cycle detection is time consuming and limits somewhat the technique's scope for rapid field detection. In this study, a novel intelligent detection approach has been developed in which a threshold was set on the relative error of α parameters, which can eliminate unnecessary time spent on detection. In this method, two full-spectrum scans were made in advance to obtain the estimated compensation voltage at different dispersion voltages, resulting in a narrowing down of the whole scan area to just the peak area(s) of interest. This intelligent detection method can reduce the detection time to 5-10% of that of the original full-spectrum scan in a single cycle.

Study by Auger spectrometry and mass spectrometry of the chemisorption of carbon monoxide on polycrystalline molybdenum

International Nuclear Information System (INIS)

Gillet, E.; Chiarena, J.C.; Gillet, M.

1976-01-01

A combination of Auger spectrometry and mass spectrometry was employed to study CO chemisorption on polycrystalline Mo surfaces at room temperature. Five adsorption states were observed and the binding parameters (E,n 0 ,tau 0 ) were calculated for the three important states. The results obtained by the two methods are in accord but the occurence of electronic desorption in Auger experiments was pointed out. Contamination effects by C atoms in such studies were investigated by repeated cycles of adsorption-desorption and a characteristic evolution of flash desorption was observed. The results are discussed in this point of view enhancing the importance of a control of the adsorption surface cleanness by a method of great sensibility like Auger spectrometry. (Auth.)

Determination of anthelmintic drug residues in milk using ultra high performance liquid chromatography-tandem mass spectrometry with rapid polarity switching.

Science.gov (United States)

Whelan, Michelle; Kinsella, Brian; Furey, Ambrose; Moloney, Mary; Cantwell, Helen; Lehotay, Steven J; Danaher, Martin

2010-07-02

A new UHPLC-MS/MS (ultra high performance liquid chromatography coupled to tandem mass spectrometry) method was developed and validated to detect 38 anthelmintic drug residues, consisting of benzimidazoles, avermectins and flukicides. A modified QuEChERS-type extraction method was developed with an added concentration step to detect most of the analytes at keeper to ensure analytes remain in solution. Using rapid polarity switching in electrospray ionisation, a single injection was capable of detecting both positively and negatively charged ions in a 13 min run time. The method was validated at two levels: the unapproved use level and at the maximum residue level (MRL) according to Commission Decision (CD) 2002/657/EC criteria. The decision limit (CCalpha) of the method was in the range of 0.14-1.9 and 11-123 microg kg(-1) for drugs validated at unapproved and MRL levels, respectively. The performance of the method was successfully verified for benzimidazoles and levamisole by participating in a proficiency study.

Neutron spectra unfolding in Bonner spheres spectrometry using neural networks

International Nuclear Information System (INIS)

Kardan, M.R.; Setayeshi, S.; Koohi-Fayegh, R.; Ghiassi-Nejad, M.

2003-01-01

The neural network method has been used for the unfolding of neutron spectra in neutron spectrometry by Bonner spheres. A back propagation algorithm was used for training of neural networks 4mm x 4 mm bare LiI(Eu) and in a polyethylene sphere set: 2, 3, 4, 5, 6, 7, 8, 10, 12, 18 inch diameter have been used for unfolding of neutron spectra. Neural networks were trained by 199 sets of neutron spectra, which were subdivided into 6, 8, 10, 12, 15 and 20 energy bins and for each of them an appropriate neural network was designed and trained. The validation was performed by the 21 sets of neutron spectra. A neural network with 10 energy bins which had a mean value of error of 6% for dose equivalent estimation of spectra in the validation set showed the best results. The obtained results show that neural networks can be applied as an effective method for unfolding neutron spectra especially when the main target is neutron dosimetry. (author)

[Improvement of the method for methylmercury determination in aquatic products using liquid chromatography online coupled with atomic fluorescence spectrometry].

Science.gov (United States)

Shang, Xiaohong; Zhao, Yunfeng; Zhang, Lei; Li, Xiaowei; Wu, Yongning

2011-07-01

The improvement method was developed for methylmercury determination using liquid chromatography online coupled with cold vapor atomic fluorescence spectrometry (LC-CV-AFS). Cysteine was used as complexing agent in mobile phase instead of mercaptoethanol. Under the optimized conditions, baseline separation of mercury species could be achieved within 8 min on a C18 column with a mobile phase of 5% (v/v) acetonitrile-1 g/L L-cysteine-50 mmol/L ammonium acetate aqueous solution. The linear range of calibration curve of methylmercury was 1-50 microg/L and the limit of detection (S/N = 3) for methylmercury was 0.3 microg/L. Ultrasonication assisted hydrochloric acid extraction was used to extract methylmercury from seafood samples. The sample extract was cleaned up by a C18 solid phase extraction (SPE) cartridge. For validation of the method, certified reference materials and spiked seafood samples were analyzed. The determined methylmercury contents of certified reference materials NIST1566b, BCR464 and GBW10029 agreed well with the certified values. The determined methylmercury values for Food Analysis Performance Assessment Scheme (FAPAS) sample 07115 were satisfied. The recoveries of methylmercury in seafood samples at three spiked levels (10, 50 and 500 microg/kg) ranged from 89% to 112%, including cooked seafood food. The precision of the method based on relative standard deviation (RSD) was not more than 7%. The present method of LC-CV-AFS is accurate, sensitive, simple, and can meet the demand of methylmercury determination in seafood.

A validated RP-HPLC method for the determination of Irinotecan hydrochloride residues for cleaning validation in production area

Directory of Open Access Journals (Sweden)

Sunil Reddy

2013-03-01

Full Text Available Introduction: cleaning validation is an integral part of current good manufacturing practices in pharmaceutical industry. The main purpose of cleaning validation is to prove the effectiveness and consistency of cleaning in a given pharmaceutical production equipment to prevent cross contamination and adulteration of drug product with other active ingredient. Objective: a rapid, sensitive and specific reverse phase HPLC method was developed and validated for the quantitative determination of irinotecan hydrochloride in cleaning validation swab samples. Method: the method was validated using waters symmetry shield RP-18 (250mm x 4.6mm 5 µm column with isocratic mobile phase containing a mixture of 0.02 M potassium di-hydrogen ortho-phosphate, pH adjusted to 3.5 with ortho-phosphoric acid, methanol and acetonitrile (60:20:20 v/v/v. The flow rate of mobile phase was 1.0 mL/min with column temperature of 25°C and detection wavelength at 220nm. The sample injection volume was 100 µl. Results: the calibration curve was linear over a concentration range from 0.024 to 0.143 µg/mL with a correlation coefficient of 0.997. The intra-day and inter-day precision expressed as relative standard deviation were below 3.2%. The recoveries obtained from stainless steel, PCGI, epoxy, glass and decron cloth surfaces were more than 85% and there was no interference from the cotton swab. The detection limit (DL and quantitation limit (QL were 0.008 and 0.023 µg ml-1, respectively. Conclusion: the developed method was validated with respect to specificity, linearity, limit of detection and quantification, accuracy, precision and solution stability. The overall procedure can be used as part of a cleaning validation program in pharmaceutical manufacture of irinotecan hydrochloride.

Determination of trace elements in ground water by two preconcentration methods using atomic absorption spectrometry

International Nuclear Information System (INIS)

Elhag, A. Y.

2004-01-01

This is a comparative study between two different methods of preconcentration done to separate the trace elements cadmium, nickel. chromium, manganese, copper, zinc, and lead in drinking (ground) water samples taken from different locations in Gezira State, central Sudan (the map); these methods are (coprecipitation) with aluminium hydroxide and by Ammonium Pyrrolidine Dithiocarbamate (APDC) using Methyl Isobutyl Ketone (MIBK) as an organic solvent; and subsequent analysis by Atomic Absorption Spectrometry (AAS) for both methods. The result of comparison showed the superiority of the (APDC) coprecipitation method over the aluminium hydroxide coprecipitation method in the total percentage recoveries of the studied trace elements in drinking (ground) water samples, such results confirm previous studies. This study also involves direct analysis of these water samples by atomic absorption spectrometry to determine the concentrations of trace elements Cadmium, Nickel, Chromium, Manganese, Copper, Zinc and Lead and compare it to the corresponding guide line values described by the World Health Organization and the maximum concentrations of trace elements in drinking water permitted by the Sudanese Standards and Metrology Organizations (SSMO), where the concentrations of some elements in some samples were found to be different than the described values by both of the organizations. The study includes a trial to throw light on the effect of the proximity of the water samples sources to the Blue Nile river on its trace elements concentrations; no relation was proved to exist in that respect.(Author)

Chemometric approach for development, optimization, and validation of different chromatographic methods for separation of opium alkaloids.

Science.gov (United States)

Acevska, J; Stefkov, G; Petkovska, R; Kulevanova, S; Dimitrovska, A

2012-05-01

The excessive and continuously growing interest in the simultaneous determination of poppy alkaloids imposes the development and optimization of convenient high-throughput methods for the assessment of the qualitative and quantitative profile of alkaloids in poppy straw. Systematic optimization of two chromatographic methods (gas chromatography (GC)/flame ionization detector (FID)/mass spectrometry (MS) and reversed-phase (RP)-high-performance liquid chromatography (HPLC)/diode array detector (DAD)) for the separation of alkaloids from Papaver somniferum L. (Papaveraceae) was carried out. The effects of various conditions on the predefined chromatographic descriptors were investigated using chemometrics. A full factorial linear design of experiments for determining the relationship between chromatographic conditions and the retention behavior of the analytes was used. Central composite circumscribed design was utilized for the final method optimization. By conducting the optimization of the methods in very rational manner, a great deal of excessive and unproductive laboratory research work was avoided. The developed chromatographic methods were validated and compared in line with the resolving power, sensitivity, accuracy, speed, cost, ecological aspects, and compatibility with the poppy straw extraction procedure. The separation of the opium alkaloids using the GC/FID/MS method was achieved within 10 min, avoiding any derivatization step. This method has a stronger resolving power, shorter analysis time, better cost/effectiveness factor than the RP-HPLC/DAD method and is in line with the "green trend" of the analysis. The RP-HPLC/DAD method on the other hand displayed better sensitivity for all tested alkaloids. The proposed methods provide both fast screening and an accurate content assessment of the six alkaloids in the poppy samples obtained from the selection program of Papaver strains.

Development and validation of analytical methods for dietary supplements

International Nuclear Information System (INIS)

Sullivan, Darryl; Crowley, Richard

2006-01-01

The expanding use of innovative botanical ingredients in dietary supplements and foods has resulted in a flurry of research aimed at the development and validation of analytical methods for accurate measurement of active ingredients. The pressing need for these methods is being met through an expansive collaborative initiative involving industry, government, and analytical organizations. This effort has resulted in the validation of several important assays as well as important advances in the method engineering procedures which have improved the efficiency of the process. The initiative has also allowed researchers to hurdle many of the barricades that have hindered accurate analysis such as the lack of reference standards and comparative data. As the availability for nutraceutical products continues to increase these methods will provide consumers and regulators with the scientific information needed to assure safety and dependable labeling

Quantitative Analysis of Ingenol in Euphorbia species via Validated Isotope Dilution Ultra-high Performance Liquid Chromatography Tandem Mass Spectrometry

Czech Academy of Sciences Publication Activity Database

Béres, T.; Dragull, K.; Pospíšil, Jiří; Tarkowská, Danuše; Dančák, M.; Bíba, Ondřej; Tarkowski, P.; Doležal, K.; Strnad, Miroslav

2018-01-01

Roč. 29, č. 1 (2018), s. 23-29 ISSN 0958-0344 R&D Projects: GA ČR GA17-14007S; GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : Euphorbia genus * ingenol * isotope-dilution method * mass spectrometry * ultra-high performance liquid chromatography Subject RIV: FD - Oncology ; Hematology OBOR OECD: Analytical chemistry Impact factor: 2.292, year: 2016

Establishment of inherent stability of pramipexole and development of validated stability indicating LC–UV and LC–MS method

Directory of Open Access Journals (Sweden)

Shubhangi M. Pawar

2013-04-01

Full Text Available Pramipexole belongs to a class of nonergot dopamine agonist recently approved for the treatment of early and advanced Parkinson's disease. A validated specific stability indicating reversed-phase liquid chromatographic method has been developed for the quantitative determination of pramipexole in bulk as well as in pharmaceutical dosage forms in the presence of degradation products. Forced degradation studies were performed by exposition of drug to hydrolytic (acidic and basic, oxidative and photolytic stress conditions, as defined under ICH guideline Q1A (R2. Significant degradation was observed under hydrolytic, oxidative and photolytic conditions and the degradation products formed were identified by LC–MS. Keywords: Degradation products, Forced degradation/stress studies, Liquid chromatography mass spectrometry, Pramipexole, Reversed-phase liquid chromatography

Comparison of Titration ICP and XRF Spectrometry Methods in Determination of Cerium in Lens Polishing Powder

International Nuclear Information System (INIS)

Ninlaphruk, Sumalee; Pichestapong, Pipat; Mungpayabal, Harinate; Jiyavaranant, Thitima; Srisukho, Supapan; Chaisai, Prapassurn

2004-10-01

Three analytical methods in determination of cerium in cerium oxide separated from monazite ore for producing lens polishing powder were compared. These methods are titration ICP and XRF spectrometry techniques. The cerium oxide sample with estimated 45% cerium content needed to be digested and converted into solution before the analysis. The analytical results shown significantly no difference between each method. However, the titration method was found to be more convenient and suitable for quality control in the production of cerium oxide as it does not require standard cerium and the complicated analytical instruments

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.

Nanoparticle-assisted laser desorption/ionization mass spectrometry: Novel sample preparation methods and nanoparticle screening for plant metabolite imaging

Energy Technology Data Exchange (ETDEWEB)

Yagnik, Gargey B. [Iowa State Univ., Ames, IA (United States)

2016-02-19

The main goal of the presented research is development of nanoparticle based matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS). This dissertation includes the application of previously developed data acquisition methods, development of novel sample preparation methods, application and comparison of novel nanoparticle matrices, and comparison of two nanoparticle matrix application methods for MALDI-MS and MALDI-MS imaging.

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....

A general screening method for doping agents in human urine by solid phase extraction and liquid chromatography/time-of-flight mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Kolmonen, Marjo [Forensic Toxicology Division, Department of Forensic Medicine, University of Helsinki (Finland) and Doping Control Laboratory, United Laboratories Ltd., Helsinki (Finland)]. E-mail: marjo.kolmonen@helsinki.fi; Leinonen, Antti [Doping Control Laboratory, United Laboratories Ltd., Helsinki (Finland); Pelander, Anna [Forensic Toxicology Division, Department of Forensic Medicine, University of Helsinki (Finland); Ojanperae, Ilkka [Forensic Toxicology Division, Department of Forensic Medicine, University of Helsinki (Finland)

2007-02-28

A general screening method based on solid phase extraction (SPE) and liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) was developed and investigated with 124 different doping agents, including stimulants, {beta}-blockers, narcotics, {beta}{sub 2}-adrenergic agonists, agents with anti-estrogenic activity, diuretics and cannabinoids. Mixed mode cation exchange/C8 cartridges were applied to SPE, and chromatography was based on gradient elution on a C18 column. Ionization of the analytes was achieved with electrospray ionization in the positive mode. Identification by LC/TOFMS was based on retention time, accurate mass and isotopic pattern. Validation of the method consisted of analysis of specificity, analytical recovery, limit of detection and repeatability. The minimum required performance limit (MRPL), established by World Anti-Doping Agency (WADA), was attained to 97 doping agents. The extraction recoveries varied between 33 and 98% and the median was 58%. Mass accuracy was always better than 5 ppm, corresponding to a maximum mass error of 0.7 mDa. The repeatability of the method for spiked urine samples, expressed as median of relative standard deviations (RSD%) at concentrations of MRPL and 10 times MRPL, were 14% and 9%, respectively. The suitability of the LC/TOFMS method for doping control was demonstrated with authentic urine samples.

Validating the JobFit system functional assessment method

Energy Technology Data Exchange (ETDEWEB)

Jenny Legge; Robin Burgess-Limerick

2007-05-15

Workplace injuries are costing the Australian coal mining industry and its communities $410 Million a year. This ACARP study aims to meet those demands by developing a safe, reliable and valid pre-employment functional assessment tool. All JobFit System Pre-Employment Functional Assessments (PEFAs) consist of a musculoskeletal screen, balance test, aerobic fitness test and job-specific postural tolerances and material handling tasks. The results of each component are compared to the applicant's job demands and an overall PEFA score between 1 and 4 is given with 1 being the better score. The reliability study and validity study were conducted concurrently. The reliability study examined test-retest, intra-tester and inter-tester reliability of the JobFit System Functional Assessment Method. Overall, good to excellent reliability was found, which was sufficient to be used for comparison with injury data for determining the validity of the assessment. The overall assessment score and material handling tasks had the greatest reliability. The validity study compared the assessment results of 336 records from a Queensland underground and open cut coal mine with their injury records. A predictive relationship was found between PEFA score and the risk of a back/trunk/shoulder injury from manual handling. An association was also found between PEFA score of 1 and increased length of employment. Lower aerobic fitness test results had an inverse relationship with injury rates. The study found that underground workers, regardless of PEFA score, were more likely to have an injury when compared to other departments. No relationship was found between age and risk of injury. These results confirm the validity of the JobFit System Functional Assessment method.

Skin penetration behaviour of sesquiterpene lactones from different Arnica preparations using a validated GC-MSD method.

Science.gov (United States)

Wagner, Steffen; Merfort, Irmgard

2007-01-04

Preparations of Arnica montana L. are widely used for the topical treatment of inflammatory diseases. The anti-inflammatory activity is mainly attributed to their sesquiterpene lactones (SLs) from the helenalin and 11alpha,13-dihydrohelenalin type. To study the penetration kinetics of SLs in Arnica preparations, a stripping method with adhesive tape and pig skin as a model was used. For the determination of SLs in the stripped layers of the stratum corneum (SC), a gas chromatography/mass spectrometry method was developed and validated. Thereby the amount of helenalin derivatives was calculated as helenalin isobutyrate, and 11alpha,13-dihydrohelenalin derivatives as 11alpha,13-dihydrohelenalin methacrylate. This GC-MSD method is suitable also to determine low amounts of SLs in Arnica preparations. The penetration behaviour of one gel preparation and two ointment preparations was investigated. The SLs of all preparations show a comparable penetration in and a permeation through the stratum corneum, the uppermost part of the skin. Interestingly, the gel preparation showed a decrease of the penetration rate over 4h, whereas the penetration rate of ointments kept constant over time. Moreover, we could demonstrate that the totally penetrated amount of SLs only depends on the kind of the formulation and of the SLs-content in the formulation but not on the SLs composition or on the used extraction agent.

A simple validated multi-analyte method for detecting drugs in oral fluid by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS).

Science.gov (United States)

Zheng, Yufang; Sparve, Erik; Bergström, Mats

2018-06-01

A UPLC-MS/MS method was developed to identify and quantitate 37 commonly abused drugs in oral fluid. Drugs of interest included amphetamines, benzodiazepines, cocaine, opiates, opioids, phencyclidine and tetrahydrocannabinol. Sample preparation and extraction are simple, and analysis times short. Validation showed satisfactory performance at relevant concentrations. The possibility of contaminated samples as well as the interpretation in relation to well-knows matrices, such as urine, will demand further study. Copyright © 2017 John Wiley & Sons, Ltd.

Content Validity of National Post Marriage Educational Program Using Mixed Methods

Science.gov (United States)

MOHAJER RAHBARI, Masoumeh; SHARIATI, Mohammad; KERAMAT, Afsaneh; YUNESIAN, Masoud; ESLAMI, Mohammad; MOUSAVI, Seyed Abbas; MONTAZERI, Ali

2015-01-01

Background: Although the validity of content of program is mostly conducted with qualitative methods, this study used both qualitative and quantitative methods for the validation of content of post marriage training program provided for newly married couples. Content validity is a preliminary step of obtaining authorization required to install the program in country's health care system. Methods: This mixed methodological content validation study carried out in four steps with forming three expert panels. Altogether 24 expert panelists were involved in 3 qualitative and quantitative panels; 6 in the first item development one; 12 in the reduction kind, 4 of them were common with the first panel, and 10 executive experts in the last one organized to evaluate psychometric properties of CVR and CVI and Face validity of 57 educational objectives. Results: The raw data of post marriage program had been written by professional experts of Ministry of Health, using qualitative expert panel, the content was more developed by generating 3 topics and refining one topic and its respective content. In the second panel, totally six other objectives were deleted, three for being out of agreement cut of point and three on experts' consensus. The validity of all items was above 0.8 and their content validity indices (0.8–1) were completely appropriate in quantitative assessment. Conclusion: This study provided a good evidence for validation and accreditation of national post marriage program planned for newly married couples in health centers of the country in the near future. PMID:26056672

Method development and validation for naratriptan determination in human plasma by HPLC with tandem mass spectrometry detection, and its application to bioequivalence study

Directory of Open Access Journals (Sweden)

Balasekhara Reddy Challa

2011-03-01

Full Text Available The authors developed a simple, sensitive and specific liquid chromatography-tandem mass spectrometry (LC-MS/MS method for the quantification of naratriptan (NP in human plasma using naratriptan-d3 (NPD3 as an internal standard (IS. Chromatographic separation was performed on a Zorbax SB-C18, 75 x 4.6 mm, 3.5 µm column with an isocratic mobile phase composed of 0.1% formic acid : acetonitrile (50:50 v/v, at a flow-rate of 0.6 mL/min. NP and NPD3 were detected with proton adducts at m/z 336.5→98.0 and 339.4→101.0 in selected reaction monitoring (SRM positive mode, respectively. The liquid-liquid extraction method was used to extract the NP and NPD3. This method was validated over a linear concentration range of 0.1-25.0 ng/mL with a correlation coefficient of (r2 > 0.9998. The Intra-day and Interday precision was found to be 1.8 to 3.6%, and 2.3 to 2.6%, and accuracy to be 101.7- 104.2% and 101.8 to 102.9%, respectively. NP was found to be stable throughout freeze-thaw (three cycles, bench top and auto sampler stability studies. This method was successfully applied for the analysis of plasma samples following oral administration of NP (2.5 mg in 31 healthy Indian male human volunteers under fasting conditions.Os autores desenvolveram um método simples, sensível e específico de cromatografia líquida-espectrometria de massa-tandem (LC-MS/MS para a quantificação de naratriptan (NP em plasma humano empregando naratriptan-d3 (NPD3 como padrão interno de referência (IS. A separação cromatográfica foi realizada em coluna Zorbax SB-C18, 75 x 4,6 mm, 3,5 μm com fase móvel isocrática composta por 0,1% ácido fórmico : acetronitrila (50:50 v/v e taxa de fluxo de 0,6 mL/min. NP e NPD3 foram detectados com adutos de prótons a m/z 336.5→98.0 e 339.4→101.0 in em modo positivo do tipo monitoramento de reação selecionada (SRM, respectivamente. Extração líquido-líquido foi empregada para extrair NP e NPD3, sendo o método validado

Method validation and dissipation kinetics of four herbicides in maize and soil using QuEChERS sample preparation and liquid chromatography tandem mass spectrometry.

Science.gov (United States)

Pang, Nannan; Wang, Tielong; Hu, Jiye

2016-01-01

A versatile liquid chromatography tandem mass spectrometry method with modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation was developed for the determination of rimsulfuron, mesotrione, fluroxypyr-meptyl, and fluroxypyr. By adjusting the amount of graphitized carbon black, the herbicide analytes could be quantified with satisfactory recoveries in the range of 80-110%. A dissipation kinetics study conducted under open field conditions at two sites during 2014 showed first order equations with half-lives between 0.6d and 3.6d, illustrating an appropriate degree of stability and safety. The dissipation kinetics were different in the different matrices. Although the herbicides had higher initial residues in straw than those in soil, they degraded faster in straw. The terminal residues for the herbicides formulated in two water dispersible granules were all below maximum residue limits. These results not only gave insights about the analytes but also contributed to environmental protection and food safety. Copyright © 2015 Elsevier Ltd. All rights reserved.

Validation of Alternative In Vitro Methods to Animal Testing: Concepts, Challenges, Processes and Tools.

Science.gov (United States)

Griesinger, Claudius; Desprez, Bertrand; Coecke, Sandra; Casey, Warren; Zuang, Valérie

This chapter explores the concepts, processes, tools and challenges relating to the validation of alternative methods for toxicity and safety testing. In general terms, validation is the process of assessing the appropriateness and usefulness of a tool for its intended purpose. Validation is routinely used in various contexts in science, technology, the manufacturing and services sectors. It serves to assess the fitness-for-purpose of devices, systems, software up to entire methodologies. In the area of toxicity testing, validation plays an indispensable role: "alternative approaches" are increasingly replacing animal models as predictive tools and it needs to be demonstrated that these novel methods are fit for purpose. Alternative approaches include in vitro test methods, non-testing approaches such as predictive computer models up to entire testing and assessment strategies composed of method suites, data sources and decision-aiding tools. Data generated with alternative approaches are ultimately used for decision-making on public health and the protection of the environment. It is therefore essential that the underlying methods and methodologies are thoroughly characterised, assessed and transparently documented through validation studies involving impartial actors. Importantly, validation serves as a filter to ensure that only test methods able to produce data that help to address legislative requirements (e.g. EU's REACH legislation) are accepted as official testing tools and, owing to the globalisation of markets, recognised on international level (e.g. through inclusion in OECD test guidelines). Since validation creates a credible and transparent evidence base on test methods, it provides a quality stamp, supporting companies developing and marketing alternative methods and creating considerable business opportunities. Validation of alternative methods is conducted through scientific studies assessing two key hypotheses, reliability and relevance of the

Development of a gas chromatography-mass spectrometry method for the determination of pesticides in gaseous and particulate phases in the atmosphere

Energy Technology Data Exchange (ETDEWEB)

Borras, E.; Sanchez, P.; Munoz, A. [Instituto Universitario Centro de Estudios Ambientales del Mediterraneo CEAM-UMH (Fundacion CEAM-UMH), 46980 Paterna, Valencia (Spain); Tortajada-Genaro, L.A., E-mail: luitorge@qim.upv.es [Instituto IDM, Departamento de Quimica, Universitat Politecnica de Valencia, Cami de Vera s/n 46022 Valencia (Spain)

2011-08-05

Highlights: {yields} An efficient method for the determination of sixteen pesticides in atmospheric samples. {yields} XAD-4 is an interesting support for collecting gas-phase pesticides, with similar performances than the conventional XAD-2. {yields} The ultrasonic extraction is cheaper, less aggressive and time-consuming with excellent analytical parameters. {yields} The method has been successfully tested by using high volume atmospheric simulation chamber and field campaigns. - Abstract: A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography-mass spectrometry (GC-MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interferences. The pesticides were benfluralin, bitertanol, buprofezin, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, ethalfluralin, fenthion, lindane, malathion, methidathion, propachlor, propanil, pyriproxifen, tebuconazol and trifluralin. Comparisons of two types of sampling filters (quartz and glass fibre) and four types of solid-phase cartridges (XAD-2, XAD-4, Florisil and Orbo-49P) showed that the most suitable supports were glass fibre filter for particulate pesticides and XAD-2 and XAD-4 cartridges for gaseous pesticides (>95% recovery). Evaluations of elution solvents for ultrasonic-assisted extraction demonstrated that isooctane is better than ethylacetate, dichloromethane, methanol or a mixture of acetone:hexane (1:1). Recovery assays and the standard addition method were performed to validate the proposed methodology. Moreover, large simulator chamber experiments allowed the best study of the gas-particle partitioning of pesticides for testing the sampling efficiency for the validation of an analytical multiresidue method for pesticides in air. Satisfactory analytical parameters were obtained, with a repeatability of 5 {+-} 1%, a

Development of a gas chromatography-mass spectrometry method for the determination of pesticides in gaseous and particulate phases in the atmosphere

International Nuclear Information System (INIS)

Borras, E.; Sanchez, P.; Munoz, A.; Tortajada-Genaro, L.A.

2011-01-01

Highlights: → An efficient method for the determination of sixteen pesticides in atmospheric samples. → XAD-4 is an interesting support for collecting gas-phase pesticides, with similar performances than the conventional XAD-2. → The ultrasonic extraction is cheaper, less aggressive and time-consuming with excellent analytical parameters. → The method has been successfully tested by using high volume atmospheric simulation chamber and field campaigns. - Abstract: A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography-mass spectrometry (GC-MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interferences. The pesticides were benfluralin, bitertanol, buprofezin, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, ethalfluralin, fenthion, lindane, malathion, methidathion, propachlor, propanil, pyriproxifen, tebuconazol and trifluralin. Comparisons of two types of sampling filters (quartz and glass fibre) and four types of solid-phase cartridges (XAD-2, XAD-4, Florisil and Orbo-49P) showed that the most suitable supports were glass fibre filter for particulate pesticides and XAD-2 and XAD-4 cartridges for gaseous pesticides (>95% recovery). Evaluations of elution solvents for ultrasonic-assisted extraction demonstrated that isooctane is better than ethylacetate, dichloromethane, methanol or a mixture of acetone:hexane (1:1). Recovery assays and the standard addition method were performed to validate the proposed methodology. Moreover, large simulator chamber experiments allowed the best study of the gas-particle partitioning of pesticides for testing the sampling efficiency for the validation of an analytical multiresidue method for pesticides in air. Satisfactory analytical parameters were obtained, with a repeatability of 5 ± 1%, a reproducibility of 13

Determination of Modafinil in Tablet Formulation Using Three New Validated Spectrophotometric Methods

International Nuclear Information System (INIS)

Basniwal, P.K.; Jain, D.; Basniwal, P.K.

2014-01-01

In this study, three new UV spectrophotometric methods viz. linear regression equation (LRE), standard absorptivity (SA) and first order derivative (FOD) method were developed and validated for determination of modafinil in tablet form. The Beer-Lamberts law was obeyed as linear in the range of 10-50 μg/ mL and all the methods were validated for linearity, accuracy, precision and robustness. These methods were successfully applied for assay of modafinil drug content in tablets in the range of 100.20 - 100.42 %, 100.11 - 100.58 % and 100.25 - 100.34 %, respectively with acceptable standard deviation (less than two) for all the methods. The validated spectrophotometric methods may be successfully applied for assay, dissolution studies, bio-equivalence studies as well as routine analysis in pharmaceutical industries. (author)

An Engineering Method of Civil Jet Requirements Validation Based on Requirements Project Principle

Science.gov (United States)

Wang, Yue; Gao, Dan; Mao, Xuming

2018-03-01

A method of requirements validation is developed and defined to meet the needs of civil jet requirements validation in product development. Based on requirements project principle, this method will not affect the conventional design elements, and can effectively connect the requirements with design. It realizes the modern civil jet development concept, which is “requirement is the origin, design is the basis”. So far, the method has been successfully applied in civil jet aircraft development in China. Taking takeoff field length as an example, the validation process and the validation method of the requirements are detailed introduced in the study, with the hope of providing the experiences to other civil jet product design.

A new method for the determination of NO2 traces using isotope dilution and mass spectrometry analysis

International Nuclear Information System (INIS)

Stevens, C.; Barat, F.; Nguyen Nghi, H.

1975-01-01

A new method for the determination of NO 2 traces, in the order of 1ppb (10 -9 ), in atmosphere and stratosphere is described. The method consists in an isotope dilution technique using 15 NO 2 , followed by the reduction of NO 2 to N 2 and a mass spectrometry analysis. A known amount of 15 NO 2 is added to the air samples. Then, NO 2 is separated from H 2 O, HNO 3 , CO 2 and N 2 O and transferred to a SiO 2 reactor by trapping at -196 deg C. In the reactor NO 2 is reduced to N 2 by reaction with electrolytic Cu heated at 580 deg C. The mass 29/mass 30 ratio corresponding to 15 N 14 N and 15 N 15 N is determined by mass spectrometry. The sensitivity of the method depends on the contamination introduced during the analysis of the sample (reagents, separation and measuring devices). The contamination is reproducible and in the order of 4.5+-0.5 10 -2 mm 3 N 2 [fr

Standard test methods for chemical analysis of ceramic whiteware materials using wavelength dispersive X-Ray fluorescence spectrometry

CERN Document Server

American Society for Testing and Materials. Philadelphia

2004-01-01

1.1 These test methods cover the determination of ten major elements (SiO2, Al2O3, Fe2O3, MgO, CaO, Na2O, K2O, TiO2, P2O5, MnO, and LOI in ceramic whitewares clays and minerals using wavelength dispersive X-ray fluorescence spectrometry (WDXRF). The sample is first ignited, then fused with lithium tetraborate and the resultant glass disc is introduced into a wavelength dispersive X-ray spectrometer. The disc is irradiated with X-rays from an X-ray tube. X-ray photons emitted by the elements in the samples are counted and concentrations determined using previously prepared calibration standards. (1) In addition to 10 major elements, the method provides a gravimetric loss-on-ignition. Note 1—Much of the text of this test method is derived directly from Major element analysis by wavelength dispersive X-ray fluorescence spectrometry, included in Ref (1). 1.2 Interferences, with analysis by WDXRF, may result from mineralogical or other structural effects, line overlaps, and matrix effects. The structure of the...

Development of a method for the simultaneous determination of multi-class pesticides in earthworms by liquid chromatography coupled to tandem electrospray mass spectrometry.

Science.gov (United States)

Daniele, Gaëlle; Lafay, Florent; Pelosi, Céline; Fritsch, Clémentine; Vulliet, Emmanuelle

2018-06-04

Agricultural intensification, and in particular the use of pesticides, leads over the years to a loss of biodiversity and a decline of ecosystem services in cultivated zones and agricultural landscapes. Among the animal communities involved in the functioning of agro-ecosystems, earthworms are ubiquitous and recognized as indicators of land uses and cultural practices. However, little data is available on the levels of pesticides in such organisms in natura, which would allow estimating their actual exposure and the potentially resulting impacts. Thus, the objective of this study was to develop a sensitive analytical methodology to detect and quantify 27 currently used pesticides in earthworms (Allolobophora chlorotica). A modified QuEChERS extraction was implemented on individual earthworms. This step was followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The whole analytical method was validated on spiked earthworm blank samples, with regard to linearity (from 1 to 100 method limit of quantification, r 2  > 0.95), intra-day precision (relative standard deviation (RSD) Graphical abstract.

In-situ gamma spectrometry method for determination of environmental gamma dose; Metodo de espectrometria gamma in situ para determinacao de dose gama ambiental

Energy Technology Data Exchange (ETDEWEB)

Conti, Claudio de Carvalho

1995-07-15

This work tries to establish a methodology for germanium detectors calibration, normally used for in situ gamma ray spectrometry, for determining the environmental exposure rate in function of the energy of the incident photons. For this purpose a computer code has been developed, based on the stripping method, for the computational spectra analysis to calculate the contribution of the partial absorption of the gamma rays (Compton effect) in the active and nonactive parts of the detector. The resulting total absorption spectrum is then converted to fluence distribution in function of the energy for the photons reaching the detector, which is then used to calculate the exposure rate or kerma in air. The unfolding and fluency convention parameters are determined by detector calibration using point gamma sources. The method is validated by comparison of the results against the calculated exposure rate at a point of interest for the standards. This method is used for the direct measurement of the exposure rate distribution in function of the energy at the site, in situ measurement technic, leading to rapid results during an emergency situation and also used for indoor measurements. (author)

Some analytical aspects of the Moessbauer spectrometry

International Nuclear Information System (INIS)

Meisel, W.

1975-01-01

Analytical applications of Moessbauer spectrometry are reviewed. Various methods of analysis (qualitative, semiquantitative and quantitative) using the Moessbauer effect are dealt with. Sensitivity and accuracy of Moessbauer spectrometry in analytical applications are discussed. (Z.S.)

Use of Tritium Accelerator Mass Spectrometry for Tree Ring Analysis

Science.gov (United States)

LOVE, ADAM H.; HUNT, JAMES R.; ROBERTS, MARK L.; SOUTHON, JOHN R.; CHIARAPPA - ZUCCA, MARINA L.; DINGLEY, KAREN H.

2010-01-01

Public concerns over the health effects associated with low-level and long-term exposure to tritium released from industrial point sources have generated the demand for better methods to evaluate historical tritium exposure levels for these communities. The cellulose of trees accurately reflects the tritium concentration in the source water and may contain the only historical record of tritium exposure. The tritium activity in the annual rings of a tree was measured using accelerator mass spectrometry to reconstruct historical annual averages of tritium exposure. Milligram-sized samples of the annual tree rings from a Tamarix located at the Nevada Test Site are used for validation of this methodology. The salt cedar was chosen since it had a single source of tritiated water that was well-characterized as it varied over time. The decay-corrected tritium activity of the water in which the salt cedar grew closely agrees with the organically bound tritium activity in its annual rings. This demonstrates that the milligram-sized samples used in tritium accelerator mass spectrometry are suited for reconstructing anthropogenic tritium levels in the environment. PMID:12144257

Mass spectrometry as a quantitative tool in plant metabolomics

Science.gov (United States)

Jorge, Tiago F.; Mata, Ana T.

2016-01-01

Metabolomics is a research field used to acquire comprehensive information on the composition of a metabolite pool to provide a functional screen of the cellular state. Studies of the plant metabolome include the analysis of a wide range of chemical species with very diverse physico-chemical properties, and therefore powerful analytical tools are required for the separation, characterization and quantification of this vast compound diversity present in plant matrices. In this review, challenges in the use of mass spectrometry (MS) as a quantitative tool in plant metabolomics experiments are discussed, and important criteria for the development and validation of MS-based analytical methods provided. This article is part of the themed issue ‘Quantitative mass spectrometry’. PMID:27644967

An indirect method for determining phosphorus in aluminium alloys by atomic-absorption spectrometry.

Science.gov (United States)

Bernal, J L; Del Nozal, M A; Deban, L; Aller, A J

1981-07-01

An indirect method is described for the determination of phosphorus in aluminium alloys. Ammonium molybdate is added to a solution of the aluminium alloy and the molybdophosphoric acid formed is selectively extracted into n-butyl acetate. The twelve molybdenum atoms associated with each phosphate ion are determined by direct atomic-absorption spectrometry with the n-butyl acetate phase in a nitrous oxide-acetylene flame, with measurement at 313.2 nm. The most suitable conditions have been established and the effect of other ions has been studied.

Development and Validation of a Stability-Indicating LC-UV Method ...

African Journals Online (AJOL)

Keywords: Ketotifen, Cetirizine, Stability indicating method, Stressed conditions, Validation. Tropical ... in biological fluids [13] are also reported. Stability indicating HPLC method is reported for ketotifen where drug is ..... paracetamol, cetirizine.

Determination of methylmercury and estimation of total mercury in seafood using high performance liquid chromatography (HPLC) and inductively coupled plasma-mass spectrometry (ICP-MS): Method development and validation

Energy Technology Data Exchange (ETDEWEB)

Hight, Susan C. [Elemental Research Branch, Center for Food Safety and Applied Nutrition, US Food and Drug Administration, 5100 Paint Branch Parkway, College Park, MD 20740-3835 (United States)]. E-mail: susan.hight@fda.gov; Cheng, John [Elemental Research Branch, Center for Food Safety and Applied Nutrition, US Food and Drug Administration, 5100 Paint Branch Parkway, College Park, MD 20740-3835 (United States)]. E-mail: john.cheng@fda.gov

2006-05-17

A method was developed for determination of methylmercury and estimation of total mercury in seafood. Mercury (Hg) compounds were extracted from 0.5 g edible seafood or 0.2 g lyophilized reference material by adding 50 ml aqueous 1% w/v L-cysteine.HCl.H{sub 2}O and heating 120 min at 60 deg. C in glass vials. Hg compounds in 50 {mu}l of filtered extract were separated by reversed-phase high performance liquid chromatography using a C-18 column and aqueous 0.1% w/v L-cysteine.HCl.H{sub 2}O + 0.1% w/v L-cysteine mobile phase at room temperature and were detected by inductively coupled plasma-mass spectrometry at mass-to-charge ratio 202. Total Hg was calculated as the mathematical sum of methyl and inorganic Hg determined in extracts. For seafoods containing 0.055-2.78 mg kg{sup -1} methylmercury and 0.014-0.137 mg kg{sup -1} inorganic Hg, precision of analyses was {<=}5% relative standard deviation (R.S.D.) for methylmercury and {<=}9% R.S.D. for inorganic Hg. Recovery of added analyte was 94% for methylmercury and 98% for inorganic Hg. Methyl and total Hg results for reference materials agreed with certified values. Limits of quantitation were 0.007 mg kg{sup -1} methylmercury and 0.005 mg kg{sup -1} inorganic Hg in edible seafood and 0.017 mg kg{sup -1} methylmercury and 0.012 mg kg{sup -1} inorganic Hg in lyophilized reference materials. Evaluation of analyte stability demonstrated that L-cysteine both stabilized and de-alkylated methylmercury, depending on holding time and cysteine concentration. Polypropylene adversely affected methylmercury stability. Total Hg results determined by this method were equivalent to results determined independently by cold vapour-atomic absorption spectrometry. Methylmercury was the predominant form of Hg in finfish. Ratios of methylmercury/total Hg determined by this method were 93-98% for finfish and 38-48% for mollusks.

Fuzzy-logic based strategy for validation of multiplex methods: example with qualitative GMO assays.

Science.gov (United States)

Bellocchi, Gianni; Bertholet, Vincent; Hamels, Sandrine; Moens, W; Remacle, José; Van den Eede, Guy

2010-02-01

This paper illustrates the advantages that a fuzzy-based aggregation method could bring into the validation of a multiplex method for GMO detection (DualChip GMO kit, Eppendorf). Guidelines for validation of chemical, bio-chemical, pharmaceutical and genetic methods have been developed and ad hoc validation statistics are available and routinely used, for in-house and inter-laboratory testing, and decision-making. Fuzzy logic allows summarising the information obtained by independent validation statistics into one synthetic indicator of overall method performance. The microarray technology, introduced for simultaneous identification of multiple GMOs, poses specific validation issues (patterns of performance for a variety of GMOs at different concentrations). A fuzzy-based indicator for overall evaluation is illustrated in this paper, and applied to validation data for different genetically modified elements. Remarks were drawn on the analytical results. The fuzzy-logic based rules were shown to be applicable to improve interpretation of results and facilitate overall evaluation of the multiplex method.

Screening for trace explosives by AccuTOF™-DART®: an in-depth validation study.

Science.gov (United States)

Sisco, Edward; Dake, Jeffrey; Bridge, Candice

2013-10-10

Ambient ionization mass spectrometry is finding increasing utility as a rapid analysis technique in a number of fields. In forensic science specifically, analysis of many types of samples, including drugs, explosives, inks, bank dye, and lotions, has been shown to be possible using these techniques [1]. This paper focuses on one type of ambient ionization mass spectrometry, Direct Analysis in Real Time Mass Spectrometry (DART-MS or DART), and its viability as a screening tool for trace explosives analysis. In order to assess viability, a validation study was completed which focused on the analysis of trace amounts of nitro and peroxide based explosives. Topics which were studied, and are discussed, include method optimization, reproducibility, sensitivity, development of a search library, discrimination of mixtures, and blind sampling. Advantages and disadvantages of this technique over other similar screening techniques are also discussed. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Tools for the Validation of Genomes and Transcriptomes with Proteomics data

DEFF Research Database (Denmark)

Pang, Chi Nam Ignatius; Aya, Carlos; Tay, Aidan

data generated from protein mass spectrometry. We are developing a set of tools which allow users to: •Co-visualise genomics, transcriptomics, and proteomics data using the Integrated Genomics Viewer (IGV).1 •Validate the existence of genes and mRNAs using peptides identified from mass spectrometry...

Method development and validation of potent pyrimidine derivative by UV-VIS spectrophotometer.

Science.gov (United States)

Chaudhary, Anshu; Singh, Anoop; Verma, Prabhakar Kumar

2014-12-01

A rapid and sensitive ultraviolet-visible (UV-VIS) spectroscopic method was developed for the estimation of pyrimidine derivative 6-Bromo-3-(6-(2,6-dichlorophenyl)-2-(morpolinomethylamino) pyrimidine4-yl) -2H-chromen-2-one (BT10M) in bulk form. Pyrimidine derivative was monitored at 275 nm with UV detection, and there is no interference of diluents at 275 nm. The method was found to be linear in the range of 50 to 150 μg/ml. The accuracy and precision were determined and validated statistically. The method was validated as a guideline. The results showed that the proposed method is suitable for the accurate, precise, and rapid determination of pyrimidine derivative. Graphical Abstract Method development and validation of potent pyrimidine derivative by UV spectroscopy.

Mercury speciation analysis in seafood by species-specific isotope dilution: method validation and occurrence data

Energy Technology Data Exchange (ETDEWEB)

Clemens, Stephanie; Guerin, Thierry [Agence Nationale de Securite Sanitaire de l' Alimentation, Laboratoire de Securite des Aliments de Maisons-Alfort, Unite des Contaminants Inorganiques et Mineraux de l' Environnement, ANSES, Maisons-Alfort (France); Monperrus, Mathilde; Donard, Olivier F.X.; Amouroux, David [IPREM UMR 5254 CNRS - Universite de Pau et des Pays de l' Adour, Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Institut des Sciences Analytiques et de Physico-chimie pour l' Environnement et les Materiaux, Pau Cedex (France)

2011-11-15

Methylmercury (MeHg) and total mercury (THg) in seafood were determined using species-specific isotope dilution analysis and gas chromatography combined with inductively coupled plasma mass spectrometry. Sample preparation methods (extraction and derivation step) were evaluated on certified reference materials using isotopically enriched Hg species. Solid-liquid extraction, derivation by propylation and automated agitation gave excellent accuracy and precision results. Satisfactory figures of merit for the selected method were obtained in terms of limit of quantification (1.2 {mu}g Hg kg{sup -1} for MeHg and 1.4 {mu}g Hg kg{sup -1} for THg), repeatability (1.3-1.7%), intermediate precision reproducibility (1.5% for MeHg and 2.2% for THg) and trueness (bias error less than 7%). By means of a recent strategy based on accuracy profiles ({beta}-expectation tolerance intervals), the selected method was successfully validated in the range of approximately 0.15-5.1 mg kg{sup -1} for MeHg and 0.27-5.2 mg kg{sup -1} for THg. Probability {beta} was set to 95% and the acceptability limits to {+-}15%. The method was then applied to 62 seafood samples representative of consumption in the French population. The MeHg concentrations were generally low (1.9-588 {mu}g kg{sup -1}), and the percentage of MeHg varied from 28% to 98% in shellfish and from 84% to 97% in fish. For all real samples tested, methylation and demethylation reactions were not significant, except in one oyster sample. The method presented here could be used for monitoring food contamination by MeHg and inorganic Hg in the future to more accurately assess human exposure. (orig.)

Matrix-assisted laser desorption ionization-time of flight mass spectrometry for direct bacterial identification from positive blood culture pellets.

Science.gov (United States)

Prod'hom, Guy; Bizzini, Alain; Durussel, Christian; Bille, Jacques; Greub, Gilbert

2010-04-01

An ammonium chloride erythrocyte-lysing procedure was used to prepare a bacterial pellet from positive blood cultures for direct matrix-assisted laser desorption-ionization time of flight (MALDI-TOF) mass spectrometry analysis. Identification was obtained for 78.7% of the pellets tested. Moreover, 99% of the MALDI-TOF identifications were congruent at the species level when considering valid scores. This fast and accurate method is promising.

Theory of error for target factor analysis with applications to mass spectrometry and nuclear magnetic resonance spectrometry

International Nuclear Information System (INIS)

Malinowski, E.R.

1978-01-01

Based on the theory of error for abstract factor analysis described earlier, a theory of error for target factor analysis is developed. The theory shows how the error in the data matrix mixes with the error in the target test vector. The apparent error in a target test is found to be a vector sum of the real error in the target vector and the real error in the predicted vector. The theory predicts the magnitudes of these errors without requiring any a priori knowledge of the error in the data matrix or the target vector. A reliability function and a spoil function are developed for the purpose of assessing the validity and the worthiness of a target vector. Examples from model data, mass spectrometry and nuclear magnetic resonance spectrometry are presented. (Auth.)

Rapid Quantification of Major Volatile Metabolites in Fermented Food and Beverages Using Gas Chromatography-Mass Spectrometry.

Science.gov (United States)

Pinu, Farhana R; Villas-Boas, Silas G

2017-07-26

Here we present a method for the accurate quantification of major volatile metabolites found in different food and beverages, including ethanol, acetic acid and other aroma compounds, using gas chromatography coupled to mass spectrometry (GC-MS). The method is combined with a simple sample preparation procedure using sodium chloride and anhydrous ethyl acetate. The GC-MS analysis was accomplished within 4.75 min, and over 80 features were detected, of which 40 were positively identified using an in-house and a commercialmass spectrometry (MS) library. We determined different analytical parameters of these metabolites including the limit of detection (LOD), limit of quantitation (LOQ) and range of quantification. In order to validate the method, we also determined detailed analytical characteristics of five major fermentation end products including ethanol, acetic acid, isoamyl alcohol, ethyl-L-lactate and, acetoin. The method showed very low technical variability for the measurements of these metabolites in different matrices (<3%) with an excellent accuracy (100% ± 5%), recovery (100% ± 10%), reproducibility and repeatability [Coefficient of variation (CV) 1-10%)]. To demonstrate the applicability of the method, we analysed different fermented products including balsamic vinegars, sourdough, distilled (whisky) and non-distilled beverages (wine and beer).

A long-term validation of the modernised DC-ARC-OES solid-sample method.

Science.gov (United States)

Flórián, K; Hassler, J; Förster, O

2001-12-01

The validation procedure based on ISO 17025 standard has been used to study and illustrate both the longterm stability of the calibration process of the DC-ARC solid sample spectrometric method and the main validation criteria of the method. In the calculation of the validation characteristics depending on the linearity(calibration), also the fulfilment of predetermining criteria such as normality and homoscedasticity was checked. In order to decide whether there are any trends in the time-variation of the analytical signal or not, also the Neumann test of trend was applied and evaluated. Finally, a comparison with similar validation data of the ETV-ICP-OES method was carried out.

A liquid chromatography with tandem mass spectrometry method for simultaneous determination of UTL-5g and its metabolites in human plasma.

Science.gov (United States)

Shaw, Jiajiu; Wiegand, Richard; Wu, Jianmei; Bao, Xun; Valeriote, Frederick; Li, Jing

2015-06-01

UTL-5g is a novel small-molecule TNF-α inhibitor under investigation as both a chemoprotective and radioprotective agent. Animal studies showed that pretreatment of UTL-5g protected kidney, liver, and platelets from cisplatin-induced toxicity. In addition, UTL-5g reduced liver and lung injuries induced by radiation in vivo. Although a number of preclinical studies have been conducted, a validated bioanalytical method for UTL-5g in human plasma has not been published. In this work, a sensitive and reproducible reverse-phase liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) assay was developed and validated for the determination of UTL-5g and its metabolites, 5-methylisoxazole-3-carboxylic acid (ISOX) and 2,4-dichloroaniline (DCA), in human plasma. The method involves a simple methanol precipitation step followed by injection of the supernatant onto a Waters 2695 HPLC system coupled with a Waters Quattro Micro™ triple quadrupole mass spectrometer. Chromatographic separation was accomplished using a Waters Nova-Pak C18 column maintained at 30°C, running at gradient mode with mobile phase consisting of 0.1% formic acid in water and 0.1% formic acid in methanol at a flow rate of 0.2mL/min. The analytes were monitored under positive electrospray ionization (ESI). Quantitation of these compounds in plasma was linear from 0.05 to 10μM. The lower limit of quantitation (LLOQ) was 0.05, 0.1, and 0.2μM for UTL-5g, ISOX and DCA, respectively. The accuracy and intra-and inter-day precisions were within the generally accepted criteria for bioanalytical method (5g and its metabolites, ISOX and DCA. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparing the Validity of Non-Invasive Methods in Measuring Thoracic Kyphosis and Lumbar Lordosis

Directory of Open Access Journals (Sweden)

Mohammad Yousefi

2012-04-01

Full Text Available Background: the purpose of this article is to study the validity of each of the non-invasive methods (flexible ruler, spinal mouse, and processing the image versus the one through-Ray radiation (the basic method and comparing them with each other.Materials and Methods: for evaluating the validity of each of these non-invasive methods, the thoracic Kyphosis and lumber Lordosis angle of 20 students of Birjand University (age mean and standard deviation: 26±2, weight: 72±2.5 kg, height: 169±5.5 cm through fours methods of flexible ruler, spinal mouse, and image processing and X-ray.Results: the results indicated that the validity of the methods including flexible ruler, spinal mouse, and image processing in measuring the thoracic Kyphosis and lumber Lordosis angle respectively have an adherence of 0.81, 0.87, 0.73, 0.76, 0.83, 0.89 (p>0.05. As a result, regarding the gained validity against the golden method of X-ray, it could be stated that the three mentioned non-invasive methods have adequate validity. In addition, the one-way analysis of variance test indicated that there existed a meaningful relationship between the three methods of measuring the thoracic Kyphosis and lumber Lordosis, and with respect to the Tukey’s test result, the image processing method is the most precise one.Conclusion as a result, this method could be used along with other non-invasive methods as a valid measuring method.

A rapid method for simultaneous determination of arsenic, cadmium and lead in drinking water by inductively coupled plasma mass spectrometry

Directory of Open Access Journals (Sweden)

Joshua Rey P. Torres

Full Text Available The raw water source of drinking water in most areas in the Philippines is typically river water and in some cases groundwater. These sources are prone to elevated levels of metals and metalloids that may cause exposure of the general population when the treatment of the water is inadequate. This work presents a simple method based on EPA Method 200.8 for the determination of total concentrations of arsenic (As, cadmium (Cd and lead (Pb in drinking water using inductively coupled plasma-mass spectrometry (ICP-MS as the element-selective detector. This was applied in the determination of these elements in the water supply in Metro Manila, Philippines. The method detection limits were 0.095 μg L-1, 0.043 μg L-1, and 0.114 μg L-1 for total As, Cd and Pb, respectively.The method was validated using National Institute of Standards and Technology (NIST 1643e certified reference material for trace elements in water and determined values were 60.4 ± 0.5 μg L-1, 6.7 ± 0.1 μg L-1, and 19.6 ± 0.5 μg L-1 for As, Cd and Pb, respectively. These determined values were in good agreement with the certified values in the reference material. Analysis of actual drinking water samples showed that most samples did not exceed the limit of the Philippine drinking water standard for the elements.

Simultaneous Determination of 25 Common Pharmaceuticals in Whole Blood Using Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry