Development and validation of a sensitive thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method for the determination of phosgene in air samples.

PubMed

Juillet, Y; Dubois, C; Bintein, F; Dissard, J; Bossée, A

2014-08-01

A new rapid, sensitive and reliable method was developed for the determination of phosgene in air samples using thermal desorption (TD) followed by gas chromatography-mass spectrometry (GC-MS). The method is based on a fast (10 min) active sampling of only 1 L of air onto a Tenax® GR tube doped with 0.5 mL of derivatizing mixture containing dimercaptotoluene and triethylamine in hexane solution. Validation of the TD-GC-MS method showed a low limit of detection (40 ppbv), acceptable repeatability, intermediate fidelity (relative standard deviation within 12 %) and excellent accuracy (>95%). Linearity was demonstrated for two concentration ranges (0.04 to 2.5 ppmv and 2.5 to 10 ppmv) owing to variation of derivatization recovery between low and high concentration levels. Due to its simple on-site implementation and its close similarity with recommended operating procedure (ROP) for chemical warfare agents vapour sampling, the method is particularly useful in the process of verification of the Chemical Weapons Convention.

Sol-gel-based SPME fiber as a reliable sampling technique for studying biogenic volatile organic compounds released from Clostridium tetani.

PubMed

Ghader, Masoud; Shokoufi, Nader; Es-Haghi, Ali; Kargosha, Kazem

2017-11-01

A novel and efficient headspace solid-phase microextraction (HS-SPME) method, followed by gas chromatography mass spectrometry (GC-MS), was developed to study volatile organic compounds (VOCs) emerging from microorganisms. Two homemade SPME fibers, a semi-polar poly (dimethylsiloxane) (PDMS) fiber, and a polar polyethylene glycol (PEG) fiber, along with two commercial fibers (PDMS and PDMS/DVB) were used to collect VOCs emerging from Clostridium tetani which was cultured in different media. The adsorbed VOCs were desorbed and identified, in vitro, using GC-MS. The adsorption efficiency was improved by optimizing the time duration of adsorption and desorption. About 50 components were identified by the proposed method. The main detected compounds appeared to be sulfur containing compounds such as butanethioic acid S-methyl ester, dimethyl trisulfide, and dimethyl tetrasulfide. These volatile sulfur containing compounds are derived from amino acids containing the sulfur element, which probably coexist in the mentioned bacterium or are added to the culture media. The developed HS-SPME-GC-MS method allowed the determination of the chemical fingerprint of Clostridium tetani volatile constituents, and thus provides a new, simple, and reliable tool for studying the growth of microorganisms. Graphical abstract Investigation of biogenic VOCs released from Clostridium tetani using SPME-GC-MS.

Analysis of flavor compounds by GC/MS after liquid-liquid extraction from fruit juices

NASA Astrophysics Data System (ADS)

Tuşa, F. D.; Moldovan, Z.; Schmutzer, G.; Magdaş, D. A.; Dehelean, A.; Vlassa, M.

2012-02-01

In this work we describe a rapid method for analysis of volatile profiles of several commercial fruit juices using GC/MS instrument after liquid-liquid extraction. Volatile flavor compounds have been identified based on mass spectrum obtained in EI mode. This method allows to analyses a wide range of flavor compounds (esters, aldehydes, alcohols, terpenoids) the procedure was rapid, simple and inexpensive. Moreover, by means of volatile compounds it could be possible to distinguish between juices of organic and conventional production and those with flavorings addition. More of 20 compounds were identified and quantified as relative chromatogram area taken on larges ion in mass spectrum.

Simple and rapid analytical method for detection of amino acids in blood using blood spot on filter paper, fast-GC/MS and isotope dilution technique.

PubMed

Kawana, Shuichi; Nakagawa, Katsuhiro; Hasegawa, Yuki; Yamaguchi, Seiji

2010-11-15

A simple and rapid method for quantitative analysis of amino acids, including valine (Val), leucine (Leu), isoleucine (Ile), methionine (Met) and phenylalanine (Phe), in whole blood has been developed using GC/MS. In this method, whole blood was collected using a filter paper technique, and a 1/8 in. blood spot punch was used for sample preparation. Amino acids were extracted from the sample, and the extracts were purified using cation-exchange resins. The isotope dilution method using ²H₈-Val, ²H₃-Leu, ²H₃-Met and ²H₅-Phe as internal standards was applied. Following propyl chloroformate derivatization, the derivatives were analyzed using fast-GC/MS. The extraction recoveries using these techniques ranged from 69.8% to 87.9%, and analysis time for each sample was approximately 26 min. Calibration curves at concentrations from 0.0 to 1666.7 μmol/l for Val, Leu, Ile and Phe and from 0.0 to 333.3 μmol/l for Met showed good linearity with regression coefficients=1. The method detection limits for Val, Leu, Ile, Met and Phe were 24.2, 16.7, 8.7, 1.5 and 12.9 μmol/l, respectively. This method was applied to blood spot samples obtained from patients with phenylketonuria (PKU), maple syrup urine disease (MSUD), hypermethionine and neonatal intrahepatic cholestasis caused by citrin deficiency (NICCD), and the analysis results showed that the concentrations of amino acids that characterize these diseases were increased. These results indicate that this method provides a simple and rapid procedure for precise determination of amino acids in whole blood. Copyright © 2010 Elsevier B.V. All rights reserved.

Method for the determination of natural ester-type gum bases used as food additives via direct analysis of their constituent wax esters using high-temperature GC/MS.

PubMed

Tada, Atsuko; Ishizuki, Kyoko; Yamazaki, Takeshi; Sugimoto, Naoki; Akiyama, Hiroshi

2014-07-01

Natural ester-type gum bases, which are used worldwide as food additives, mainly consist of wax esters composed of long-chain fatty acids and long-chain fatty alcohols. There are many varieties of ester-type gum bases, and thus a useful method for their discrimination is needed in order to establish official specifications and manage their quality control. Herein is reported a rapid and simple method for the analysis of different ester-type gum bases used as food additives by high-temperature gas chromatography/mass spectrometry (GC/MS). With this method, the constituent wax esters in ester-type gum bases can be detected without hydrolysis and derivatization. The method was applied to the determination of 10 types of gum bases, including beeswax, carnauba wax, lanolin, and jojoba wax, and it was demonstrated that the gum bases derived from identical origins have specific and characteristic total ion chromatogram (TIC) patterns and ester compositions. Food additive gum bases were thus distinguished from one another based on their TIC patterns and then more clearly discriminated using simultaneous monitoring of the fragment ions corresponding to the fatty acid moieties of the individual molecular species of the wax esters. This direct high-temperature GC/MS method was shown to be very useful for the rapid and simple discrimination of varieties of ester-type gum bases used as food additives.

Method for the determination of natural ester-type gum bases used as food additives via direct analysis of their constituent wax esters using high-temperature GC/MS

PubMed Central

Tada, Atsuko; Ishizuki, Kyoko; Yamazaki, Takeshi; Sugimoto, Naoki; Akiyama, Hiroshi

2014-01-01

Natural ester-type gum bases, which are used worldwide as food additives, mainly consist of wax esters composed of long-chain fatty acids and long-chain fatty alcohols. There are many varieties of ester-type gum bases, and thus a useful method for their discrimination is needed in order to establish official specifications and manage their quality control. Herein is reported a rapid and simple method for the analysis of different ester-type gum bases used as food additives by high-temperature gas chromatography/mass spectrometry (GC/MS). With this method, the constituent wax esters in ester-type gum bases can be detected without hydrolysis and derivatization. The method was applied to the determination of 10 types of gum bases, including beeswax, carnauba wax, lanolin, and jojoba wax, and it was demonstrated that the gum bases derived from identical origins have specific and characteristic total ion chromatogram (TIC) patterns and ester compositions. Food additive gum bases were thus distinguished from one another based on their TIC patterns and then more clearly discriminated using simultaneous monitoring of the fragment ions corresponding to the fatty acid moieties of the individual molecular species of the wax esters. This direct high-temperature GC/MS method was shown to be very useful for the rapid and simple discrimination of varieties of ester-type gum bases used as food additives. PMID:25473499

Optimization of matrix solid-phase dispersion for the rapid determination of salicylate and benzophenone-type UV absorbing substances in marketed fish.

PubMed

Tsai, Dung-Ying; Chen, Chien-Liang; Ding, Wang-Hsien

2014-07-01

A simple and effective method for the rapid determination of five salicylate and benzophenone-type UV absorbing substances in marketed fish is described. The method involves the use of matrix solid-phase dispersion (MSPD) prior to their determination by on-line silylation gas chromatography tandem mass spectrometry (GC-MS/MS). The parameters that affect the extraction efficiency were optimized using a Box-Behnken design method. The optimal extraction conditions involved dispersing 0.5g of freeze-dried powdered fish with 1.0g of Florisil using a mortar and pestle. This blend was then transferred to a solid-phase extraction (SPE) cartridge containing 1.0g of octadecyl bonded silica (C18), as the clean-up co-sorbent. The target analytes were then eluted with 7mL of acetonitrile. The extract was derivatized on-line in the GC injection-port by reaction with a trimethylsilylating (TMS) reagent. The TMS-derivatives were then identified and quantitated by GC-MS/MS. The limits of quantitation (LOQs) were less than 0.1ng/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effective and sensitive determination of eleven disinfection byproducts in drinking water by DLLME and GC-MS.

PubMed

On, Jiwon; Pyo, Heesoo; Myung, Seung-Woon

2018-10-15

The aim of this study was to optimize the dispersive liquid-liquid microextraction (DLLME) parameters for simultaneous analysis through DLLME-gas chromatography-mass spectrometry (GC-MS) of six iodo-trihalomethanes, four haloacetonitriles, and one halonitromethane, which are residual disinfection products found in drinking water. Eleven disinfection by-product (DBPs) remaining in aqueous samples were extracted and concentrated using a simple, rapid, and environmentally friendly DLLME method, and then analyzed simultaneously by GC-MS. The optimized DLLME parameters were a sample volume of 5 mL, 100 μL of dichloromethane as the extraction solvent, 1 mL of methanol as the dispersion solvent, an extraction time of 60 s, and 1.5 g of sodium chloride for the salting out effect. The enrichment factor values obtained using the established DLLME-GC-MS method were 19.8-141.5, and the limit of detection and limit of quantification were 0.22-1.19 μg/L and 0.75-3.98 μg/L, respectively. The calibration curves had correlation coefficients (r 2 ) of 0.9958-0.9992 in the concentration range of 0.5-40 μg/L, and they exhibited good linearity in quantitative analysis. This new method could be useful for analyzing eleven DBPs that remain in drinking water. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of PBDEs in soil, dust, spiked lake water, and human serum samples by hollow fiber-liquid phase microextraction combined with GC-ICP-MS.

PubMed

Xiao, Qin; Hu, Bin; Duan, Jiankun; He, Man; Zu, Wanqing

2007-10-01

A novel method for the analysis of four polybrominated diphenyl ethers (PBDEs) in environmental and human serum samples based on hollow fiber-liquid phase microextraction (HF-LPME) followed by gas chromatography-inductively coupled plasma mass spectrometric (GC-ICP-MS) detection has been developed. The organic solvent in the porous hollow fiber was first dipped into the sample for extraction at a given time, and the retracted organic phase was introduced into the GC-ICP-MS for analysis. The addition of methanol has a strong effect on the HF-LPME extraction efficiency. Other significant parameters affecting the extraction efficiency of HF-LPME were also studied. HF-LPME was effective to isolate the analytes from the complex matrix. Under the optimized conditions, the detection limits of the proposed method varied from 15.2 to 40.5 ng/L. In general, the relative standard deviations (RSDs) were less than 10%. Good linearity was obtained with the correlation coefficients all better than 0.999. The proposed method is simple, quick, few microliters of organic solvent required, and is especially suitable for the analysis of the real sample with small amount available. The overall process of HF-LPME with GC-ICP-MS was applied successfully for the determination of polybrominated diphenyl ethers (PBDEs) in environmental and spiked human serum samples, and the results were satisfactory.

Simple and Fast Sample Preparation Followed by Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS) for the Analysis of 2- and 4-Methylimidazole in Cola and Dark Beer.

PubMed

Choi, Sol Ji; Jung, Mun Yhung

2017-04-01

We have developed a simple and fast sample preparation technique in combination with a gas chromatography-tandem mass spectrometry (GC-MS/MS) for the quantification of 2-methylimidazole (2-MeI) and 4-methylimidazole (4-MeI) in colas and dark beers. Conventional sample preparation technique for GC-MS requires laborious and time-consuming steps consisting of sample concentration, pH adjustment, ion pair extraction, centrifugation, back-extraction, centrifugation, derivatization, and extraction. Our sample preparation technique consists of only 2 steps (in situ derivation and extraction) which requires less than 3 min. This method provided high linearity, low limit of detection and limit of quantification, high recovery, and high intra- and interday repeatability. It was found that internal standard method with diluted stable isotope (4-MeI-d 6 ) and 2-ethylimidazole (2-EI) could not correctly compensate the matrix effects. Thus, standard addition technique was used for the quantification of 2- and 4-MeI. The established method was successfully applied to colas and dark beers for the determination of 2-MeI and 4-MeI. The 4-MeI contents in colas and dark beers ranged from 8 to 319 μg/L and from trace to 417 μg/L, respectively. Small quantity (0 to 8 μg/L) of 2-MeI was found only in dark beers. The contents of 4-MeI (22 μg/L) in colas obtained from fast food restaurants were significantly lower than those (177 μg/L) in canned or bottled colas. © 2017 Institute of Food Technologists®.

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013.

PubMed

Paoloni, Angela; Alunni, Sabrina; Pelliccia, Alessandro; Pecorelli, Ivan

2016-01-01

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.

Development and validation of a fast and simple multi-analyte procedure for quantification of 40 drugs relevant to emergency toxicology using GC-MS and one-point calibration.

PubMed

Meyer, Golo M J; Weber, Armin A; Maurer, Hans H

2014-05-01

Diagnosis and prognosis of poisonings should be confirmed by comprehensive screening and reliable quantification of xenobiotics, for example by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS). The turnaround time should be short enough to have an impact on clinical decisions. In emergency toxicology, quantification using full-scan acquisition is preferable because this allows screening and quantification of expected and unexpected drugs in one run. Therefore, a multi-analyte full-scan GC-MS approach was developed and validated with liquid-liquid extraction and one-point calibration for quantification of 40 drugs relevant to emergency toxicology. Validation showed that 36 drugs could be determined quickly, accurately, and reliably in the range of upper therapeutic to toxic concentrations. Daily one-point calibration with calibrators stored for up to four weeks reduced workload and turn-around time to less than 1 h. In summary, the multi-analyte approach with simple liquid-liquid extraction, GC-MS identification, and quantification over fast one-point calibration could successfully be applied to proficiency tests and real case samples. Copyright © 2013 John Wiley & Sons, Ltd.

Analysis of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues in chlorine-treated water by gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS).

PubMed

Planas, Carles; Ventura, Francesc; Caixach, Josep; Martín, Jordi; Boleda, M Rosa; Paraira, Miquel

2015-11-01

A simple, selective and sensitive method for the analysis of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues (BMXs) in chlorine-treated water has been developed. The method is based on gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS), previous liquid-liquid extraction (LLE) of a smaller sample volume compared to other methods and on-line derivatization with a silylation reactive. GC-QqQ-MS/MS has been raised as an alternative easier to perform than gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) for the analysis of MX and BMXs, and it allows to achieve low LODs (0.3 ng/L for MX and 0.4-0.9 ng/L for BMXs). This technique had not been previously described for the analysis of MX and BMXs. Quality parameters were calculated and real samples related to 3 drinking water treatment plants (DWTPs), tap water and both untreated and chlorinated groundwater were analyzed. Concentrations of 0.3-6.6 ng/L for MX and 1.0-7.3 ng/L for BMXs were detected. Results were discussed according to five of the main factors affecting MX and BMXs formation in chlorine-treated water (organic precursors, influence of bromide ions, evolution of MX and BMXs in the drinking water distribution system, groundwater chlorination and infiltration of water coming from chlorination processes in groundwater). Copyright © 2015 Elsevier B.V. All rights reserved.

Methods for the analysis of organophosphorus flame retardants-Comparison of GC-EI-MS, GC-NCI-MS, LC-ESI-MS/MS, and LC-APCI-MS/MS.

PubMed

Tokumura, Masahiro; Miyake, Yuichi; Wang, Qi; Nakayama, Hayato; Amagai, Takashi; Ogo, Sayaka; Kume, Kazunari; Kobayashi, Takeshi; Takasu, Shinji; Ogawa, Kumiko

2018-04-16

Organophosphorus flame retardants (PFRs) are extensively used as alternatives to banned polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). In this study, we analyzed 14 PFRs by means of four mass-spectrometry-based methods: gas chromatography combined with electron-impact mass spectrometry (GC-EI-MS) or negative-chemical-ionization mass spectrometry (GC-NCI-MS) and liquid chromatography combined with tandem mass spectrometry using electrospray ionization (LC-ESI-MS/MS) or atmospheric pressure chemical ionization (LC-APCI-MS/MS). The limits of quantification (LOQs) for LC-ESI-MS/MS and LC-APCI-MS/MS (0.81-970 pg) were 1-2 orders of magnitude lower than the LOQs for GC-EI-MS and GC-NCI-MS (2.3-3900 pg). LC-APCI-MS/MS showed the lowest LOQs (mean = 41 pg; median = 3.4 pg) for all but two of the PFRs targeted in this study. For LC-APCI-MS/MS, the lowest LOQ was observed for tributyl phosphate (TBP) (0.81 pg), and the highest was observed for tris(butoxyethyl) phosphate (TBOEP) (36 pg). The results of this study indicate that LC-APCI-MS/MS is the optimum analytical method for the target PFRs, at least in terms of LOQ.

Development of water-phase derivatization followed by solid-phase microextraction and gas chromatography/mass spectrometry for fast determination of valproic acid in human plasma.

PubMed

Deng, Chunhui; Li, Ning; Ji, Jie; Yang, Bei; Duan, Gengli; Zhang, Xiangmin

2006-01-01

In this study, a simple, rapid, and sensitive method was developed and validated for the quantification of valproic acid (VPA), an antiepileptic drug, in human plasma, which was based on water-phase derivatization followed by headspace solid-phase microextraction (HS-SPME) and gas chromatography/mass spectrometry (GC/MS). In the proposed method, VPA in plasma was rapidly derivatized with a mixture of isobutyl chloroformate, ethanol and pyridine under mild conditions (room temperature, aqueous medium), and the VPA ethyl ester formed was headspace-extracted and simultaneously concentrated using the SPME technique. Finally, the analyte extracted on SPME fiber was analyzed by GC/MS. The experimental parameters and method validations were studied. The optimal conditions were obtained: PDMS fiber, stirring rate of 1100 rpm, sample temperature of 80 degrees C, extraction time of 20 min, NaCl concentration of 30%. The proposed method had a limit of quantification (0.3 microg/mL), good recovery (89-97%) and precision (RSD value less than 10%). Because the proposed method combined a rapid water-phase derivatization with a fast, simple and solvent-free sample extraction and concentration technique of SPME, the sample preparation time was less than 25 min. This much shortens the whole analysis time of VPA in plasma. The validated method has been successfully used to analyze VPA in human plasma samples for application in pharmacokinetic studies. All these results show that water-phase derivatization followed by HS-SPME and GC/MS is an alternative and powerful method for fast determination of VPA in biological fluids. Copyright 2006 John Wiley & Sons, Ltd.

Technical Note: Fast two-dimensional GC-MS with thermal extraction for anhydro-sugars in fine aerosols

EPA Science Inventory

A fast two-dimensional gas chromatography (GC-MS) method that uses heart-cutting and thermal extraction (TE) and requires no chemical derivatization is developed for the determination of anhydro-sugars in fine aerosols. Evaluation of the TE-GC-GC-MS method shows high average rela...

An improved facile method for extraction and determination of steroidal saponins in Tribulus terrestris by focused microwave-assisted extraction coupled with GC-MS.

PubMed

Li, Tianlin; Zhang, Zhuomin; Zhang, Lan; Huang, Xinjian; Lin, Junwei; Chen, Guonan

2009-12-01

An improved fast method for extraction of steroidal saponins in Tribulus terrestris based on the use of focus microwave-assisted extraction (FMAE) is proposed. Under optimized conditions, four steroidal saponins were extracted from Tribulus terrestris and identified by GC-MS, which are Tigogenin (TG), Gitogenin (GG), Hecogenin (HG) and Neohecogenin (NG). One of the most important steroidal saponins, namely TG was quantified finally. The recovery of TG was in the range of 86.7-91.9% with RSD<5.2%. The convention heating reflux extraction was also conducted in order to validate the reliability of this new FMAE method. The yield of total steroidal saponins was 90.3% in a one-step FMAE, while the yield of 65.0% was achieved during heating reflux extraction, and the extraction time was reduced from 3 h to 5 min by using less solvent. The method was successfully applied to analyze the steroidal saponins of Tribulus terrestris from different areas of occurrence. The difference in chromatographic characteristics of steroidal saponins was proved to be related to the different areas of occurrence. The results showed that FMAE-GC-MS is a simple, rapid, solvent-saving method for the extraction and determination of steroidal saponins in Tribulus terrestris.

Determination of ametryn herbicide by bioassay and gas chromatography-mass spectrometry in analysis of residues in drinking water.

PubMed

Queiroz, R H; Lanchote, V L; Bonato, P S; Tozato, E; de Carvalho, D; Gomes, M A; Cerdeira, A L

1999-06-01

A simple, rapid and quantitative bioassay method was compared to a gas chromatography/mass spectrometry (GC/MS) procedure for the analysis of ametryn in surface and groundwater. This method was based on the activity of ametryn in inhibiting the growth of the primary root and shoot of germinating letuce, Lactuca sativa L. seed. The procedure was sensitive to 0.01 microgram/l and was applicable from this concentration up to 0.6 microgram/l. Initial surface sterilization of the seed, selection of pregerminated seed of certain root lengths and special equipment are not necessary. So, we concluded that the sensitivity of the bioassay method is compatible with the chromatographic method (GC-MS). However, the study of the correlation between methods suggests that the bioassay should be used only as a screening technique for the evaluation of ametryn residues in water.

Simultaneous dispersive liquid-liquid microextraction derivatisation and gas chromatography mass spectrometry analysis of subcritical water extracts of sweet and sour cherry stems.

PubMed

Švarc-Gajić, Jaroslava; Clavijo, Sabrina; Suárez, Ruth; Cvetanović, Aleksandra; Cerdà, Víctor

2018-03-01

Cherry stems have been used in traditional medicine mostly for the treatment of urinary tract infections. Extraction with subcritical water, according to its selectivity, efficiency and other aspects, differs substantially from conventional extraction techniques. The complexity of plant subcritical water extracts is due to the ability of subcritical water to extract different chemical classes of different physico-chemical properties and polarities in a single run. In this paper, dispersive liquid-liquid microextraction (DLLME) with simultaneous derivatisation was optimised for the analysis of complex subcritical water extracts of cherry stems to allow simple and rapid preparation prior to gas chromatography-mass spectrometry (GC-MS). After defining optimal extracting and dispersive solvents, the optimised method was used for the identification of compounds belonging to different chemical classes in a single analytical run. The developed sample preparation protocol enabled simultaneous extraction and derivatisation, as well as convenient coupling with GC-MS analysis, reducing the analysis time and number of steps. The applied analytical protocol allowed simple and rapid chemical screening of subcritical water extracts and was used for the comparison of subcritical water extracts of sweet and sour cherry stems. Graphical abstract DLLME GC MS analysis of cherry stem extracts obtained by subcritical water.

Urine Multi-drug Screening with GC-MS or LC-MS-MS Using SALLE-hybrid PPT/SPE.

PubMed

Lee, Junhui; Park, Jiwon; Go, Ahra; Moon, Heesung; Kim, Sujin; Jung, Sohee; Jeong, Wonjoon; Chung, Heesun

2018-05-14

To intoxicated patients in the emergency room, toxicological analysis can be considerably helpful for identifying the involved toxicants. In order to develop a urine multi-drug screening (UmDS) method, gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS) were used to determine targeted and unknown toxicants in urine. A GC-MS method in scan mode was validated for selectivity, limit of detection (LOD) and recovery. An LC-MS-MS multiple reaction monitoring (MRM) method was validated for lower LOD, recovery and matrix effect. The results of the screening analysis were compared with patient medical records to check the reliability of the screen. Urine samples collected from an emergency room were extracted through a combination of salting-out assisted liquid-liquid extraction (SALLE) and hybrid protein precipitation/solid phase extraction (hybrid PPT/SPE) plates and examined by GC-MS and LC-MS-MS. GC-MS analysis was performed as unknown drug screen and LC-MS-MS analysis was conducted as targeted drug screen. After analysis by GC-MS, a library search was conducted using an in-house library established with the automated mass spectral deconvolution and identification system (AMDISTM). LC-MS-MS used Cliquid®2.0 software for data processing and acquisition in MRM mode. An UmDS method by GC-MS and LC-MS-MS was developed by using a SALLE-hybrid PPT/SPE and in-house library. The results of UmDS by GC-MS and LC-MS-MS showed that toxicants could be identified from 185 emergency room patient samples containing unknown toxicants. Zolpidem, acetaminophen and citalopram were the most frequently encountered drugs in emergency room patients. The UmDS analysis developed in this study can be used effectively to detect toxic substances in a short time. Hence, it could be utilized in clinical and forensic toxicology practices.

Improving Student Understanding of Qualitative and Quantitative Analysis via GC/MS Using a Rapid SPME-Based Method for Determination of Trihalomethanes in Drinking Water

ERIC Educational Resources Information Center

Huang, Shu Rong; Palmer, Peter T.

2017-01-01

This paper describes a method for determination of trihalomethanes (THMs) in drinking water via solid-phase microextraction (SPME) GC/MS as a means to develop and improve student understanding of the use of GC/MS for qualitative and quantitative analysis. In the classroom, students are introduced to SPME, GC/MS instrumentation, and the use of MS…

Simultaneous determination of trace migration of phthalate esters in honey and royal jelly by GC-MS.

PubMed

Zhou, Jinhui; Qi, Yitao; Wu, Hongmei; Diao, Qingyun; Tian, Feifei; Li, Yi

2014-03-01

A simple, rapid, and reliable liquid-liquid extraction coupled to GC-MS method was developed and validated for the quantification of 22 phthalate esters (PAEs) in honey and royal jelly. Instrument parameters for GC-MS were tested to obtain the satisfactory separation between 22 PAEs with high sensitivity. The extraction procedure was optimized in order to achieve the best recovery. The following criteria were used to validate the developed method: linearity, LOD, lower LOQ, precision, accuracy, matrix effect and carry-over. Correlation coefficients were >0.999 by applying the linear regression model based on the least-squares method with a weighting factor (1/x). The intra- and interday precision were within 12.7% in terms of RSD, and the accuracy was within -11.8% in terms of relative error. The mean extraction recoveries ranged between 80.1 and 110.9% for honey and royal jelly. No significant matrix effect and carry-over for PAEs were observed for the analysis of honey and royal jelly samples. A total of 20 real samples were analyzed for a mini-survey using the developed method. Seven PAEs in honey samples and five PAEs in royal jelly samples were found, indicating potential contamination with several PAEs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of the Reference Method Isotope Dilution Gas Chromatography Mass Spectrometry (ID/GC/MS) to Establish Metrological Traceability for Calibration and Control of Blood Glucose Test Systems

PubMed Central

Andreis, Elisabeth; Küllmer, Kai

2014-01-01

Self-monitoring of blood glucose (BG) by means of handheld BG systems is a cornerstone in diabetes therapy. The aim of this article is to describe a procedure with proven traceability for calibration and evaluation of BG systems to guarantee reliable BG measurements. Isotope dilution gas chromatography mass spectrometry (ID/GC/MS) is a method that fulfills all requirements to be used in a higher-order reference measurement procedure. However, this method is not applicable for routine measurements because of the time-consuming sample preparation. A hexokinase method with perchloric acid (PCA) sample pretreatment is used in a measurement procedure for such purposes. This method is directly linked to the ID/GC/MS method by calibration with a glucose solution that has an ID/GC/MS-determined target value. BG systems are calibrated with whole blood samples. The glucose levels in such samples are analyzed by this ID/GC/MS-linked hexokinase method to establish traceability to higher-order reference material. For method comparison, the glucose concentrations in 577 whole blood samples were measured using the PCA-hexokinase method and the ID/GC/MS method; this resulted in a mean deviation of 0.1%. The mean deviation between BG levels measured in >500 valid whole blood samples with BG systems and the ID/GC/MS was 1.1%. BG systems allow a reliable glucose measurement if a true reference measurement procedure, with a noninterrupted traceability chain using ID/GC/MS linked hexokinase method for calibration of BG systems, is implemented. Systems should be calibrated by means of a traceable and defined measurement procedure to avoid bias. PMID:24876614

Rapid Monitoring of Pharmacological Volatiles of Night-Flowering Evening-Primrose According to Flower Opening or Closing by Fast Gas Chromatography/Surface Acoustic Wave Sensor (Electronic zNose).

PubMed

Oh, Se Yeon

2018-05-01

Aroma is important in night-flowering species, as visually they can not be observed well. Thus, the analysis of the volatiles of evening-primrose is of great interest in biological fields and therapy. Furthermore, the analysis of volatiles demands rapid and simple procedure, because volatiles decompose. The aim of this study is to show the rapid monitoring of the volatiles of evening-primrose according to the flowering or closing by fast gas chromatography/surface acoustic wave GC/SAW. Moreover, calibration according to the sensor temperature of the GC/SAW was performed, achieving a high reproducibility and excellent sensitivity. GC/SAW is an effective analytical method that provides on-line measurements without pretreatment of sample. Headspace solid-phase micro-extraction coupled to gas chromatography mass spectrometry (HS-SPME-GC-MS) and dynamic headspace trapping and extraction with GC-MS were employed to confirm the identification of the volatiles of evening-primrose compared to GC/SAW. Linalool was found to be the dominant component, comprising 96.4-25.2% of the total amount, according to the opening or closing. Interestingly, the amount of indole also varied according to the opening or closing (3.0-0.0%) such as linalool. Also, while the sensitivity increased with the reduction in the sensor temperature of the GC/SAW, the reproducibility showed a tendency to decrease. The results showed that flower opening is related to the volatiles emission, which is pharmacological and plant defensive. GC/SAW can be a useful analytical method for the rapid monitoring of volatiles of evening-primrose according to the opening or closing as it provides second unit analysis, as well as simple, and aroma pattern recognition. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Identification of volatiles from pineapple (Ananas comosus L.) pulp by comprehensive two-dimensional gas chromatography and gas chromatography/mass spectrometry.

PubMed

Pedroso, Marcio P; Ferreira, Ernesto C; Hantao, Leandro W; Bogusz, Stanislau; Augusto, Fabio

2011-07-01

Combining qualitative data from the chromatographic structure of 2-D gas chromatography with flame ionization detection (GC×GC-FID) and that from gas chromatography-mass spectrometry (GC/MS) should result in a more accurate assignment of the peak identities than the simple analysis by GC/MS, where coelution of analytes is unavoidable in highly complex samples (rendering spectra unsuitable for qualitative purposes) or for compounds in very low concentrations. Using data from GC×GC-FID combined with GC/MS can reveal coelutions that were not detected by mass spectra deconvolution software. In addition, some compounds can be identified according to the structure of the GC×GC-FID chromatogram. In this article, the volatile fractions of fresh and dehydrated pineapple pulp were evaluated. The extraction of the volatiles was performed by dynamic headspace extraction coupled to solid-phase microextraction (DHS-SPME), a technique appropriate for slurries or solid matrices. Extracted analytes were then analyzed by GC×GC-FID and GC/MS. The results obtained using both techniques were combined to improve compound identifications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Open Probe fast GC-MS - combining ambient sampling ultra-fast separation and in-vacuum ionization for real-time analysis.

PubMed

Keshet, U; Alon, T; Fialkov, A B; Amirav, A

2017-07-01

An Open Probe inlet was combined with a low thermal mass ultra-fast gas chromatograph (GC), in-vacuum electron ionization ion source and a mass spectrometer (MS) of GC-MS for obtaining real-time analysis with separation. The Open Probe enables ambient sampling via sample vaporization in an oven that is open to room air, and the ultra-fast GC provides ~30-s separation, while if no separation is required, it can act as a transfer line with 2 to 3-s sample transfer time. Sample analysis is as simple as touching the sample, pushing the sample holder into the Open Probe oven and obtaining the results in 30 s. The Open Probe fast GC was mounted on a standard Agilent 7890 GC that was coupled with an Agilent 5977A MS. Open Probe fast GC-MS provides real-time analysis combined with GC separation and library identification, and it uses the low-cost MS of GC-MS. The operation of Open Probe fast GC-MS is demonstrated in the 30-s separation and 50-s full analysis cycle time of tetrahydrocannabinol and cannabinol in Cannabis flower, sub 1-min analysis of trace trinitrotoluene transferred from a finger onto a glass surface, vitamin E in canola oil, sterols in olive oil, polybrominated flame retardants in plastics, alprazolam in Xanax drug pill and free fatty acids and cholesterol in human blood. The extrapolated limit of detection for pyrene is <1 fg, but the concentration is too high and the software noise calculation is untrustworthy. The broad range of compounds amenable for analysis is demonstrated in the analysis of reserpine. The possible use with alternate standard GC-MS and Open Probe fast GC-MS is demonstrated in the analysis of heroin in its street drug powder. The use of Open Probe with the fast GC acting as a transfer line is demonstrated in <10-s analysis without separation of ibuprofen and estradiol. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

GC and GC-MS determination of fluoroacetic acid and phenoxy acid herbicides via triphasal extractive pentafluorobenzylation using a polymer-bound phase-transfer catalyst.

PubMed

Miki, A; Tsuchihashi, H; Yamashita, M

1998-01-01

A simple and sensitive gas chromatography and gas chromatography-mass spectrometry (GC-MS) procedure has been developed for fluoroacetic acid (FA) and phenoxy acid herbicides (PAHs) via triphasal extractive pentafluorobenzylation. The triphasal system consisted of an aqueous sample, the extraction solvent toluene containing pentafluorobenzyl bromide as the derivatization reagent, and polymer-bound tri-n-butyl-methylphosphonium bromide as a phase-transfer catalyst, FA spiked in beverages, such as orange juice and milk, was extracted as its pentafluorobenzyl (PFB) derivative under moderate conditions (i.e., at a pH value of 6.5 at 60 degrees C). The detection limits were 0.10-0.20 microgram/mL by GC with electron-capture detection (GC-ECD), and 0.42-0.50 microgram/mL by full-scan GC-MS. PAHs were also detectable in the same manner within the detection limits of 0.05-0.10 microgram/mL by GC-ECD and 0.13-0.25 microgram/mL by full-scan GC-MS. Urine and serum which both contained 2,4-dichlorophenoxyacetic acid could also be analyzed by GC-MS after the triphasal pentafluorobenzylation. The detection limit was 0.20 microgram/mL in the full-scan mode and 10 ng/mL in the selected ion monitoring mode both for the urine and serum.

Direct screening of herbal blends for new synthetic cannabinoids by MALDI-TOF MS.

PubMed

Gottardo, Rossella; Chiarini, Anna; Dal Prà, Ilaria; Seri, Catia; Rimondo, Claudia; Serpelloni, Giovanni; Armato, Ubaldo; Tagliaro, Franco

2012-01-01

Since 2004, a number of herbal blends containing different synthetic compounds mimicking the pharmacological activity of cannabinoids and displaying a high toxicological potential have appeared in the market. Their availability is mainly based on the so-called "e-commerce", being sold as legal alternatives to cannabis and cannabis derivatives. Although highly selective, sensitive, accurate, and quantitative methods based on GC-MS and LC-MS are available, they lack simplicity, rapidity, versatility and throughput, which are required for product monitoring. In this context, matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) offers a simple and rapid operation with high throughput. Thus, the aim of the present work was to develop a MALDI-TOF MS method for the rapid qualitative direct analysis of herbal blend preparations for synthetic cannabinoids to be used as front screening of confiscated clandestine preparations. The sample preparation was limited to herbal blend leaves finely grinding in a mortar and loading onto the MALDI plate followed by addition of 2 µl of the matrix/surfactant mixture [α-cyano-4-hydroxy-cinnamic acid/cetyltrimethylammonium bromide (CTAB)]. After drying, the sample plate was introduced into the ion source for analysis. MALDI-TOF conditions were as follows: mass spectra were analyzed in the range m/z 150-550 by averaging the data from 50 laser shots and using an accelerating voltage of 20 kV. The described method was successfully applied to the screening of 31 commercial herbal blends, previously analyzed by GC-MS. Among the samples analyzed, 21 contained synthetic cannabinoids (namely JWH-018, JWH-073, JWH-081, JWH-250, JWH-210, JWH-019, and AM-694). All the results were in agreement with GC-MS, which was used as the reference technique. Copyright © 2012 John Wiley & Sons, Ltd.

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

PubMed

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 comparable data. In addition, results from analyses of specimens from the German External Quality Assessment Scheme (G-EQUAS) suggested that the GC-FPD method produced accurate results that can be reasonably compared to other studies. Copyright © 2013 Elsevier GmbH. All rights reserved.

A Robust Static Headspace GC-FID Method to Detect and Quantify Formaldehyde Impurity in Pharmaceutical Excipients

PubMed Central

Al-Khayat, Mohammad Ammar; Karabet, Francois; Al-Mardini, Mohammad Amer

2018-01-01

Formaldehyde is a highly reactive impurity that can be found in many pharmaceutical excipients. Trace levels of this impurity may affect drug product stability, safety, efficacy, and performance. A static headspace gas chromatographic method was developed and validated to determine formaldehyde in pharmaceutical excipients after an effective derivatization procedure using acidified ethanol. Diethoxymethane, the derivative of formaldehyde, was then directly analyzed by GC-FID. Despite the simplicity of the developed method, however, it is characterized by its specificity, accuracy, and precision. The limits of detection and quantification of formaldehyde in the samples were of 2.44 and 8.12 µg/g, respectively. This method is characterized by using simple and economic GC-FID technique instead of MS detection, and it is successfully used to analyze formaldehyde in commonly used pharmaceutical excipients. PMID:29686930

Evaluation of a Fast and Simple Sample Preparation Method for Polybrominated Diphenyl Ether (PBDE) Flame Retardants and Dichlorodiphenyltrichloroethane (DDT) Pesticides in Fish for Analysis by ELISA Compared with GC-MS/MS.

PubMed

Sapozhnikova, Yelena; Simons, Tawana; Lehotay, Steven J

2015-05-13

A simple, fast, and cost-effective sample preparation method, previously developed and validated for the analysis of organic contaminants in fish using low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS), was evaluated for the analysis of polybrominated diphenyl ethers (PBDEs) and dichlorodiphenyltrichloroethane (DDT) pesticides using enzyme-linked immunosorbent assay (ELISA). The sample preparation technique was based on the quick, easy, cheap, rugged, effective, and safe (QuEChERS) approach with filter-vial dispersive solid phase extraction (d-SPE). Incurred PBDEs and DDTs were analyzed in three types of fish with 3-10% lipid content: Pacific croaker, salmon, and National Institute of Standards and Technology (NIST) Standard Reference Material 1947 (Lake Michigan fish tissue). LPGC-MS/MS and ELISA results were in agreement: 108-111 and 65-82% accuracy ELISA versus LPGC-MS/MS results for PBDEs and DDTs, respectively. Similar detection limits were achieved for ELISA and LPGC-MS/MS. Matrix effects (MEs) were significant (e.g., -60%) for PBDE measurement in ELISA, but not a factor in the case of DDT pesticides. This study demonstrated that the sample preparation method can be adopted for semiquantitative screening analysis of fish samples by commercial kits for PBDEs and DDTs.

A new purge-and-trap headspace technique to analyse volatile organohalogens from fluid inclusions of rocks and minerals

NASA Astrophysics Data System (ADS)

Mulder, Ines; Huber, Stefan; Schöler, Heinfried

2010-05-01

Recently, advances were made in the detection of low boiling point volatile organohalogens (VOCs) at trace gas concentrations of air samples employing sophisticated and complex experimental setups (Sive et al. 2005, Miller et al. 2008) while conventional fluid inclusion gas analysis via GC/MS (gas chromatography coupled with mass spectrometry) do not include halogenated VOCs in their analytical routine (e.g. Samson et al. 2003). At the same time Svensen et al. (2009) have just confirmed the release of chlorinated and brominated VOC from halites after heat treatment using GC/MS into which they injected compounds previously trapped on adsorption tubes. Already in 1998, Harnish and Eisenhauer reported the presence of CF4 and SF6 released from natural fluorite and granite samples after milling but appear to have received little resonance in the scientific community. In this work we present the development of a new method for the analysis of halogenated VOCs from fluid inclusions. The mineral or rock sample is milled in an air-tight tempered steel container that fits into a regular planetary mill. Starting at a particle size of around 2-3 mm a final mean particle fineness of 1000 to 750 nm for quartz and fluorites, respectively, is achieved. The grinding container is equipped with two septa that can be pierced by the two needles through which the sample is connected to the GC/MS system and through which the gases are purged similar to a standard purge-and-trap system. The gases are trapped at liquid nitrogen temperatures before entering directly onto the column of the GC/MS system. Compounds that were released during grinding are separated and detected by an ion trap mass spectrometer. To prevent contamination with fine particles a 0.5 µm sintered steel filter element is interconnected after the sample needle. Optimizations and calibrations were conducted using diluted pure gases. First results show that this modified GC/MS purge-and-trap method appears to be an effective, simple and relatively low cost alternative for VOC analysis that opens up new territories in GC/MS analysis of fluid inclusions.

Simultaneous Determination of Benzene and Toluene in Pesticide Emulsifiable Concentrate by Headspace GC-MS

PubMed Central

Jiang, Hua; Yang, Jing; Fan, Li; Li, Fengmin; Huang, Qiliang

2013-01-01

The toxic inert ingredients in pesticide formulations are strictly regulated in many countries. In this paper, a simple and efficient headspace-gas chromatography-mass spectrometry (HSGC-MS) method using fluorobenzene as an internal standard (IS) for rapid simultaneous determination of benzene and toluene in pesticide emulsifiable concentrate (EC) was established. The headspace and GC-MS conditions were investigated and developed. A nonpolar fused silica Rtx-5 capillary column (30 m × 0.20 mm i.d. and 0.25 μm film thickness) with temperature programming was used. Under optimized headspace conditions, equilibration temperature of 120°C, equilibration time of 5 min, and sample size of 50 μL, the regression of the peak area ratios of benzene and toluene to IS on the concentrations of analytes fitted a linear relationship well at the concentration levels ranging from 3.2 g/L to 16.0 g/L. Standard additions of benzene and toluene to blank different matrix solutions 1ead to recoveries of 100.1%–109.5% with a relative standard deviation (RSD) of 0.3%–8.1%. The method presented here stands out as simple and easily applicable, which provides a way for the determination of toxic volatile adjuvant in liquid pesticide formulations. PMID:23607048

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-time-of-flight MS comparing organic and integrated pest management farming.

PubMed

Fernandes, Virgínia C; Lehotay, Steven J; Geis-Asteggiante, Lucía; Kwon, Hyeyoung; Mol, Hans G J; van der Kamp, Henk; Mateus, Nuno; Domingues, Valentina F; Delerue-Matos, Cristina

2014-01-01

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 µg kg(-1) for fluazifop-p-butyl to 50 µg kg(-1) for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

Sensitive and selective determination of polycyclic aromatic hydrocarbons in mainstream cigarette smoke using a graphene-coated solid-phase microextraction fiber prior to GC/MS.

PubMed

Wang, Xiaoyu; Wang, Yuan; Qin, Yaqiong; Ding, Li; Chen, Yi; Xie, Fuwei

2015-08-01

A simple method has been developed for the simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAHs) in mainstream cigarette smoke. The procedure is based on employing a homemade graphene-coated solid-phase microextraction (SPME) fiber for extraction prior to GC/MS. In comparison to commercial 100-μm poly(dimethyl siloxane) (PDMS) fiber, the graphene-coated SPME fiber exhibits advantageous cleanup and preconcentration efficiencies. By collecting the particulate phase 5 cigarettes, the LODs and LOQs of 16 target PAHs were 0.02-0.07 and 0.07-0.22 ng/cigarette, respectively, and all of the linear correlation efficiencies were larger than 0.995. The validation results also indicate that the method has good repeatability (RSD between 4.2% and 9.5%) and accuracy (spiked recoveries between 80% and 110%). The developed method was applied to analyze two Kentucky reference cigarettes (1R5F and 3R4F) and six Chinese brands of cigarettes. In addition, the PAH concentrations in the particulate phase of the smoke from the 1R5F Kentucky cigarettes were in good agreement with recently reported results. Due to easy operation and good validation results, this SPME-GC/MS method may be an excellent alternative for trace analysis of PAHs in cigarette smoke. Copyright © 2015 Elsevier B.V. All rights reserved.

Urinary Amino Acid Analysis: A Comparison of iTRAQ®-LC-MS/MS, GC-MS, and Amino Acid Analyzer

PubMed Central

Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L.; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J.

2009-01-01

Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) of propyl chloroformate and iTRAQ® derivatized amino acids, respectively, to conventional amino acid analysis. The GC-MS method builds on the direct derivatization of amino acids in diluted urine with propyl chloroformate, GC separation and mass spectrometric quantification of derivatives using stable isotope labeled standards. The LC-MS/MS method requires prior urinary protein precipitation followed by labeling of urinary and standard amino acids with iTRAQ® tags containing different cleavable reporter ions distinguishable by MS/MS fragmentation. Means and standard deviations of percent technical error (%TE) computed for 20 amino acids determined by amino acid analyzer, GC-MS, and iTRAQ®-LC-MS/MS analyses of 33 duplicate and triplicate urine specimens were 7.27±5.22, 21.18±10.94, and 18.34±14.67, respectively. Corresponding values for 13 amino acids determined in a second batch of 144 urine specimens measured in duplicate or triplicate were 8.39±5.35, 6.23±3.84, and 35.37±29.42. Both GC-MS and iTRAQ®-LC-MS/MS are suited for high-throughput amino acid analysis, with the former offering at present higher reproducibility and completely automated sample pretreatment, while the latter covers more amino acids and related amines. PMID:19481989

Urinary amino acid analysis: a comparison of iTRAQ-LC-MS/MS, GC-MS, and amino acid analyzer.

PubMed

Kaspar, Hannelore; Dettmer, Katja; Chan, Queenie; Daniels, Scott; Nimkar, Subodh; Daviglus, Martha L; Stamler, Jeremiah; Elliott, Paul; Oefner, Peter J

2009-07-01

Urinary amino acid analysis is typically done by cation-exchange chromatography followed by post-column derivatization with ninhydrin and UV detection. This method lacks throughput and specificity. Two recently introduced stable isotope ratio mass spectrometric methods promise to overcome those shortcomings. Using two blinded sets of urine replicates and a certified amino acid standard, we compared the precision and accuracy of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) of propyl chloroformate and iTRAQ derivatized amino acids, respectively, to conventional amino acid analysis. The GC-MS method builds on the direct derivatization of amino acids in diluted urine with propyl chloroformate, GC separation and mass spectrometric quantification of derivatives using stable isotope labeled standards. The LC-MS/MS method requires prior urinary protein precipitation followed by labeling of urinary and standard amino acids with iTRAQ tags containing different cleavable reporter ions distinguishable by MS/MS fragmentation. Means and standard deviations of percent technical error (%TE) computed for 20 amino acids determined by amino acid analyzer, GC-MS, and iTRAQ-LC-MS/MS analyses of 33 duplicate and triplicate urine specimens were 7.27+/-5.22, 21.18+/-10.94, and 18.34+/-14.67, respectively. Corresponding values for 13 amino acids determined in a second batch of 144 urine specimens measured in duplicate or triplicate were 8.39+/-5.35, 6.23+/-3.84, and 35.37+/-29.42. Both GC-MS and iTRAQ-LC-MS/MS are suited for high-throughput amino acid analysis, with the former offering at present higher reproducibility and completely automated sample pretreatment, while the latter covers more amino acids and related amines.

High Throughput Analytical Techniques for the Determination and Confirmation of Residues of 653 Multiclass Pesticides and Chemical Pollutants in Tea by GC/MS, GC/MS/MS, and LC/MS/MS: Collaborative Study, First Action 2014.09.

PubMed

Pang, Guo-Fang; Fan, Chun-Lin; Cao, Yan-Zhong; Yan, Fang; Li, Yan; Kang, Jian; Chen, Hui; Chang, Qiao-Ying

2015-01-01

Thirty laboratories from fom North and South America, Europe, and Asia participated in this AOAC collaborative study (15 from China; five from Germany; two each from Italy and the United States; and one each from the Republic of Korea, Canada, Spain, Japan, Belgium, and India). Participants represented government regulatory, commercial testing, university, research institute, and private laboratories. The single-laboratory validated (SLV) tea method was evaluated in the collaborative study to determine the recovery and reproducibility of the method under multilaboratory conditions. Since there were no restrictions regarding the type of analytical instrumentation to use for the analyses, laboratories used a combination of equipment that included GC/MS, GC/MS/MS, and LC/MS/MS instruments from 22 different manufacturers, 21 brands of GC and LC columns, 13 different GC temperature programming profiles, 11 LC gradient elution programs, and six different vendor manufactured SPE cartridges. Even though all the analytical performance parameters for all the 653 compounds had been determined in the SLV study, guidance was obtained from an expert review panel of the AOAC Method-Centric Committee on Pesticide Residues to conduct the multilaboratory collaborative study based on 20 selected compounds that can be analyzed by GC/MS and 20 compounds that can be analyzed by LC/MS/MS. Altogether, 560 samples covering the 40 selected pesticides were analyzed in the study. These samples included green tea and oolong tea samples fortified typically at the European Union maximum residue limit for regulatory guidance and compliance, aged tea samples incurred with 20 pesticides, and green tea and oolong tea samples incurred with five pesticides. The analysis of the 560 samples generated a total of 82 459 test results by the 30 participating laboratories. One laboratory failed to meet the proficiency requirements in the precollaborative study. Therefore, its data submitted for the collaborative study were excluded from further analysis and interpretation. The results presented are therefore the 6638 analytical results obtained from the 29 remaining laboratories, which included 1977 results generated by GC/MS, 1704 results by GC/MS/MS, and 2957 results by LC/MS/MS. It was determined after application of the Grubbs and Dixon tests for outliers to the data sets that there were 65 outlier results from the 1977 GC/MS results (3.3%), 65 outlier results from the 1704 GC/MS/MS results (3.8%), and 57 outlier results out of 2957 LC/MS/MS results (1.9%), representing 0.98, 0.98, and 0.86%, respectively, of the 6638 results generated in the study. Analysis with the AOAC statistical software package also confirmed that the method is rugged, and average recovery, average concentration, RSDr, RSDR, and HorRat values all meet recovery and reproducibility criteria for use in multiple laboratories. The Study Director is recommending this method for adoption as an AOAC First Action Official MethodSM.

Comparison of GC-MS and FTIR methods for quantifying naphthenic acids in water samples.

PubMed

Scott, Angela C; Young, Rozlyn F; Fedorak, Phillip M

2008-11-01

The extraction of bitumen from the oil sands in Canada releases toxic naphthenic acids into the process-affected waters. The development of an ideal analytical method for quantifying naphthenic acids (general formula C(n)H(2n+Z)O(2)) has been impeded by the complexity of these mixtures and the challenges of differentiating naphthenic acids from other naturally-occurring organic acids. The oil sands industry standard FTIR method was compared with a newly-developed GC-MS method. Naphthenic acids concentrations were measured in extracts of surface and ground waters from locations within the vicinity of and away from the oil sands deposits and in extracts of process-affected waters. In all but one case, FTIR measurements of naphthenic acids concentrations were greater than those determined by GC-MS. The detection limit of the GC-MS method was 0.01 mg L(-1) compared to 1 mg L(-1) for the FTIR method. The results indicated that the GC-MS method is more selective for naphthenic acids, and that the FTIR method overestimates their concentrations.

Pesticide residues in cashew apple, guava, kaki and peach: GC-μECD, GC-FPD and LC-MS/MS multiresidue method validation, analysis and cumulative acute risk assessment.

PubMed

Jardim, Andréia Nunes Oliveira; Mello, Denise Carvalho; Goes, Fernanda Caroline Silva; Frota Junior, Elcio Ferreira; Caldas, Eloisa Dutra

2014-12-01

A multiresidue method for the determination of 46 pesticides in fruits was validated. Samples were extracted with acidified ethyl acetate, MgSO4 and CH3COONa and cleaned up by dispersive SPE with PSA. The compounds were analysed by GC-FPD, GC-μECD or LC-MS/MS, with LOQs from 1 to 8 μg/kg. The method was used to analyse 238 kaki, cashew apple, guava, and peach fruit and pulp samples, which were also analysed for dithiocarbamates (DTCs) using a spectrophotometric method. Over 70% of the samples were positive, with DTC present in 46.5%, λ-cyhalothrin in 37.1%, and omethoate in 21.8% of the positive samples. GC-MS/MS confirmed the identities of the compounds detected by GC. None of the pesticides found in kaki, cashew apple and guava was authorised for these crops in Brazil. The risk assessment has shown that the cumulative acute intake of organophosphorus or pyrethroid compounds from the consumption of these fruits is unlikely to pose a health risk to consumers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Carbohydrate profiling of bacteria by gas chromatography-mass spectrometry and their trace detection in complex matrices by gas chromatography-tandem mass spectrometry.

PubMed

Fox, A

1999-05-28

Bacterial cellular polysaccharides are composed of a variety of sugar monomers. These sugars serve as chemical markers to identify specific species or genera or to determine their physiological status. Some of these markers can also be used for trace detection of bacteria or their constituents in complex clinical or environmental matrices. Analyses are performed, in our hands, employing hydrolysis followed by the alditol acetate derivatization procedure. Substantial improvements have been made to sample preparation including simplification and computer-controlled automation. For characterization of whole cell bacterial hydrolysates, sugars are analyzed by gas chromatography-mass spectrometry (GC-MS). Simple chromatograms are generated using selected ion monitoring (SIM). Using total ion GC-MS, sugars can be readily identified. In more complex clinical and environmental samples, markers for bacteria are present at sufficiently low concentrations that more advanced instrumentation, gas chromatography-tandem mass spectrometry (GC-MS-MS), is preferred for optimal analysis. Using multiple reaction monitoring, MS-MS is used (replacing more conventional SIM) to ignore extraneous chromatographic peaks. Triple quadrupole and ion trap GC-MS-MS instruments have both been used successfully. Absolute chemical identification of sugar markers at trace levels is achieved, using MS-MS, by the product spectrum.

Determination of red blood cell fatty acid profiles: Rapid and high-confident analysis by chemical ionization-gas chromatography-tandem mass spectrometry.

PubMed

Schober, Yvonne; Wahl, Hans Günther; Renz, Harald; Nockher, Wolfgang Andreas

2017-01-01

Cellular fatty acid (FA) profiles have been acknowledged as biomarkers in various human diseases. Nevertheless, common FA analysis by gas chromatography mass spectrometry (GC-MS) requires long analysis time. Hence, there is a need for feasible methods for high throughput analysis in clinical studies. FA was extracted from red blood cells (RBC) and derivatized to fatty acid methyl esters (FAME). A method using gas chromatography tandem mass spectrometry (GC-MS/MS) with ammonia-induced chemical ionization (CI) was developed for the analysis of FA profiles in human RBC. We compared this method with classical single GC-MS using electron impact ionization (EI). The FA profiles of 703 RBC samples were determined by GC-MS/MS. In contrast to EI ammonia-induced CI resulted in adequate amounts of molecular ions for further fragmentation of FAME. Specific fragments for confident quantification and fragmentation were determined for 45 FA. The GC-MS/MS method has a total run time of 9min compared to typical analysis times of up to 60min in conventional GC-MS. Intra and inter assay variations were <10% for all FA analyzed. Analysis of RBC FA composition revealed an age-dependent increase of the omega-3 eicosapentaenoic and docosahexaenoic acid, and a decline of the omega-6 linoleic acid with a corresponding rise of the omega-3 index. The combination of ammonia-induced CI and tandem mass spectrometry after GC separation allows for high-throughput, robust and confident analysis of FA profiles in the clinical laboratory. Copyright © 2016. Published by Elsevier B.V.

Prototype of an Interface for Hyphenating Distillation with Gas Chromatography and Mass Spectrometry

PubMed Central

Tang, Ya-Ru; Yang, Hui-Hsien; Urban, Pawel L.

2017-01-01

Chemical analysis of complex matrices—containing hundreds of compounds—is challenging. Two-dimensional separation techniques provide an efficient way to reduce complexity of mixtures analyzed by mass spectrometry (MS). For example, gasoline is a mixture of numerous compounds, which can be fractionated by distillation techniques. However, coupling conventional distillation with other separations as well as MS is not straightforward. We have established an automatic system for online coupling of simple microscale distillation with gas chromatography (GC) and electron ionization MS. The developed system incorporates an interface between the distillation condenser and the injector of a fused silica capillary GC column. Development of this multidimensional separation (distillation-GC-MS) was preceded by a series of preliminary off-line experiments. In the developed technique, the components with different boiling points are fractionated and instantly analyzed by GC-MS. The obtained data sets illustrate dynamics of the distillation process. An important advantage of the distillation-GC-MS technique is that raw samples can directly be analyzed without removal of the non-volatile matrix residues that could contaminate the GC injection port and the column. Distilling the samples immediately before the injection to the GC column may reduce possible matrix effects—especially in the early phase of separation, when molecules with different volatilities co-migrate. It can also reduce losses of highly volatile components (during fraction collection and transfer). The two separation steps are partly orthogonal, what can slightly increase selectivity of the entire analysis. PMID:28337400

[Study for the revision of analytical method for tris (2,3-dibromopropyl) phosphate with restriction in textiles].

PubMed

Mimura, Mayumi; Nakashima, Harunobu; Yoshida, Jin; Yoshida, Toshiaki; Kawakami, Tsuyoshi; Isama, Kazuo

2014-01-01

The official analytical method for tris(2,3-dibromopropyl)phosphate (TDBPP), which is banned from use in textile products by the "Act on Control of Household Products Containing Harmful Substances", requires revision. This study examined an analytical method for TDBPP by GC/MS using a capillary column. Thermal decomposition of TDBPP was observed by GC/MS measurement using capillary column, unlike in the case of gas chromatography/flame photometric detector (GC/FPD) measurement based on a direct injection method using a capillary megabore column. A quadratic curve, Y=2572X(1.416), was obtained for the calibration curve of GC/FPD in the concentration range 2.0-100 μg/mL. The detection limit was 1.0 μg/mL under S/N=3. The reproducibility for repetitive injections was satisfactory. A pretreatment method was established using methanol extraction, followed by liquid-liquid partition and purification with a florisil cartridge column. The recovery rate of this method was ～100%. TDBPP was not detected in any of the five commercial products that this study analyzed. To understand the cause of TDBPP decomposition during GC/MS (electron ionization; EI) measurement using capillary column, GC/MS (chemical ionization; CI), GC/FPD, and gas chromatography/flame ionization detector (GC/FID) measurements were conducted. It was suggested that TDBPP might thermally decompose both during GC injection, especially through a splitless injection method, and in the column or ion sources. To attempt GC/MS measurement, an injection part comprising quartz liner was used and the column length was halved (15 m); thus, only one peak could be obtained.

DETERMINATION OF 16 LARGEST PEAKS IN COMMERCIAL TECHNICAL TOXAPHENE BY GC/MS

EPA Science Inventory

Under typical temperature and high vacuum associated with GC/MS technique, Toxaphene decomposes and produces countless fragments which are impractical to quantify. A GC/MS method has been developed using the lowest possible temperature to resolve more peaks and lower the interfer...

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

PubMed

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

2017-03-21

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

Development of a simple and sensitive method for the characterization of odorous waste gas emissions by means of solid-phase microextraction (SPME) and GC-MS/olfactometry.

PubMed

Kleeberg, K K; Liu, Y; Jans, M; Schlegelmilch, M; Streese, J; Stegmann, R

2005-01-01

A solid-phase microextraction (SPME) method has been developed for the extraction of odorous compounds from waste gas. The enriched compounds were characterized by gas chromatography-mass spectrometry (GC-MS) and gas chromatography followed by simultaneous flame ionization detection and olfactometry (GC-FID/O). Five different SPME fiber coatings were tested, and the carboxen/polydimethylsiloxane (CAR/PDMS) fiber showed the highest ability to extract odorous compounds from the waste gas. Furthermore, parameters such as exposure time, desorption temperature, and desorption time have been optimized. The SPME method was successfully used to characterize an odorous waste gas from a fat refinery prior to and after waste gas treatment in order to describe the treatment efficiency of the used laboratory scale plant which consisted of a bioscrubber/biofilter combination and an activated carbon adsorber. The developed method is a valuable approach to provide detailed information of waste gas composition and complements existing methods for the determination of odors. However, caution should be exercised if CAR/PDMS fibers are used for the quantification of odorous compounds in multi-component matrices like waste gas emissions since the relative affinity of each analyte was shown to differ according to the total amount of analytes present in the sample.

Quantitative Determination of Caffeine in Beverages Using a Combined SPME-GC/MS Method

NASA Astrophysics Data System (ADS)

Pawliszyn, Janusz; Yang, Min J.; Orton, Maureen L.

1997-09-01

Solid-phase microextraction (SPME) combined with gas chromatography/mass spectrometry (GC/MS) has been applied to the analysis of various caffeinated beverages. Unlike the current methods, this technique is solvent free and requires no pH adjustments. The simplicity of the SPME-GC/MS method lends itself to a good undergraduate laboratory practice. This publication describes the analytical conditions and presents the data for determination of caffeine in coffee, tea, and coke. Quantitation by isotopic dilution is also illustrated.

Picogram determination of N-nitrosodimethylamine in water.

PubMed

Hu, Ruikang; Zhang, Lifeng; Yang, Zhaoguang

2008-01-01

N-nitrosodimethylamine (NDMA) persistence within surface waters is a major concern for downstream communities exploiting these waters as drinking water supplies. The objective of this study is to develop a novel and efficient analytical method for NDMA via different technologies: pulsed splitless gas chromatography-nitrogen phosphorus detector (GC-NPD), large volume injection (LVI) gas chromatography-mass spectrometry (GC/MS) via programmable temperature vaporizer (PTV) inlet or PTV-gas chromatography-triple quadruple mass spectrometry (GC-MS/MS) and continuous liquid-liquid extraction. It was found that the sensitivity required for NDMA analysis by GC-NPD can only be achieved when the NPD bead is extremely clean. LVI via PTV can greatly improve GC-MS system sensitivity for analyzing NDMA. With the help of DB-624 (25 m x 200 microm x 1.12 microm) connected with DB-5MS (30 m x 250 microm x 0.25 microm) in series, PTV-GC/MS could overcome the matrix interference for the trace analysis of NDMA. Variable instrument conditions were studied in detail, with the optimized process being validated via precision and accuracy studies. PTV- triple quadruple GC-MS/MS system could efficiently remove the interference on a single DB-5MS (30 m x 250 microm x 0.25 microm) column with good sensitivity and selectivity. The developed methods have been successfully applied to test NDMA in different types of water samples with satisfactory results. (c) IWA Publishing 2008.

Quantitative Determination of Perfluorochemicals and Fluorotelomer Alcohols in Plants from Biosolid-Amended Fields using LC/MS/MS and GC/MS

EPA Science Inventory

Analytical methods for determining perfluorochemicals (PFCs) and fluorotelomer alcohols (FTOHs) in plants using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and gas chromatography/mass spectrometry (GC/MS) were developed, and applied to quantify a suite of analytes i...

Direct immersion single drop micro-extraction method for multi-class pesticides analysis in mango using GC-MS.

PubMed

Pano-Farias, Norma S; Ceballos-Magaña, Silvia G; Muñiz-Valencia, Roberto; Jurado, Jose M; Alcázar, Ángela; Aguayo-Villarreal, Ismael A

2017-12-15

Due the negative effects of pesticides on environment and human health, more efficient and environmentally friendly methods are needed. In this sense, a simple, fast, free from memory effects and economical direct-immersion single drop micro-extraction (SDME) method and GC-MS for multi-class pesticides determination in mango samples was developed. Sample pre-treatment using ultrasound-assisted solvent extraction and factors affecting the SDME procedure (extractant solvent, drop volume, stirring rate, ionic strength, time, pH and temperature) were optimized using factorial experimental design. This method presented high sensitive (LOD: 0.14-169.20μgkg -1 ), acceptable precision (RSD: 0.7-19.1%), satisfactory recovery (69-119%) and high enrichment factors (20-722). Several obtained LOQs are below the MRLs established by the European Commission; therefore, the method could be applied for pesticides determination in routing analysis and custom laboratories. Moreover, this method has shown to be suitable for determination of some of the studied pesticides in lime, melon, papaya, banana, tomato, and lettuce. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Rapid determination of volatile organic compounds in workplace air by protable gas chromatography-mass spectrometer].

PubMed

Zhu, H B; Su, C J; Tang, H F; Ruan, Z; Liu, D H; Wang, H; Qian, Y L

2017-10-20

Objective: To establish a method for rapid determination of 47 volatile organic compounds in the air of workplace using portable gas chromatography - mass spectrometer(GC - MS). Methods: The mixed standard gas with different concentration levels was made by using the static gas distribution method with the high purity nitrogen as dilution gas. The samples were injected into the GC - MS by a hand - held probe. Retention time and characteristic ion were used for qualitative analysis,and the internal standard method was usd for quantitation. Results: The 47 poisonous substances were separated and determined well. The linear range of this method was 0.2 - 16.0 mg/m(3),and the relative standard deviation of 45 volatile ovganic compounds was 3.8% - 15.8%. The average recovery was 79.3% - 119.0%. Conclusion: The method is simple,accurate,sensitive,has good separation effect,short analysis period, can be used for qualitative and quantitative analysis of volatile organic compounds in the workplace, and also supports the rapid identification and detection of occupational hazards.

Analysis of Bisphenol A, Alkylphenols, and Alkylphenol Ethoxylates in NIST SRM 2585 and Indoor House Dust by Gas Chromatography-Tandem Mass Spectrometry (GC/MS/MS).

PubMed

Fan, Xinghua; Kubwabo, Cariton; Wu, Fang; Rasmussen, Pat E

2018-06-26

Background: Ingestion of house dust has been demonstrated to be an important exposure pathway to several contaminants in young children. These compounds include bisphenol A (BPA), alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analysis of these compounds in house dust is challenging because of the complex composition of the sample matrix. Objective: The objective was to develop a simple and sensitive method to measure BPA, APs, and APEOs in indoor house dust. Methods: An integrated method that involved solvent extraction using sonication, sample cleanup by solid-phase extraction, derivatization by 2,2,2-trifluoro- N -methyl- N -(trimethylsilyl)acetamide, and analysis by GC coupled with tandem MS was developed for the simultaneous determination of BPA, APs, and APEOs in NIST Standard Reference Material (SRM) 2585 (Organic contaminants in house dust) and in settled house dust samples. Results: Target analytes included BPA, 4- tert -octylphenol (OP), OP monoethoxylate, OP diethoxylate, 4- n -nonylphenol (4 n NP), 4 n NP monoethoxylate (4 n NP 1 EO), branched nonylphenol (NP), NP monoethoxylate, NP diethoxylate, NP triethoxylate, and NP tetraethoxylate. The method was sensitive, with method detection limits ranging from 0.05 to 5.1 μg/g, and average recoveries between 82 and 115%. All target analytes were detected in SRM 2585 and house dust except 4 n NP and 4 n NP 1 EO. Conclusions: The method is simple and fast, with high sensitivity and good reproducibility. It is applicable to the analysis of target analytes in similar matrixes, such as sediments, soil, and biosolids. Highlights: Values measured in SRM 2585 will be useful for future research in method development and method comparison.

Benefit of the Use of GCxGC/MS Profiles for 1D GC/MS Data Treatment Illustrated by the Analysis of Pyrolysis Products from East Asian Handmade Papers

NASA Astrophysics Data System (ADS)

Han, Bin; Lob, Silvia; Sablier, Michel

2018-06-01

In this study, we report the use of pyrolysis-GCxGC/MS profiles for an optimized treatment of data issued from pyrolysis-GC/MS combined with the automatic deconvolution software Automated Mass Spectral Deconvolution and Identification System (AMDIS). The method was illustrated by the characterization of marker compounds of East Asian handmade papers through the examination of pyrolysis-GCxGC/MS data to get information which was used for manually identifying low concentrated and co-eluting compounds in 1D GC/MS data. The results showed that the merits of a higher separation power for co-eluting compounds and a better sensitivity for low concentration compounds offered by a GCxGC system can be used effectively for AMDIS 1D GC/MS data treatment: (i) the compound distribution in pyrolysis-GCxGC/MS profiles can be used as "peak finder" for manual check of low concentration and co-eluting compound identification in 1D GC/MS data, and (ii) pyrolysis-GCxGC/MS profiles can provide better quality mass spectra with observed higher match factors in the AMDIS automatic match process. The combination of 2D profile with AMDIS was shown to contribute efficiently to a better characterization of compound profiles in the chromatograms obtained by 1D analysis in focusing on the mass spectral identification. [Figure not available: see fulltext.

De novo synthesis of trideuteromethyl esters of amino acids for use in GC-MS and GC-tandem MS exemplified for ADMA in human plasma and urine: standardization, validation, comparison and proof of evidence for their aptitude as internal standards.

PubMed

Tsikas, Dimitrios

2009-08-01

Asymmetric dimethylarginine (ADMA, N(G),N(G)-dimethyl-L-arginine) is an endogenous inhibitor of nitric oxide (NO) synthesis, a potential risk factor for cardiovascular diseases and a powerful biochemical parameter in clinical studies. In our previous work we have reported on a GC-tandem MS method for the accurate and precise quantification of ADMA in biological fluids using de novo synthesized [(2)H(3)]-methyl ester ADMA (d(3)Me-ADMA) as internal standard (IS). This method provides basal ADMA concentrations in biological fluids that agree with those obtained by other groups using other validated methods for ADMA. Unanimously, de novo synthesized stable-isotope labeled analogues are considered not ideal IS, because they must be prepared in a matrix different from the biological sample. Recently, [2,3,3,4,4,5,5-(2)H(7)]-ADMA (d(7)-ADMA) has become commercially available and we took this opportunity to test the reliability of the de novo synthesized d(3)Me-ADMA as an IS for ADMA in GC-tandem MS. In this article, we report on the re-validation of the previously reported GC-tandem MS method for ADMA in human plasma and urine using d(7)-ADMA as IS, and on comparative quantitative analyses of ADMA by GC-tandem MS using d(7)-ADMA and d(3)Me-ADMA. After thorough standardization of d(7)-ADMA and methods validation, we obtained by GC-tandem MS very similar ADMA concentrations in plasma and urine using d(7)-ADMA and d(3)Me-ADMA. The present study gives a proof of evidence for the aptitude of (2)H(3)-ADMA as IS in GC-tandem MS and suggests that de novo synthesis of stable-isotope labeled alkyl esters of amino acids and amino acid derivates may be a generally applicable method in mass spectrometry-based methods for amino acids. This approach is especially useful for amino acids for which no stable-isotope labeled analogues are commercially available.

Development of a multianalyte method based on micro-matrix-solid-phase dispersion for the analysis of fragrance allergens and preservatives in personal care products.

PubMed

Celeiro, Maria; Guerra, Eugenia; Lamas, J Pablo; Lores, Marta; Garcia-Jares, Carmen; Llompart, Maria

2014-05-30

An effective, simple and low cost sample preparation method based on matrix solid-phase dispersion (MSPD) followed by gas chromatography-mass spectrometry (GC-MS) or gas chromatography-triple quadrupole-mass spectrometry (GC-MS/MS) has been developed for the rapid simultaneous determination of 38 cosmetic ingredients, 25 fragrance allergens and 13 preservatives. All target substances are frequently used in cosmetics and personal care products and they are subjected to use restrictions or labeling requirements according to the EU Cosmetic Directive. The extraction procedure was optimized on real non-spiked rinse-off and leave-on cosmetic products by means of experimental designs. The final miniaturized process required the use of only 0.1g of sample and 1 mL of organic solvent, obtaining a final extract ready for analysis. The micro-MSPD method was validated showing satisfactory performance by GC-MS and GC-MS/MS analysis. The use of GC coupled to triple quadrupole mass detection allowed to reach very low detection limits (low ng g(-1)) improving, at the same time, method selectivity. In an attempt to improve the chromatographic analysis of preservatives, the inclusion of a derivatization step was also assessed. The proposed method was applied to a broad range of cosmetics and personal care products (shampoos, body milk, moisturizing milk, toothpaste, hand creams, gloss lipstick, sunblock, deodorants and liquid soaps among others), demonstrating the extended use of these substances. The concentration levels were ranging from the sub parts per million to the parts per mill. The number of target fragrance allergens per samples was quite high (up to 16). Several fragrances (linalool, farnesol, hexylcinnamal, and benzyl benzoate) have been detected at levels >0.1% (1,000 μg g(-1)). As regards preservatives, phenoxyethanol was the most frequently found additive reaching quite high concentration (>1,500 μg g(-1)) in five cosmetic products. BHT was detected in eight samples, in two of them (a baby care product and a lipstick) at high concentrations (>1,000 μg g(-1)). Methyl paraben was also found at high levels (>1,700 μg g(-1)) in three leave-on samples. Finally, triclosan was found at the maximum concentration limit (0.3%) laid down by the European regulation in two deodorant samples, and the total paraben concentration was close to the maximum concentration permitted (0.8%) in one leave-on sample (body milk). Copyright © 2014 Elsevier B.V. All rights reserved.

Automated Signal Processing Applied to Volatile-Based Inspection of Greenhouse Crops

PubMed Central

Jansen, Roel; Hofstee, Jan Willem; Bouwmeester, Harro; van Henten, Eldert

2010-01-01

Gas chromatograph–mass spectrometers (GC-MS) have been used and shown utility for volatile-based inspection of greenhouse crops. However, a widely recognized difficulty associated with GC-MS application is the large and complex data generated by this instrument. As a consequence, experienced analysts are often required to process this data in order to determine the concentrations of the volatile organic compounds (VOCs) of interest. Manual processing is time-consuming, labour intensive and may be subject to errors due to fatigue. The objective of this study was to assess whether or not GC-MS data can also be automatically processed in order to determine the concentrations of crop health associated VOCs in a greenhouse. An experimental dataset that consisted of twelve data files was processed both manually and automatically to address this question. Manual processing was based on simple peak integration while the automatic processing relied on the algorithms implemented in the MetAlign™ software package. The results of automatic processing of the experimental dataset resulted in concentrations similar to that after manual processing. These results demonstrate that GC-MS data can be automatically processed in order to accurately determine the concentrations of crop health associated VOCs in a greenhouse. When processing GC-MS data automatically, noise reduction, alignment, baseline correction and normalisation are required. PMID:22163594

Origin Discrimination of Osmanthus fragrans var. thunbergii Flowers using GC-MS and UPLC-PDA Combined with Multivariable Analysis Methods.

PubMed

Zhou, Fei; Zhao, Yajing; Peng, Jiyu; Jiang, Yirong; Li, Maiquan; Jiang, Yuan; Lu, Baiyi

2017-07-01

Osmanthus fragrans flowers are used as folk medicine and additives for teas, beverages and foods. The metabolites of O. fragrans flowers from different geographical origins were inconsistent in some extent. Chromatography and mass spectrometry combined with multivariable analysis methods provides an approach for discriminating the origin of O. fragrans flowers. To discriminate the Osmanthus fragrans var. thunbergii flowers from different origins with the identified metabolites. GC-MS and UPLC-PDA were conducted to analyse the metabolites in O. fragrans var. thunbergii flowers (in total 150 samples). Principal component analysis (PCA), soft independent modelling of class analogy analysis (SIMCA) and random forest (RF) analysis were applied to group the GC-MS and UPLC-PDA data. GC-MS identified 32 compounds common to all samples while UPLC-PDA/QTOF-MS identified 16 common compounds. PCA of the UPLC-PDA data generated a better clustering than PCA of the GC-MS data. Ten metabolites (six from GC-MS and four from UPLC-PDA) were selected as effective compounds for discrimination by PCA loadings. SIMCA and RF analysis were used to build classification models, and the RF model, based on the four effective compounds (caffeic acid derivative, acteoside, ligustroside and compound 15), yielded better results with the classification rate of 100% in the calibration set and 97.8% in the prediction set. GC-MS and UPLC-PDA combined with multivariable analysis methods can discriminate the origin of Osmanthus fragrans var. thunbergii flowers. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

A simple methodological validation of the gas/particle fractionation of polycyclic aromatic hydrocarbons in ambient air

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Kim, Ki-Hyun

2015-07-01

The analysis of polycyclic aromatic hydrocarbons (PAH) in ambient air requires the tedious experimental steps of both sampling and pretreatment (e.g., extraction or clean-up). To replace pre-existing conventional methods, a simple, rapid, and novel technique was developed to measure gas-particle fractionation of PAH in ambient air based on ‘sorbent tube-thermal desorption-gas chromatograph-mass spectrometer (ST-TD-GC-MS)’. The separate collection and analysis of ambient PAHs were achieved independently by two serially connected STs. The basic quality assurance confirmed good linearity, precision, and high sensitivity to eliminate the need for complicated pretreatment procedures with the detection limit (16 PAHs: 13.1 ± 7.04 pg). The analysis of real ambient PAH samples showed a clear fractionation between gas (two-three ringed PAHs) and particulate phases (five-six ringed PAHs). In contrast, for intermediate (four ringed) PAHs (fluoranthene, pyrene, benz[a]anthracene, and chrysene), a highly systematic/gradual fractionation was established. It thus suggests a promising role of ST-TD-GC-MS as measurement system in acquiring a reliable database of airborne PAH.

Results of the first provisional technical secretariat interlaboratory comparison test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stuff, J.R.; Hoffland, L.

1995-06-01

The principal task of this laboratory in the first Provisional Technical Secretariat (PTS) Interlaboratory Comparison Test was to verify and test the extraction and preparation procedures outlined in the Recommended Operating Procedures for Sampling and Analysis in the Verification of Chemical Disarmament in addition to our laboratory extraction methods and our laboratory analysis methods. Sample preparation began on 16 May 1994 and analysis was completed on 12 June 1994. The analytical methods used included NMR ({sup 1}H and {sup 31}P) GC/AED, GC/MS (EI and methane CI), GC/IRD, HPLC/IC, HPLC/TSP/MS, MS/MS(Electrospray), and CZE.

NHEXAS PHASE I ARIZONA STUDY--STANDARD OPERATING PROCEDURE FOR ANALYSIS OF PESTICIDE SAMPLES BY GC/MS (BCO-L-15.1)

EPA Science Inventory

The purpose of this SOP is to describe the methods used for detection and quantification by gas chromatography/mass spectrometry (GC/MS) of pesticides in a variety of matrices, including air, house dust, soil, and handwipes. This analysis involves automated gas GC/MS analysis us...

Gas chromatography-electron ionization-mass spectrometry quantitation of valproic acid and gabapentin, using dried plasma spots, for therapeutic drug monitoring in in-home medical care.

PubMed

Ikeda, Kayo; Ikawa, Kazuro; Yokoshige, Satoko; Yoshikawa, Satoshi; Morikawa, Norifumi

2014-12-01

A simple and sensitive gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) method using dried plasma spot testing cards was developed for determination of valproic acid and gabapentin concentrations in human plasma from patients receiving in-home medical care. We have proposed that a simple, easy and dry sampling method is suitable for in-home medical patients for therapeutic drug monitoring. Therefore, in the present study, we used recently developed commercially available easy handling cards: Whatman FTA DMPK-A and Bond Elut DMS. In-home medical care patients can collect plasma using these simple kits. The spots of plasma on the cards were extracted into methanol and then evaporated to dryness. The residues were trimethylsilylated using N-methyl-N-trimethylsilyltrifluoroacetamide. For GC-EI-MS analysis, the calibration curves on both cards were linear from 10 to 200 µg/mL for valproic acid, and from 0.5 to 10 µg/mL for gabapentin. Intra- and interday precisions in plasma were both ≤13.0% (coefficient of variation), and the accuracy was between 87.9 and 112% for both cards within the calibration curves. The limits of quantification were 10 µg/mL for valproic acid and 0.5 µg/mL for gabapentin on both cards. We believe that the present method will be useful for in-home medical care. Copyright © 2014 John Wiley & Sons, Ltd.

Development and evaluation of an enzyme-linked immunosorbent assay (ELISA) method for the measurement of 2,4-dichlorophenoxyacetic acid in human urine.

PubMed

Chuang, Jane C; Emon, Jeanette M Van; Durnford, Joyce; Thomas, Kent

2005-09-15

An enzyme-linked immunosorbent assay (ELISA) method was developed to quantitatively measure 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. Samples were diluted (1:5) with phosphate-buffered saline containing 0.05% Tween and 0.02% sodium azide, with analysis by a 96-microwell plate immunoassay format. No clean up was required as dilution step minimized sample interferences. Fifty urine samples were received without identifiers from a subset of pesticide applicators and their spouses in an EPA pesticide exposure study (PES) and analyzed by the ELISA method and a conventional gas chromatography/mass spectrometry (GC/MS) procedure. For the GC/MS analysis, urine samples were extracted with acidic dichloromethane (DCM); methylated by diazomethane and fractionated by a Florisil solid phase extraction (SPE) column prior to GC/MS detection. The percent relative standard deviation (%R.S.D.) of the 96-microwell plate triplicate assays ranged from 1.2 to 22% for the urine samples. Day-to-day variation of the assay results was within +/-20%. Quantitative recoveries (>70%) of 2,4-D were obtained for the spiked urine samples by the ELISA method. Quantitative recoveries (>80%) of 2,4-D were also obtained for these samples by the GC/MS procedure. The overall method precision of these samples was within +/-20% for both the ELISA and GC/MS methods. The estimated quantification limit for 2,4-D in urine was 30ng/mL by ELISA and 0.2ng/mL by GC/MS. A higher quantification limit for the ELISA method is partly due to the requirement of a 1:5 dilution to remove the urine sample matrix effect. The GC/MS method can accommodate a 10:1 concentration factor (10mL of urine converted into 1mL organic solvent for analysis) but requires extraction, methylation and clean up on a solid phase column. The immunoassay and GC/MS data were highly correlated, with a correlation coefficient of 0.94 and a slope of 1.00. Favorable results between the two methods were achieved despite the vast differences in sample preparation. Results indicated that the ELISA method could be used as a high throughput, quantitative monitoring tool for human urine samples to identify individuals with exposure to 2,4-D above the typical background levels.

The development and testing of a volatile organics concentrator for use in monitoring Space Station water quality

NASA Technical Reports Server (NTRS)

Bodek, Itamar; Ehntholt, Daniel J.; Stolki, Thomas J.; Trabanino, Rudy; Hinsdale, Lloyd; Webb, Johanna; Sauer, Richard L.

1992-01-01

The Volatile Organics Concentrator (VOC) system, designed to attach to a gas chromatograph/mass spectrometer (GC/MS) for the analyses of volatile organic compounds in water on Space Station Freedom, is described. Organic volatiles are collected and concentrated in the VOC by means of two primary solid sorbent tubes and desorbed into the GC/MS system. The paper describes the results of testing the VOC breadboard using a GC/MS system. Evaluations performed on 39 organic compounds recovered from water samples were compared with data for these compounds using direct injection/GC/MS and purge and trap/GC/MS procedures. The results demonstrate that the VOC/GC/MS system's detection limits for the 39 compounds analyzed are comparable to those of the EPA Method 524.2, and for many compounds reaching a factor of 5 lower.

Determination of different recreational drugs in sweat by headspace solid-phase microextraction gas chromatography mass spectrometry (HS-SPME GC/MS): Application to drugged drivers.

PubMed

Gentili, Stefano; Mortali, Claudia; Mastrobattista, Luisa; Berretta, Paolo; Zaami, Simona

2016-09-10

A procedure based on headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography/mass spectrometry (GC/MS) has been developed for the determination of most commonly used drugs of abuse in sweat of drivers stopped during roadside controls. DrugWipe 5A sweat screening device was used to collect sweat by a specific pad rubbed gently over forehead skin surface. The procedure involved an acid hydrolysis, a HS-SPME extraction for drugs of abuse but Δ(9)-tetrahydrocannabinol, which was directly extracted in alkaline medium HS-SPME conditions, a GC separation of analytes by a capillary column and MS detection by electron impact ionisation. The method was linear from the limit of quantification (LOQ) to 50ng drug per pad (r(2)≥0.99), with an intra- and inter-assay precision and accuracy always less than 15% and an analytical recovery between 95.1% and 102.8%, depending on the considered analyte. Using the validated method, sweat from 60 apparently intoxicated drivers were found positive to one or more drugs of abuse, showing sweat patches testing as a viable economic and simple alternative to conventional (blood and/or urine) and non conventional (oral fluid) testing of drugs of abuse in drugged drivers. Copyright © 2016 Elsevier B.V. All rights reserved.

Gas Chromatography-Tandem Mass Spectrometry of Lignin Pyrolyzates with Dopant-Assisted Atmospheric Pressure Chemical Ionization and Molecular Structure Search with CSI:FingerID

NASA Astrophysics Data System (ADS)

Larson, Evan A.; Hutchinson, Carolyn P.; Lee, Young Jin

2018-06-01

Dopant-assisted atmospheric pressure chemical ionization (dAPCI) is a soft ionization method rarely used for gas chromatography-mass spectrometry (GC-MS). The current study combines GC-dAPCI with tandem mass spectrometry (MS/MS) for analysis of a complex mixture such as lignin pyrolysis analysis. To identify the structures of volatile lignin pyrolysis products, collision-induced dissociation (CID) MS/MS using a quadrupole time-of-flight mass spectrometer (QTOFMS) and pseudo MS/MS through in-source collision-induced dissociation (ISCID) using a single stage TOFMS are utilized. To overcome the lack of MS/MS database, Compound Structure Identification (CSI):FingerID is used to interpret CID spectra and predict best matched structures from PubChem library. With this approach, a total of 59 compounds were positively identified in comparison to only 22 in NIST database search of GC-EI-MS dataset. This study demonstrates the effectiveness of GC-dAPCI-MS/MS to overcome the limitations of traditional GC-EI-MS analysis when EI-MS database is not sufficient. [Figure not available: see fulltext.

Diethylstilbestrol in fish tissue determined through subcritical fluid extraction and with GC-MS

NASA Astrophysics Data System (ADS)

Qiao, Qinghui; Shi, Nianrong; Feng, Xiaomei; Lu, Jie; Han, Yuqian; Xue, Changhu

2016-06-01

As the key point in sex hormone analysis, sample pre-treatment technology has attracted scientists' attention all over the world, and the development trend of sample preparation forwarded to faster and more efficient technologies. Taking economic and environmental concerns into account, subcritical fluid extraction as a faster and more efficient method has stood out as a sample pre-treatment technology. This new extraction technology can overcome the shortcomings of supercritical fluid and achieve higher extraction efficiency at relatively low pressures and temperatures. In this experiment, a simple, sensitive and efficient method has been developed for the determination of diethylstilbestrol (DES) in fish tissue using subcritical 1,1,1,2-tetrafluoroethane (R134a) extraction in combination with gas chromatography-mass spectrometry (GC-MS). After extraction, freezing-lipid filtration was utilized to remove fatty co-extract. Further purification steps were performed with C18 and NH2 solid phase extraction (SPE). Finally, the analyte was derived by heptafluorobutyric anhydride (HFBA), followed by GC-MS analysis. Response surface methodology (RSM) was employed to optimizing the extraction condition, and the optimized was as follows: extraction pressure, 4.3 MPa; extraction temperature, 26°C; amount of co-solvent volume, 4.7 mL. Under this condition, at a spiked level of 1, 5, 10 μg kg-1, the mean recovery of DES was more than 90% with relative standard deviations (RSDs) less than 10%. Finally, the developed method has been successfully used to analyzing the real samples.

High-Throughput Analytical Techniques for the Determination of the Residues of 653 Multiclass Pesticides and Chemical Pollutants in Tea, Part VII: A GC-MS, GC-MS/MS, and LC-MS/MS Study of the Degradation Profiles of Pesticide Residues in Green Tea.

PubMed

Chang, Qiao-Ying; Pang, Guo-Fang; Fan, Chun-Lin; Chen, Hui; Yang, Fang; Li, Jie; Wen, Bi-Fang

2016-11-01

GC-MS, GC-tandem MS (MS/MS), and LC-MS/MS were used to mathematically define the degradation profiles of pesticide residues in two field trials. Nineteen pesticides were studied in the first field trial and 11 in the second. The results of the field trials demonstrated that the degradation profiles of pesticide residues in green tea can be described with power functions to successfully estimate the amount of time, following pesticide application, pesticide residues appearing in tea in concentrations at and/or above the maximum residue limit (MRL) decrease to concentrations below the MRL. Stability tests on green tea samples stored at room temperature were conducted to determine whether pesticide-incurred green tea samples prepared according to the method used in the field trials would be suitable for the preparation of reference standards for laboratory-proficiency testing trials. This paper reports the results of a GC-MS, GC-MS/MS, and LC-MS/MS study, as well as the suitability of the samples prepared under these conditions for use as pesticide reference standards in tea analysis.

Gas chromatograph-mass spectrometer (GC/MS) system for quantitative analysis of reactive chemical compounds

DOEpatents

Grindstaff, Quirinus G.

1992-01-01

Described is a new gas chromatograph-mass spectrometer (GC/MS) system and method for quantitative analysis of reactive chemical compounds. All components of such a GC/MS system external to the oven of the gas chromatograph are programmably temperature controlled to operate at a volatilization temperature specific to the compound(s) sought to be separated and measured.

Determination of vitamins D2 and D3 in selected food matrices by online high-performance liquid chromatography-gas chromatography-mass spectrometry (HPLC-GC-MS).

PubMed

Nestola, Marco; Thellmann, Andrea

2015-01-01

An online normal-phase liquid chromatography-gas chromatography-mass spectrometry (HPLC-GC-MS) method was developed for the determination of vitamins D2 and D3 in selected food matrices. Transfer of the sample from HPLC to GC was realized by large volume on-column injection; detection was performed with a time-of-flight mass spectrometer (TOF-MS). Typical GC problems in the determination of vitamin D such as sample degradation or sensitivity issues, previously reported in the literature, were not observed. Determination of total vitamin D content was done by quantitation of its pyro isomer based on an isotopically labelled internal standard (ISTD). Extracted ion traces of analyte and ISTD showed cross-contribution, but non-linearity of the calibration curve was not determined inside the chosen calibration range by selection of appropriate quantifier ions. Absolute limits of detection (LOD) and quantitation (LOQ) for vitamins D2 and D3 were calculated as approximately 50 and 150 pg, respectively. Repeatability with internal standard correction was below 2 %. Good agreement between quantitative results of an established high-performance liquid chromatography with UV detection (HPLC-UV) method and HPLC-GC-MS was found. Sterol-enriched margarine was subjected to HPLC-GC-MS and HPLC-MS/MS for comparison, because HPLC-UV showed strong matrix interferences. HPLC-GC-MS produced comparable results with less manual sample cleanup. In summary, online hyphenation of HPLC and GC allowed a minimization in manual sample preparation with an increase of sample throughput.

A method for addressing differences in concentrations of fipronil and three degradates obtained by two different laboratory methods

USGS Publications Warehouse

Crawford, Charles G.; Martin, Jeffrey D.

2017-07-21

In October 2012, the U.S. Geological Survey (USGS) began measuring the concentration of the pesticide fipronil and three of its degradates (desulfinylfipronil, fipronil sulfide, and fipronil sulfone) by a new laboratory method using direct aqueous-injection liquid chromatography tandem mass spectrometry (DAI LC–MS/MS). This method replaced the previous method—in use since 2002—that used gas chromatography/mass spectrometry (GC/MS). The performance of the two methods is not comparable for fipronil and the three degradates. Concentrations of these four chemical compounds determined by the DAI LC–MS/MS method are substantially lower than the GC/MS method. A method was developed to correct for the difference in concentrations obtained by the two laboratory methods based on a methods comparison field study done in 2012. Environmental and field matrix spike samples to be analyzed by both methods from 48 stream sites from across the United States were sampled approximately three times each for this study. These data were used to develop a relation between the two laboratory methods for each compound using regression analysis. The relations were used to calibrate data obtained by the older method to the new method in order to remove any biases attributable to differences in the methods. The coefficients of the equations obtained from the regressions were used to calibrate over 16,600 observations of fipronil, as well as the three degradates determined by the GC/MS method retrieved from the USGS National Water Information System. The calibrated values were then compared to over 7,800 observations of fipronil and to the three degradates determined by the DAI LC–MS/MS method also retrieved from the National Water Information System. The original and calibrated values from the GC/MS method, along with measures of uncertainty in the calibrated values and the original values from the DAI LC–MS/MS method, are provided in an accompanying data release.

[Optimization for supercritical CO2 extraction with response surface methodology of Prunus armeniaca oil].

PubMed

Chen, Fei-Fei; Wu, Yan; Ge, Fa-Huan

2012-03-01

To optimize the extraction conditions of Prunus armeniaca oil by Supercritical CO2 extraction and identify its components by GC-MS. Optimized of SFE-CO extraction by response surface methodology and used GC-MS to analysis Prunus armeniaca oil compounds. Established the model of an equation for the extraction rate of Prunus armeniaca oil by supercritical CO2 extraction, and the optimal parameters for the supercritical CO2 extraction determined by the equation were: the extraction pressure was 27 MPa, temperature was 39 degrees C, the extraction rate of Prunus armeniaca oil was 44.5%. 16 main compounds of Prunus armeniaca oil extracted by supercritical CO2 were identified by GC-MS, unsaturated fatty acids were 92.6%. This process is simple, and can be used for the extraction of Prunus armeniaca oil.

A novel approach to transforming a non-targeted metabolic profiling method to a pseudo-targeted method using the retention time locking gas chromatography/mass spectrometry-selected ions monitoring.

PubMed

Li, Yong; Ruan, Qiang; Li, Yanli; Ye, Guozhu; Lu, Xin; Lin, Xiaohui; Xu, Guowang

2012-09-14

Non-targeted metabolic profiling is the most widely used method for metabolomics. In this paper, a novel approach was established to transform a non-targeted metabolic profiling method to a pseudo-targeted method using the retention time locking gas chromatography/mass spectrometry-selected ion monitoring (RTL-GC/MS-SIM). To achieve this transformation, an algorithm based on the automated mass spectral deconvolution and identification system (AMDIS), GC/MS raw data and a bi-Gaussian chromatographic peak model was developed. The established GC/MS-SIM method was compared with GC/MS-full scan (the total ion current and extracted ion current, TIC and EIC) methods, it was found that for a typical tobacco leaf extract, 93% components had their relative standard deviations (RSDs) of relative peak areas less than 20% by the SIM method, while 88% by the EIC method and 81% by the TIC method. 47.3% components had their linear correlation coefficient higher than 0.99, compared with 5.0% by the EIC and 6.2% by TIC methods. Multivariate analysis showed the pooled quality control samples clustered more tightly using the developed method than using GC/MS-full scan methods, indicating a better data quality. With the analysis of the variance of the tobacco samples from three different planting regions, 167 differential components (p<0.05) were screened out using the RTL-GC/MS-SIM method, but 151 and 131 by the EIC and TIC methods, respectively. The results show that the developed method not only has a higher sensitivity, better linearity and data quality, but also does not need complicated peak alignment among different samples. It is especially suitable for the screening of differential components in the metabolic profiling investigation. Copyright © 2012 Elsevier B.V. All rights reserved.

Evaluation of coal-related model compounds using a tandem mass spectrometry.

PubMed

Li, Guo-Sheng; Dong, Xueming; Fan, Xing; You, Chun-Yan; Wu, Ge; Zhao, Yun-Peng; Lu, Yao; Wei, Xian-Yong; Ma, Feng-Yun

2018-05-08

Gas chromotography/mass spectrometry (GC/MS) is a routine and basic instrumental method for the analysis of complex coal conversion products in chemical industry. To further enhance practical potentials of GC/MS in chemical industry, a tandem MS method for the selection of ion pair applied in monitoring coal conversions was established by using GC/quadrupole time-of-flight MS (GC/Q-TOF MS). The corresponding fragmentation pathways were explored and suitable ion pairs were screened. Fourteen coal-related model compounds (CRMCs) were analyzed using a GC/Q-TOF MS with different collision induced dissociation (CID) energies (5-20 eV). The fragmentation pathways can offer a better understanding of chemical bond breaking, hydrogen transfer, rearrangement reactions and elimination of neutral fragments for CRMCs during the CID process. The precursor ions of aromatic hydrocarbons without alkyl chain were hard to fragment with a CID energy of 20 eV. But aromatic hydrocarbons with branched chains were prone to fragment via the loss of alkyl chains and further fragmented through ring-open reactions. Compared to C alk -C ar bond, C ar -C ar bond was hard to fragment duo to its high bond dissociation energy. The existence of heteroatoms facilitated fragmentation that was conducive to screening ion pair. The CID technique of GC/Q-TOF MS will contribute to the studies on the organic composition of coals and building monitoring methods for coal conversions via fragmentation and ion pair selection. This article is protected by copyright. All rights reserved.

Single solid phase extraction method for the simultaneous analysis of polar and non-polar pesticides in urine samples by gas chromatography and ultra high pressure liquid chromatography coupled to tandem mass spectrometry.

PubMed

Cazorla-Reyes, Rocío; Fernández-Moreno, José Luis; Romero-González, Roberto; Frenich, Antonia Garrido; Vidal, José Luis Martínez

2011-07-15

A new multiresidue method has been developed and validated for the simultaneous extraction of more than two hundred pesticides, including non-polar and polar pesticides (carbamates, organochlorine, organophosphorous, pyrethroids, herbicides and insecticides) in urine at trace levels by gas and ultra high pressure liquid chromatography coupled to ion trap and triple quadrupole mass spectrometry, respectively (GC-IT-MS/MS, UHPLC-QqQ-MS/MS). Non-polar and polar pesticides were simultaneously extracted from urine samples by a simple and fast solid phase extraction (SPE) procedure using C(18) cartridges as sorbent, and dichloromethane as elution solvent. Recovery was in the range of 60-120%. Precision values expressed as relative standard deviation (RSD) were lower than 25%. Identification and confirmation of the compounds were performed by the use of retention time windows, comparison of spectra (GC-amenable compounds) or the estimation of the ion ratio (LC-amenable compounds). For GC-amenable pesticides, limits of detection (LODs) ranged from 0.001 to 0.436 μg L(-1) and limits of quantification (LOQs) from 0.003 to 1.452 μg L(-1). For LC-amenable pesticides, LODs ranged from 0.003 to 1.048 μg L(-1) and LOQs ranged from 0.011 to 3.494 μg L(-1). Finally, the optimized method was applied to the analysis of fourteen real samples of infants from agricultural population. Some pesticides such as methoxyfenozide, tebufenozide, piperonyl butoxide and propoxur were found at concentrations ranged from 1.61 to 24.4 μg L(-1), whereas methiocarb sulfoxide was detected at trace levels in two samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of handheld and portable spectrometers for screening acrylamide content in commercial potato chips.

PubMed

Ayvaz, Huseyin; Rodriguez-Saona, Luis E

2015-05-01

The most common methods for acrylamide analysis in foods require the use of LC-MS/MS and GC-MS. Although these methods have great analytical performance, they need intensive sample preparation, highly specialised instrumentation, and are time consuming. In this study, portable and handheld infrared spectrometers were evaluated as rapid methods for screening acrylamide in potato chips and their performances were compared to those of benchtop infrared systems. The acrylamide content of 64 commercial potato chips (169-2453 μg/kg) was determined by LC-MS/MS. Spectral data were collected using mid-infrared (MIR) and near-infrared (NIR) spectrometers. Partial least squares regression (PLSR) calibration models were developed to predict acrylamide levels. Overall, good linear correlation was found between the predicted acrylamide levels and actual measured acrylamide concentrations by LC-MS/MS (rPred > 0.90 and SEP < 100 μg/kg). Our results indicate that portable and handheld spectrometers can be used as simple and rapid alternatives for acrylamide analysis in potato chips. Copyright © 2014 Elsevier Ltd. All rights reserved.

Unstable simple volatiles and gas chromatography-tandem mass spectrometry analysis of essential oil from the roots bark of Oplopanax horridus extracted by supercritical fluid extraction.

PubMed

Shao, Li; Bao, Mei-Hua; Ouyang, Dong-Sheng; Wang, Chong-Zhi; Yuan, Chun-Su; Zhou, Hong-Hao; Huang, Wei-Hua

2014-11-27

Volatile oil from the root bark of Oplopanax horridus is regarded to be responsible for the clinical uses of the title plant as a respiratory stimulant and expectorant. Therefore, a supercritical fluid extraction method was first employed to extract the volatile oil from the roots bark of O. horridus, which was subsequently analyzed by GC/MS. Forty-eight volatile compounds were identified by GC/MS analysis, including (S,E)-nerolidol (52.5%), τ-cadinol (21.6%) and S-falcarinol (3.6%). Accordingly, the volatile oil (100 g) was subjected to chromatographic separation and purification. As a result, the three compounds, (E)-nerolidol (2 g), τ-cadinol (62 mg) and S-falcarinol (21 mg), were isolated and purified from the volatile oil, the structures of which were unambiguously elucidated by detailed spectroscopic analysis including 1D- and 2D-NMR techniques.

Separation and Identification of a Mixture of Group 6 Transition-Metal Carbonyl Compounds Using GC-MS in the General Chemistry Curriculum

ERIC Educational Resources Information Center

Fong, Lawrence K.

2004-01-01

Students in the general chemistry course are advised to scrutinize data obtained by gas chromatograph (GC) for segregation, and mass spectroscopy (MS) for recognizing combination of group 6 transition-metal carbonyl compounds. The GC-MS method arouses students' interest, as it can be applied to real-world situations, such as the routine…

Detecting a wide range of environmental contaminants in human blood samples--combining QuEChERS with LC-MS and GC-MS methods.

PubMed

Plassmann, Merle M; Schmidt, Magdalena; Brack, Werner; Krauss, Martin

2015-09-01

Exposure to environmental pollution and consumer products may result in an uptake of chemicals into human tissues. Several studies have reported the presence of diverse environmental contaminants in human blood samples. However, previously developed multi-target methods for the analysis of human blood include a fairly limited amount of compounds stemming from one or two related compound groups. Thus, the sample preparation method QuEChERS (quick easy cheap effective rugged and safe) was tested for the extraction of 64 analytes covering a broad compound domain followed by detection using liquid and gas chromatography coupled to mass spectrometry (LC- and GC-MS). Forty-seven analytes showed absolute recoveries above 70% in the first QuEChERS step, being a simple liquid-liquid extraction (LLE) using acetonitrile and salt. The second QuEChERS step, being a dispersive solid phase extraction, did not result in an overall improvement of recoveries or removal of background signals. Using solely the LLE step, eight analytes could subsequently be detected in human blood samples from the German Environmental Specimen Bank. Using a LC-multiple reaction monitoring (MRM) method with a triple quadrupole instrument, better recoveries were achieved than with an older LC-high-resolution (HR) MS full scan orbitrap instrument, which required a higher concentration factor of the extracts. However, the application of HRMS full scan methods could be used for the detection of additional compounds retrospectively.

Methods of Analysis - Determination of Pyrethroid Insecticides in Water and Sediment Using Gas Chromatography/Mass Spectrometry

USGS Publications Warehouse

Hladik, Michelle; Smalling, Kelly L.; Kuivila, Kathryn

2009-01-01

A method for the determination of 14 pyrethroid insecticides in environmental water and sediment samples is described. The method was developed by the U.S. Geological Survey in response to increasing concern over the effects of pyrethroids on aquatic organisms. The pyrethroids included in this method are ones that are applied to many agricultural and urban areas. Filtered water samples are extracted for pyrethroids using solid-phase extraction (SPE) with no additional cleanup steps. Sediment and soil samples are extracted using a microwave-assisted extraction system, and the pyrethroids of interest are separated from co-extracted matrix interferences by passing the extracts through stacked graphitized carbon and alumina SPE cartridges, along with the use of high-performance liquid chromatography and gel-permeation chromatography (HPLC/GPC). Quantification of the pyrethroids from the extracted water and sediment samples is done using gas chromatography with mass spectrometry (GC/MS) or gas chromatography with tandem mass spectrometry (GC/MS/MS). Recoveries in test water samples fortified at 10 ng/L ranged from 83 to 107 percent, and recoveries in test sediment samples fortified at 10 ug/kg ranged from 82 to 101 percent; relative standard deviations ranged from 5 to 9 percent in the water samples and 3 to 9 percent in the sediment samples. Method detection limits (MDLs), calculated using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), in water ranged from 2.0 to 6.0 ng/L using GC/MS and 0.5 to 1.0 ng/L using GC/MS/MS. For sediment, the MDLs ranged from 1.0 to 2.6 ug/kg dry weight using GC/MS and 0.2 to 0.5 ug/kg dry weight using GC/MS/MS. The matrix-spike recoveries for each compound, when averaged for 12 environmental water samples, ranged from 84 to 96 percent, and when averaged for 27 environmental sediment samples, ranged from 88 to 100 percent.

Optimization of separation and detection conditions for the multiresidue analysis of pesticides in grapes by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

PubMed

Banerjee, Kaushik; Patil, Sangram H; Dasgupta, Soma; Oulkar, Dasharath P; Patil, Shubhangi B; Savant, Rahul; Adsule, Pandurang G

2008-05-09

A comprehensive GCxGC-TOFMS method was optimized for multiresidue analysis of pesticides using a combination of a non-polar (RTX-5MS, 10 m x 0.18 mm x 0.2 microm) and a polar capillary column (TR-50MS, 1 m x 0.1 mm x 0.1 microm), connected in series through a dual stage thermal modulator. The method resolved the co-elution problems as observed in full scan one-dimensional GC-MS analysis and allowed chromatographic separation of 51 pesticides within 24 min run time with library-searchable mass spectrometric confirmation. Four pesticides, viz. chlorpyrifos-methyl, vinclozoline, parathion-methyl and heptachlor could be baseline separated on GCxGC, which were otherwise closely eluting and interfering each other's detection in 1D GC-MS run. Similarly, it could be possible to separate myclobutanil, buprofezin, flusilazole and oxyfluorfen on GCxGC. Although in 1D GC-MS, these closely eluting compounds could be identified through deconvolution algorithm and 'peak-find' option of the Chromatof software but the spectral purity significantly improved on GCxGC analysis. Thorough optimization was accomplished for the oven temperature programming, ion source temperature and GCxGC parameters like modulation period, duration of hot pulses, modulation-offset temperature, acquisition rate, etc. to achieve best possible separation of the test compounds. The limit of detection significantly improved by 2-12 times on GCxGC-TOFMS against GC-TOFMS because of sharper and narrower peak shapes. The method was tested for grape matrix after preparing the samples using previously described method and recoveries of the entire test pesticides were within 70-110% at 10 ng/g level of fortification. GCxGC-TOFMS was found to be an excellent technique for library-based screening of pesticides with high accuracy and sensitivity.

Analysis of acrylamide by LC-MS/MS and GC-MS in processed Japanese foods.

PubMed

Ono, H; Chuda, Y; Ohnishi-Kameyama, M; Yada, H; Ishizaka, M; Kobayashi, H; Yoshida, M

2003-03-01

Acrylamide concentrations in processed foods (63 samples covering 31 product types) from Japan were analysed by LC-MS/MS and GC-MS methods. The limit of detection and limit of quantification of acrylamide were 0.2 ng x ml(-1) (6 fmol) and 0.8 ng x ml(-1) (22 fmol), respectively, by LC-MS/MS, and those of 2,3-dibromopropionamide derived from acrylamide were 12 ng x ml(-1) (52 fmol) and 40 ng x ml(-1) (170 fmol), respectively, by GC-MS. Repeatability given as RSD was <5 and <15% for the LC-MS/MS and GC-MS methods, respectively. High correlation (r(2) - 0.946) was observed between values obtained by the two methods. Most potato crisps and whole potato-based fried snacks showed acrylamide concentrations >1000 microg x kg(-1). The concentrations in non-whole potato-based snacks, rice crackers processed by grilling or frying, and candied sweet potatoes were lower compared with those in the potato crisps and the whole potato-based fried snacks. One of the whole potato-based fried snacks, however, showed low acrylamide concentration (<50 microg x kg(-1)) suggesting the formation of acrylamide is strongly influenced by processing conditions. Acrylamide concentrations in instant precooked noodles and won-tons were <100 microg x kg(-1) with only one exception. Roasted barley grains for 'Mugi-cha' tea contained 200-600 microg x kg(-1) acrylamide.

Hair testing for cocaine and metabolites by GC/MS: criteria to quantitatively assess cocaine use.

PubMed

López-Guarnido, O; Álvarez, I; Gil, F; Rodrigo, L; Cataño, H C; Bermejo, A M; Tabernero, M J; Pla, A; Hernández, A F

2013-08-01

A simple, rapid and sensitive method has been developed and validated for the determination of cocaine and its main metabolites (benzoylecgonine and cocaethylene) in human hair. The method involved solid-phase extraction with an Oasis HLB extraction cartridge and subsequent analysis by GC/MS. The limit of detection was 0.01 ng mg(-1) for cocaine, 0.04 for benzoylecgonine and 0.03 for cocaethylene. The method validation included linearity (with a correlation coefficient >0.99 over the range 0.2-50 ng mg(-1) ), intra- and inter-day precision (always lower than 12%) and accuracy (mean relative error always below 17%) to meet the bioanalytical acceptance criteria. The procedure was further applied to 40 hair samples from self-reported cocaine users arrested by the police who provided a positive urine-analysis for cocaine, and was demonstrated to be suitable for its application in forensic toxicology. New approaches were raised to detect false-negative results that allow a better interpretation of hair testing results. Copyright © 2012 John Wiley & Sons, Ltd.

VOLATILE ORGANO-METALLOIDS IN BIO-SOLID MATERIALS: ANALYSIS BY VACUUM DISTILLATION-GC/MS

EPA Science Inventory

An analytical method based on vacuum distillation-gas chromatography-mass spectrometry (VD-GC-MS)

was developed for determining volatile organo-metalloid contaminants in bio-solid materials. Method

performance was evaluated for dimethylselenide (DMSe), dimethyldisel...

Headspace-SPME-GC/MS as a simple cleanup tool for sensitive 2,6-diisopropylphenol analysis from lipid emulsions and adaptable to other matrices.

PubMed

Pickl, Karin E; Adamek, Viktor; Gorges, Roland; Sinner, Frank M

2011-07-15

Due to increased regulatory requirements, the interaction of active pharmaceutical ingredients with various surfaces and solutions during production and storage is gaining interest in the pharmaceutical research field, in particular with respect to development of new formulations, new packaging material and the evaluation of cleaning processes. Experimental adsorption/absorption studies as well as the study of cleaning processes require sophisticated analytical methods with high sensitivity for the drug of interest. In the case of 2,6-diisopropylphenol - a small lipophilic drug which is typically formulated as lipid emulsion for intravenous injection - a highly sensitive method in the concentration range of μg/l suitable to be applied to a variety of different sample matrices including lipid emulsions is needed. We hereby present a headspace-solid phase microextraction (HS-SPME) approach as a simple cleanup procedure for sensitive 2,6-diisopropylphenol quantification from diverse matrices choosing a lipid emulsion as the most challenging matrix with regard to complexity. By combining the simple and straight forward HS-SPME sample pretreatment with an optimized GC-MS quantification method a robust and sensitive method for 2,6-diisopropylphenol was developed. This method shows excellent sensitivity in the low μg/l concentration range (5-200μg/l), good accuracy (94.8-98.8%) and precision (intraday-precision 0.1-9.2%, inter-day precision 2.0-7.7%). The method can be easily adapted to other, less complex, matrices such as water or swab extracts. Hence, the presented method holds the potential to serve as a single and simple analytical procedure for 2,6-diisopropylphenol analysis in various types of samples such as required in, e.g. adsorption/absorption studies which typically deal with a variety of different surfaces (steel, plastic, glass, etc.) and solutions/matrices including lipid emulsions. Copyright © 2011 Elsevier B.V. All rights reserved.

Screening and monitoring microbial xenobiotics' biodegradation by rapid, inexpensive and easy to perform microplate UV-absorbance measurements.

PubMed

Herzog, Bastian; Lemmer, Hilde; Horn, Harald; Müller, Elisabeth

2014-02-22

Evaluation of xenobiotics biodegradation potential, shown here for benzotriazoles (corrosion inhibitors) and sulfamethoxazole (sulfonamide antibiotic) by microbial communities and/or pure cultures normally requires time intensive and money consuming LC/GC methods that are, in case of laboratory setups, not always needed. The usage of high concentrations to apply a high selective pressure on the microbial communities/pure cultures in laboratory setups, a simple UV-absorbance measurement (UV-AM) was developed and validated for screening a large number of setups, requiring almost no preparation and significantly less time and money compared to LC/GC methods. This rapid and easy to use method was evaluated by comparing its measured values to LC-UV and GC-MS/MS results. Furthermore, its application for monitoring and screening unknown activated sludge communities (ASC) and mixed pure cultures has been tested and approved to detect biodegradation of benzotriazole (BTri), 4- and 5-tolyltriazole (4-TTri, 5-TTri) as well as SMX. In laboratory setups, xenobiotics concentrations above 1.0 mg L(-1) without any enrichment or preparation could be detected after optimization of the method. As UV-AM does not require much preparatory work and can be conducted in 96 or even 384 well plate formats, the number of possible parallel setups and screening efficiency was significantly increased while analytic and laboratory costs were reduced to a minimum.

Screening and monitoring microbial xenobiotics’ biodegradation by rapid, inexpensive and easy to perform microplate UV-absorbance measurements

PubMed Central

2014-01-01

Background Evaluation of xenobiotics biodegradation potential, shown here for benzotriazoles (corrosion inhibitors) and sulfamethoxazole (sulfonamide antibiotic) by microbial communities and/or pure cultures normally requires time intensive and money consuming LC/GC methods that are, in case of laboratory setups, not always needed. Results The usage of high concentrations to apply a high selective pressure on the microbial communities/pure cultures in laboratory setups, a simple UV-absorbance measurement (UV-AM) was developed and validated for screening a large number of setups, requiring almost no preparation and significantly less time and money compared to LC/GC methods. This rapid and easy to use method was evaluated by comparing its measured values to LC-UV and GC-MS/MS results. Furthermore, its application for monitoring and screening unknown activated sludge communities (ASC) and mixed pure cultures has been tested and approved to detect biodegradation of benzotriazole (BTri), 4- and 5-tolyltriazole (4-TTri, 5-TTri) as well as SMX. Conclusions In laboratory setups, xenobiotics concentrations above 1.0 mg L-1 without any enrichment or preparation could be detected after optimization of the method. As UV-AM does not require much preparatory work and can be conducted in 96 or even 384 well plate formats, the number of possible parallel setups and screening efficiency was significantly increased while analytic and laboratory costs were reduced to a minimum. PMID:24558966

Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum.

PubMed

Geng, Dawei; Jogsten, Ingrid Ericson; Dunstan, Jody; Hagberg, Jessika; Wang, Thanh; Ruzzin, Jerome; Rabasa-Lhoret, Rémi; van Bavel, Bert

2016-07-01

A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS. Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous determination of rhamnose, xylitol, arabitol, fructose, glucose, inositol, sucrose, maltose in jujube (Zizyphus jujube Mill.) extract: comparison of HPLC-ELSD, LC-ESI-MS/MS and GC-MS.

PubMed

Sun, Shihao; Wang, Hui; Xie, Jianping; Su, Yue

2016-01-01

Jujube extract is commonly used as a food additive and flavoring. The sensory properties of the extract, especially sweetness, are a critical factor determining the product quality and therefore affecting consumer acceptability. Small molecular carbohydrates make major contribution to the sweetness of the jujube extract, and their types and contents in the extract have direct influence on quality of the product. So, an appropriate qualitative and quantitative method for determination of the carbohydrates is vitally important for quality control of the product. High performance liquid chromatography-evaporative light scattering detection (HPLC-ELSD), liquid chromatography-electronic spay ionization tandem mass spectrometry (LC-ESI-MS/MS), and gas chromatography-mass spectrometry (GC-MS) methods have been developed and applied to determining small molecular carbohydrates in jujube extract, respectively. Eight sugars and alditols were identified from the extract, including rhamnose, xylitol, arabitol, fructose, glucose, inositol, sucrose, and maltose. Comparisons were carried out to investigate the performance of the methods. Although the methods have been found to perform satisfactorily, only three sugars (fructose, glucose and inositol) could be detected by all these methods. Meanwhile, a similar quantitative result for the three sugars can be obtained by the methods. Eight sugars and alditols in the jujube extract were determined by HPLC-ELSD, LC-ESI-MS/MS and GC-MS, respectively. The LC-ELSD method and the LC-ESI-MS/MS method with good precision and accuracy were suitable for quantitative analysis of carbohydrates in jujube extract; although the performance of the GC-MS method for quantitative analysis was inferior to the other methods, it has a wider scope in qualitative analysis. A multi-analysis technique should be adopted in order to obtain complete constituents of about the carbohydrates in jujube extract, and the methods should be employed according to the purpose of analysis.

Multiresidue pesticide analysis in ginseng and spinach by nontargeted and targeted screening procedures.

PubMed

Hayward, Douglas G; Wong, Jon W; Zhang, Kai; Chang, James; Shi, Feng; Banerjee, Kaushik; Yang, Paul

2011-01-01

Five different mass spectrometers interfaced to GC or LC were evaluated for their application to targeted and nontargeted screening of pesticides in two foods, spinach and ginseng. The five MS systems were capillary GC/MS/MS, GC-high resolution time-of-flight (GC/HR-TOF)-MS, TOF-MS interfaced with a comprehensive multidimensional GC (GCxGC/TOF-MS), an MS/MS ion trap hybrid mass (qTrap) system interfaced with an ultra-performance liquid chromatograph (UPLC-qTrap), and UPLC interfaced to an orbital trap high resolution mass spectrometer (UPLC/Orbitrap HR-MS). Each MS system was tested with spinach and ginseng extracts prepared through a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure. Each matrix was fortified at 10 and 50 ng/g for spinach or 25 and 100 ng/g for ginseng with subsets of 486 pesticides, isomers, and metabolites representing most pesticide classes. HR-TOF-MS was effective in a targeted search for characteristic accurate mass ions and identified 97% of 170 pesticides in ginseng at 25 ng/g. A targeted screen of either ginseng or spinach found 94-95% of pesticides fortified for analysis at 10 ng/g with GC/MS/MS or LC/MS/MS using multiple reaction monitoring (MRM) procedures. Orbitrap-MS successfully found 89% of 177 fortified pesticides in spinach at 25 ng/g using a targeted search of accurate mass pseudomolecular ions in the positive electrospray ionization mode. A comprehensive GCxGC/TOF-MS system provided separation and identification of 342 pesticides and metabolites in a single 32 min acquisition with standards. Only 67 or 81% of the pesticides were identified in ginseng and spinach matrixes at 25 ng/g or 10 ng/g, respectively. MS/MS or qTrap-MS operated in the MRM mode produced the lowest false-negative rates, at 10 ng/g. Improvements to instrumentation, methods, and software are needed for efficient use of nontargeted screens in parallel with triple quadrupole MS.

EPA Method 525.3 - Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)

EPA Science Inventory

Method 525.3 is an analytical method that uses solid phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) for the identification and quantitation of 125 selected semi-volatile organic chemicals in drinking water.

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

PubMed

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.

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

PubMed Central

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

2011-01-01

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. PMID:29403714

Determination of short chain chlorinated paraffins in water by stir bar sorptive extraction-thermal desorption-gas chromatography-triple quadrupole tandem mass spectrometry.

PubMed

Tölgyessy, P; Nagyová, S; Sládkovičová, M

2017-04-21

A simple, robust, sensitive and environment friendly method for the determination of short chain chlorinated paraffins (SCCPs) in water using stir bar sorptive extraction (SBSE) coupled to thermal desorption-gas chromatography-triple quadrupole tandem mass spectrometry (TD-GC-QqQ-MS/MS) was developed. SBSE was performed using 100mL of water sample, 20mL of methanol as a modifier, and a commercial sorptive stir bar (with 10mm×0.5mm PDMS layer) during extraction period of 16h. After extraction, the sorptive stir bar was thermally desorbed and online analysed by GC-MS/MS. Method performance was evaluated for MilliQ and surface water spiked samples. For both types of matrices, a linear dynamic range of 0.5-3.0μgL -1 with correlation coefficients >0.999 and relative standard deviations (RSDs) of the relative response factors (RRFs) <12% was established. The limits of quantification (LOQs) of 0.06 and 0.08μgL -1 , and the precision (repeatability) of 6.4 and 7.7% (RSDs) were achieved for MilliQ and surface water, respectively. The method also showed good robustness, recovery and accuracy. The obtained performance characteristics indicate that the method is suitable for screening and monitoring and compliance checking with environmental quality standards (EQS, set by the EU) for SCCPs in surface waters. Copyright © 2017 Elsevier B.V. All rights reserved.

Modified Method for Detection of Benzoylecgonine in Human Urine by GC-MS: Derivatization Using Pentafluoropropanol/Acetic Anhydride.

PubMed

Serafin, Michelle C; Paulemon, Kasandra M; Fuller, Zachary J; Bronner, William E

2017-05-01

An existing GC-MS method for detecting benzoylecgonine (BZE) in urine was modified by changing derivatizing reagents. This method modification presents a cost-effective alternative derivatization procedure for the detection of BZE in urine by GC-MS. The combination of pentafluoropropanol and acetic anhydride was found to produce the same reaction product for BZE as pentafluoropropanol with pentafluoropropionic anhydride, while reducing reagent cost. With no anhydride present, derivatization of BZE by pentafluoropropanol did not occur. Published by Oxford University Press 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Development of a GC-MS-SPME Method for the Determination of Amines in Meteorites

NASA Astrophysics Data System (ADS)

Hilts, R. W.; Skelhorne, A. W.; Simkus, D.; Herd, C. D. K.

2016-08-01

A GC-MS-SPME analytical method for the direct determination of amines in aqueous solution has been developed. The key step in the procedure is the conversion of the amines into their non-volatile ammonium salts by protonation with HCl.

Evaluation of Immunoassay for the Determination of Pesticides at a Large-Scale Groundwater Contamination Site

USGS Publications Warehouse

Dombrowski, T.R.; Thurman, E.M.; Mohrman, G.B.

1996-01-01

Pesticide concentrations in ground water at Rocky Mountain Arsenal (RMA) near Denver, Colorado, were determined using solid-phase extraction (SPE) gas chromatography/mass spectrometry (GC/MS) procedures and enzyme-linked immunosorbent assay (ELISA) for cyclodiene insecticides and triazine herbicides. Matrix interferences resulted in inconclusive results for some GC/MS analyses due to baseline disturbances and co-elution, but ELISA analyses consistently gave definitive results in a minimum amount of time. ELISA was used initially as a screening method, and pesticide concentrations and plume extents identified by ELISA were confirmed by SPE-GC/MS. A high degree of correlation was seen between results from GC/MS and ELISA methods for the triazine herbicides (correlation coefficient (R2) = 0.99). All areas with high pesticide concentrations were found to be within the boundaries of RMA.

Use of a deuterated internal standard with pyrolysis-GC/MS dimeric marker analysis to quantify tire tread particles in the environment.

PubMed

Unice, Kenneth M; Kreider, Marisa L; Panko, Julie M

2012-11-08

Pyrolysis(pyr)-GC/MS analysis of characteristic thermal decomposition fragments has been previously used for qualitative fingerprinting of organic sources in environmental samples. A quantitative pyr-GC/MS method based on characteristic tire polymer pyrolysis products was developed for tread particle quantification in environmental matrices including soil, sediment, and air. The feasibility of quantitative pyr-GC/MS analysis of tread was confirmed in a method evaluation study using artificial soil spiked with known amounts of cryogenically generated tread. Tread concentration determined by blinded analyses was highly correlated (r2 ≥ 0.88) with the known tread spike concentration. Two critical refinements to the initial pyrolysis protocol were identified including use of an internal standard and quantification by the dimeric markers vinylcyclohexene and dipentene, which have good specificity for rubber polymer with no other appreciable environmental sources. A novel use of deuterated internal standards of similar polymeric structure was developed to correct the variable analyte recovery caused by sample size, matrix effects, and ion source variability. The resultant quantitative pyr-GC/MS protocol is reliable and transferable between laboratories.

Electronic cigarette solutions and resultant aerosol profiles.

PubMed

Herrington, Jason S; Myers, Colton

2015-10-30

Electronic cigarettes (e-cigarettes) are growing in popularity exponentially. Despite their ever-growing acceptance, their aerosol has not been fully characterized. The current study focused on evaluating e-cigarette solutions and their resultant aerosol for potential differences. A simple sampling device was developed to draw e-cigarette aerosol into a multi-sorbent thermal desorption (TD) tube, which was then thermally extracted and analyzed via a gas chromatography (GC) mass spectrometry (GC-MS) method. This novel application provided detectable levels of over one hundred fifteen volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) from a single 40mL puff. The aerosol profiles from four commercially available e-cigarettes were compared to their respective solution profiles with the same GC-MS method. Solution profiles produced upwards of sixty four unidentified and identified (some only tentatively) constituents and aerosol profiles produced upwards of eighty two compounds. Results demonstrated distinct analyte profiles between liquid and aerosol samples. Most notably, formaldehyde, acetaldehyde, acrolein, and siloxanes were found in the aerosol profiles; however, these compounds were never present in the solutions. These results implicate the aerosolization process in the formation of compounds not found in solutions; have potential implications for human health; and stress the need for an emphasis on electronic cigarette aerosol testing. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Fast quantitative analysis of boric acid by gas chromatography-mass spectrometry coupled with a simple and selective derivatization reaction using triethanolamine.

PubMed

Zeng, Li-Min; Wang, Hao-Yang; Guo, Yin-Long

2010-03-01

A fast, selective, and sensitive GC-MS method has been developed and validated for the determination of boric acid in the drinking water by derivatization with triethanolamine. This analytic strategy successfully converts the inorganic, nonvolatile boric acid B(OH)(3) present in the drinking water to a volatile triethanolamine borate B(OCH(2)CH(2))(3)N in a quantitative manner, which facilitates the GC measurement. The SIM mode was applied in the analysis and showed high accuracy, specificity, and reproducibility, as well as reducing the matrix effect effectively. The calibration curve was obtained from 0.01 microg/mL to 10.0 microg/mL with a satisfactory correlation coefficient of 0.9988. The limit of detection for boric acid was 0.04 microg/L. Then the method was applied for detection of the amount of boric acid in bottled drinking water and the results are in accordance with the reported concentration value of boric acid. This study offers a perspective into the utility of GC-MS as an alternate quantitative tool for detection of B(OH)(3), even for detection of boron in various other samples by digesting the boron compounds to boric acid. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Evaluation of the matrix effect on gas chromatography--mass spectrometry with carrier gas containing ethylene glycol as an analyte protectant.

PubMed

Fujiyoshi, Tomoharu; Ikami, Takahito; Sato, Takashi; Kikukawa, Koji; Kobayashi, Masato; Ito, Hiroshi; Yamamoto, Atsushi

2016-02-19

The consequences of matrix effects in GC are a major issue of concern in pesticide residue analysis. The aim of this study was to evaluate the applicability of an analyte protectant generator in pesticide residue analysis using a GC-MS system. The technique is based on continuous introduction of ethylene glycol into the carrier gas. Ethylene glycol as an analyte protectant effectively compensated the matrix effects in agricultural product extracts. All peak intensities were increased by this technique without affecting the GC-MS performance. Calibration curves for ethylene glycol in the GC-MS system with various degrees of pollution were compared and similar response enhancements were observed. This result suggests a convenient multi-residue GC-MS method using an analyte protectant generator instead of the conventional compensation method for matrix-induced response enhancement adding the mixture of analyte protectants into both neat and sample solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Catalytic pyrolysis-GC/MS of lignin from several sources

USDA-ARS?s Scientific Manuscript database

Lignin from four different sources extracted by various methods were pyrolyzed at 650 degree C using analytical pyrolysis methods, py-GC/MS. Pyrolysis was carried out in the absence and presence of two heterogeneous catalysts , an acidic zeolite (HZSM-5) catalyst and a mixed metal oxide catalyst (Co...

Rapid Identification of Synthetic Cannabinoids in Herbal Incenses with DART-MS and NMR.

PubMed

Marino, Michael A; Voyer, Brandy; Cody, Robert B; Dane, A John; Veltri, Mercurio; Huang, Ling

2016-01-01

The usage of herbal incenses containing synthetic cannabinoids has caused an increase in medical incidents and triggered legislations to ban these products throughout the world. Law enforcement agencies are experiencing sample backlogs due to the variety of the products and the addition of new and still-legal compounds. In our study, proton nuclear magnetic resonance (NMR) spectroscopy was employed to promptly screen the synthetic cannabinoids after their rapid, direct detection on the herbs and in the powders by direct analysis in real time mass spectrometry (DART-MS). A simple sample preparation protocol was employed on 50 mg of herbal sample matrices for quick NMR detection. Ten synthetic cannabinoids were discovered in fifteen herbal incenses. The combined DART-MS and NMR methods can be used to quickly screen synthetic cannabinoids in powder and herbal samples, serving as a complementary approach to conventional GC-MS or LC-MS methods. © 2015 American Academy of Forensic Sciences.

Diagnosis of glutaric aciduria type 1 by measuring 3-hydroxyglutaric acid in dried urine spots by liquid chromatography tandem mass spectrometry.

PubMed

Al-Dirbashi, Osama Y; Kölker, Stefan; Ng, Dione; Fisher, Lawrence; Rupar, Tony; Lepage, Nathalie; Rashed, Mohamed S; Santa, Tomofumi; Goodman, Stephen I; Geraghty, Michael T; Zschocke, Johannes; Christensen, Ernst; Hoffmann, Georg F; Chakraborty, Pranesh

2011-02-01

Accumulation of glutaric acid (GA) and 3-hydroxyglutaric acid (3HGA) in body fluids is the biochemical hallmark of type 1 glutaric aciduria (GA1), a disorder characterized by acute striatal degeneration and a subsequent dystonia. To date, methods for quantification of 3HGA are mainly based on stable isotope dilution gas chromatography mass spectrometry (GC-MS) and require extensive sample preparation. Here we describe a simple liquid chromatography tandem MS (LC-MS/MS) method to quantify this important metabolite in dried urine spots (DUS). This method is based on derivatization with 4-[2-(N,N-dimethylamino)ethylaminosulfonyl]-7-(2-aminoethylamino)-2,1,3-benzoxadiazole (DAABD-AE). Derivatization was adopted to improve the chromatographic and mass spectrometric properties of the studied analytes. Derivatization was performed directly on a 3.2-mm disc of DUS as a sample without extraction. Sample mixture was heated at 60°C for 45 min, and 5 μl of the reaction solution was analyzed by LC-MS/MS. Reference ranges obtained were in excellent agreement with the literature. The method was applied retrospectively for the analysis of DUS samples from established low- and high-excreter GA1 patients as well as controls (n = 100). Comparison of results obtained versus those obtained by GC-MS was satisfactory (n = 14). In populations with a high risk of GA1, this approach will be useful as a primary screening method for high- or low-excreter variants. In these populations, however, DUS analysis should not be implemented before completing a parallel comparative study with the standard screening method (i.e., molecular testing). In addition, follow-up DUS GA and 3HGA testing of babies with elevated dried blood spot C5DC acylcarnitines will be useful as a first-tier diagnostic test, thus reducing the number of cases requiring enzymatic and molecular analyses to establish or refute the diagnosis of GA1.

[In-situ measurement of background atmospheric HCFC-142b using GC-MS and GC-ECD method].

PubMed

Guo, Li-feng; Yao, Bo; Zhou, Ling-xi; Li, Pei-chang; Xu, Lin

2013-05-01

Custom-made GC-MS and GC-ECD in-situ measurement systems were established at the Shangdianzi GAW Regional station. From May 2010 to May 2011, the precisions for GC-MS and GC-ECD systems were 0.23% and 0.88%, respectively, and the HCFC-142b mole fraction during the observation period ranged from 21 x 10(-12) to 355 x 10(-12). The result of the independent-sample T test was P > 0.05, and there was no significant difference in HCFC-142b mole fraction measured by the two systems. The small difference of HCFC-142b mole fraction measured by GC-MS and GC-ECD might be associated with the different sampling time and precision of the two systems. A statistical filter of "robust local regression" was applied to separate HCFC-142b background and pollution data. The mean difference, median difference, 25 and 75 percent difference of background data measured by GC-MS and GC-ECD were all within the precisions. The pollution events captured by the two systems showed similar characters. Results from both systems showed a higher HCFC-142b level in summer and autumn than in winter. The pollution mole fraction of the two systems showed similar seasonal changes.

Fast, sensitive and reliable multi-residue method for routine determination of 34 pesticides from various chemical groups in water samples by using dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry.

PubMed

Tankiewicz, Maciej; Biziuk, Marek

2018-02-01

A simple and efficient dispersive liquid-liquid microextraction technique (DLLME) was developed by using a mixture of two solvents: 40 μL of tetrachlorethylene (extraction solvent) and 1.0 mL of methanol (disperser solvent), which was rapidly injected with a syringe into 10 mL of water sample. Some important parameters affecting the extraction efficiency, such as type and volume of solvents, water sample volume, extraction time, temperature, pH adjustment and salt addition effect were investigated. Simultaneous determination of 34 commonly used pesticides was performed by using gas chromatography coupled with mass spectrometry (GC-MS). The procedure has been validated in order to obtain the highest efficiency at the lowest concentration levels of analytes to fulfill the requirements of regulations on maximum residue limits. Under the optimum conditions, the linearity range was within 0.0096-100 μg L -1 . The limits of detection (LODs) of the developed DLLME-GC-MS methodology for all investigated pesticides were in the range of 0.0032 (endrin)-0.0174 (diazinon) μg L -1 and limits of quantification (LOQs) from 0.0096 to 0.052 μg L -1 . At lower concentration of 1 μg L -1 for each pesticide, recoveries ranged between 84% (tebufenpyrad) and 108% (deltamethrin) with relative standard deviations (RSDs) (n = 7) from 1.1% (metconazole) to 11% (parathion-mehtyl). This methodology was successfully applied to check contamination of environmental samples. The procedure has proved to be selective, sensitive and precise for the simultaneous determination of various pesticides. The optimized analytical method is very simple and rapid (less than 5 min). Graphical abstract Analytical procedure for testing water samples consists of dispersive liquid-liquid microextraction (DLLME) and gas chromatography coupled with mass spectrometry (GC-MS).

Comprehensive two-dimensional gas chromatography in combination with rapid scanning quadrupole mass spectrometry in perfume analysis.

PubMed

Mondello, Luigi; Casillia, Alessandro; Tranchida, Peter Quinto; Dugo, Giovanni; Dugo, Paola

2005-03-04

Single column gas chromatography (GC) in combination with a flame ionization detector (FID) and/or a mass spectrometer is routinely employed in the determination of perfume profiles. The latter are to be considered medium to highly complex matrices and, as such, can only be partially separated even on long capillaries. Inevitably, several monodimensional peaks are the result of two or more overlapping components, often hindering reliable identification and quantitation. The present investigation is based on the use of a comprehensive GC (GC x GC) method, in vacuum outlet conditions, for the near to complete resolution of a complex perfume sample. A rapid scanning quadrupole mass spectrometry (qMS) system, employed for the assignment of GC x GC peaks, supplied high quality mass spectra. The validity of the three-dimensional (3D) GC x GC-qMS application was measured and compared to that of GC-qMS analysis on the same matrix. Peak identification, in all applications, was achieved through MS spectra library matching and the interactive use of linear retention indices (LRI).

A fast and reliable method for GHB quantitation in whole blood by GC-MS/MS (TQD) for forensic purposes.

PubMed

Castro, André L; Tarelho, Sónia; Dias, Mário; Reis, Flávio; Teixeira, Helena M

2016-02-05

Gamma-hydroxybutyric acid (GHB) is an endogenous compound with a story of clinical use since the 1960s. However, due to its secondary effects, it has become a controlled substance, entering the illicit market. A fully validated, sensitive and reproducible method for the quantification of GHB by methanolic precipitation and GC-MS/MS (TQD) in whole blood is presented. Using 100μL of whole blood, obtained results included a LOD and LLOQ of 0.1mg/L and a recovery of 86% in a working range between 0.1 and 100mg/L. This method is sensitive and specific to detect the presence of GHB in small amounts of whole blood (both ante-mortem or post-mortem), and is, to the authors' knowledge, the first GC-MS-MS TQD method that uses different precursor ions and product ions for the identification of GHB and GHB-D6 (internal standard). Hence, this method may be especially useful for the study of endogenous values in this biological sample. Copyright © 2015 Elsevier B.V. All rights reserved.

The limitations on organic detection in Mars-like soils by thermal volatilization-gas chromatography-MS and their implications for the Viking results.

PubMed

Navarro-González, Rafael; Navarro, Karina F; de la Rosa, José; Iñiguez, Enrique; Molina, Paola; Miranda, Luis D; Morales, Pedro; Cienfuegos, Edith; Coll, Patrice; Raulin, François; Amils, Ricardo; McKay, Christopher P

2006-10-31

The failure of Viking Lander thermal volatilization (TV) (without or with thermal degradation)-gas chromatography (GC)-MS experiments to detect organics suggests chemical rather than biological interpretations for the reactivity of the martian soil. Here, we report that TV-GC-MS may be blind to low levels of organics on Mars. A comparison between TV-GC-MS and total organics has been conducted for a variety of Mars analog soils. In the Antarctic Dry Valleys and the Atacama and Libyan Deserts we find 10-90 mug of refractory or graphitic carbon per gram of soil, which would have been undetectable by the Viking TV-GC-MS. In iron-containing soils (jarosites from Rio Tinto and Panoche Valley) and the Mars simulant (palogonite), oxidation of the organic material to carbon dioxide (CO(2)) by iron oxides and/or their salts drastically attenuates the detection of organics. The release of 50-700 ppm of CO(2) by TV-GC-MS in the Viking analysis may indicate that an oxidation of organic material took place. Therefore, the martian surface could have several orders of magnitude more organics than the stated Viking detection limit. Because of the simplicity of sample handling, TV-GC-MS is still considered the standard method for organic detection on future Mars missions. We suggest that the design of future organic instruments for Mars should include other methods to be able to detect extinct and/or extant life.

Development of an analytical method coupling cell membrane chromatography with gas chromatography-mass spectrometry via microextraction by packed sorbent and its application in the screening of volatile active compounds in natural products.

PubMed

Li, Miao; Wang, Sicen; He, Langchong

2015-01-01

Natural products (NPs) are important sources of lead compounds in modern drug discovery. To facilitate the screening of volatile active compounds in NPs, we have developed a new biochromatography method that uses rat vascular smooth muscle cells (VSMC), which are rich in L-type calcium channels (LCC), to prepare the stationary phase. This integrated method, which couples cell membrane chromatography (CMC) with gas chromatography-mass spectrometry (GC-MS) via microextraction by packed sorbent (MEPS) technology, has been termed VSMC/CMC-MEPS-GC-MS. Methodological validation confirmed its specificity, reliability and convenience. Screening results for Radix Angelicae Dahuricae and Fructus Cnidii obtained using VSMC/CMC-MEPS-GC-MS were consistent with those obtained using VSMC/CMC-offline-GC-MS. MEPS connection plays as simplified solid-phase extraction and replaces the uncontrollable evaporation operation in reported offline connections, so our new method is supposed to be more efficient and reliable than the offline ones, especially for compounds that are volatile, thermally unstable or difficult to purify. In application, senkyunolide A and ligustilide were preliminary identified as the volatile active components in Rhizoma Chuanxiong. We have thus confirmed the suitability of VSMC/CMC-MEPS-GC-MS for volatile active compounds screening in NP. Copyright © 2014 Elsevier B.V. All rights reserved.

Analysis of volatile compounds responsible for kiwifruit aroma by desiccated headspace gas chromatography-mass spectrometry.

PubMed

Zhang, Chun-Yun; Zhang, Qiong; Zhong, Cai-Hong; Guo, Ming-Quan

2016-04-01

A new method for desiccated headspace (DHS) sampling of aqueous sample to GC-MS for the analysis of volatile compounds responsible for kiwifruit aroma in different kiwifruit cultivars has been developed based on the complete hydrate formation between the sample solvent (water) with anhydrous salt (calcium chloride) at an elevated temperature (above the boiling point of the aqueous sample) in a non-contact format, which overcame the water-effect challenge to directly introduce aqueous sample into GC-MS analysis. By means of DHS, the volatile compounds in three different kiwifruit cultivars were analyzed and compared under the optimized operating conditions, mainly time and temperature for headspace equilibration, column temperature program for GC-MS measurement. As a result, 20 peaks of volatile compounds responsible for kiwifruit aroma were detected and remarkable differences were found in the relative contents of three major volatile compounds among the three different kiwifruit cultivars, i.e., acetaldehyde, ethanol and furfural. The DHS sampling technique used in the present method can make the GC-MS analysis of volatile compounds in the aqueous sample within complex matrix possible without contaminating the GC-MS instrument. In terms of the analysis of volatile compounds in kiwifruit, the present method enabled a direct measurement on the filtrate of the aqueous kiwifruit pulp, without intermediate trap phase for the extraction of analytes, which will be more reliable and simpler as compared with any other headspace method in use. Thus, DHS coupled with GC-MS will be a new valuable tool available for the kiwifruit related research and organoleptic quality control. Copyright © 2016 Elsevier B.V. All rights reserved.

Quantification of dimethylsulfoniopropionate (DMSP) in Acropora spp. of reef-building coral using mass spectrometry with deuterated internal standard.

PubMed

Swan, Hilton B; Deschaseaux, Elisabeth S M; Jones, Graham B; Eyre, Bradley D

2017-03-01

Dimethylsulfoniopropionate (DMSP) in scleractinian coral is usually analysed indirectly as dimethylsulfide (DMS) using gas chromatography (GC) with a sulfur-specific detector. We developed a headspace GC method for mass spectral analysis of DMSP in branching coral where hexa-deuterated DMSP (d 6 -DMSP) was added to samples and standards to optimise the analytical precision and quantitative accuracy. Using this indirect HS-GC-MS method, we show that common coral sample handling techniques did not alter DMSP concentrations in Acropora aspera and that endogenous DMS was insignificant compared to the store of DMSP in A. aspera. Field application of the indirect HS-GC-MS method in all seasons over a 5-year period at Heron Island in the southern Great Barrier Reef indicated that healthy colonies of A. aspera ordinarily seasonally conserve their branch tip store of DMSP; however, this store increased to a higher concentration under extended thermal stress conditions driven by a strong El Niño Southern Oscillation event. A liquid chromatography mass spectral method (LC-MS) was subsequently developed for direct analysis of DMSP in branching coral, also utilising the d 6 -DMSP internal standard. The quantitative comparison of DMSP in four species of Acropora coral by indirect HS-GC-MS and direct LC-MS analyses gave equivalent concentrations in A. aspera only; in the other three species, HS-GC-MS gave consistently higher concentrations, indicating that indirect analysis of DMSP may lead to artificially high values for some coral species. Graphical Abstract Dimethylsulfoniopropionate (DMSP) was quantified in Acropora spp. of branching coral using deuterated stable isotope dilution mass spectrometry.

Graphene oxide-based dispersive solid-phase extraction combined with in situ derivatization and gas chromatography-mass spectrometry for the determination of acidic pharmaceuticals in water.

PubMed

Naing, Nyi Nyi; Li, Sam Fong Yau; Lee, Hian Kee

2015-12-24

A fast and low-cost sample preparation method of graphene based dispersive solid-phase extraction combined with gas chromatography-mass spectrometric (GC-MS) analysis, was developed. The procedure involves an initial extraction with water-immiscible organic solvent, followed by a rapid clean-up using amine functionalized reduced graphene oxide as sorbent. Simple and fast one-step in situ derivatization using trimethylphenylammonium hydroxide was subsequently applied on acidic pharmaceuticals serving as model analytes, ibuprofen, gemfibrozil, naproxen, ketoprofen and diclofenac, before GC-MS analysis. Extraction parameters affecting the derivatization and extraction efficiency such as volume of derivatization agent, effect of desorption solvent, effect of pH and effect of ionic strength were investigated. Under the optimum conditions, the method demonstrated good limits of detection ranging from 1 to 16ngL(-1), linearity (from 0.01 to 50 and 0.05 to 50μgL(-1), depending on the analytes) and satisfactory repeatability of extractions (relative standard deviations, below 13%, n=3). Copyright © 2015 Elsevier B.V. All rights reserved.

Rapid gas chromatography with flame photometric detection of multiple organophosphorus pesticides in Salvia miltiorrhizae after ultrasonication assisted one-step extraction.

PubMed

Zhang, Shanshan; Liu, Xiaofei; Qin, Jia'an; Yang, Meihua; Zhao, Hongzheng; Wang, Yong; Guo, Weiying; Ma, Zhijie; Kong, Weijun

2017-11-15

A simple and rapid gas chromatography-flame photometric detection (GC-FPD) method was developed for the determination of 12 organophosphorus pesticides (OPPs) in Salvia miltiorrhizae by using ultrasonication assisted one-step extraction (USAE) without any clean-up steps. Some crucial parameters such as type of extraction solvent were optimized to improve the method performance for trace analysis. Any clean-up steps were negligent as no interferences were detected in the GC-FPD chromatograms for sensitive detection. Under the optimized conditions, limits of detection (LODs) and quantitation (LOQs) for all pesticides were in the range of 0.001-0.002mg/kg and 0.002-0.01mg/kg and 0.002-0.01mg/kg, respectively, which were all below the regulatory maximum residue limits suggested. RSDs for method precision (intra- and inter-day variations) were lower than 6.8% in approval with international regulations. Average recovery rates for all pesticides at three fortification levels (0.5, 1.0 and 5.0mg/kg) were in the range of 71.2-101.0% with relative standard deviations (RSDs) <13%. The developed method was evaluated for its feasibility in the simultaneous pre-concentration and determination of 12 OPPs in 32 batches of real S. miltiorrhizae samples. Only one pesticide (dimethoate) out of the 12 targets was simultaneously detected in four samples at concentrations of 0.016-0.02mg/kg. Dichlorvos and omethoate were found in the same sample from Sichuan province at 0.004 and 0.027mg/kg, respectively. Malathion and monocrotophos were determined in the other two samples at 0.014 and 0.028mg/kg, respectively. All the positive samples were confirmed by LC-MS/MS. The simple, reliable and rapid USAE-GC-FPD method with many advantages over traditional techniques would be preferred for trace analysis of multiple pesticides in more complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

PCI-GC-MS-MS approach for identification of non-amino organic acid and amino acid profiles.

PubMed

Luan, Hemi; Yang, Lin; Ji, Fenfen; Cai, Zongwei

2017-03-15

Alkyl chloroformate have been wildly used for the fast derivatization of metabolites with amino and/or carboxyl groups, coupling of powerful separation and detection systems, such as GC-MS, which allows the comprehensive analysis of non-amino organic acids and amino acids. The reagents involving n-alkyl chloroformate and n-alcohol are generally employed for providing symmetric labeling terminal alkyl chain with the same length. Here, we developed an asymmetric labeling strategy and positive chemical ionization gas chromatography-tandem mass spectrometry (PCI-GC-MS-MS) approach for determination of non-amino organic acids and amino acids, as well as the short chain fatty acids. Carboxylic and amino groups could be selectively labelled by propyl and ethyl groups, respectively. The specific neutral loss of C 3 H 8 O (60Da), C 3 H 5 O 2 (74Da) and C 4 H 8 O 2 (88Da) were useful in the selective identification for qualitative analysis of organic acids and amino acid derivatives. PCI-GC-MS-MS using multiple reaction monitoring (MRM) was applied for semi-quantification of typical non-amino organic acids and amino acids. This method exhibited a wide range of linear range, good regression coefficient (R 2 ) and repeatability. The relative standard deviation (RSD) of targeted metabolites showed excellent intra- and inter-day precision (<5%). Our method provided a qualitative and semi-quantitative PCI-GC-MS-MS, coupled with alkyl chloroformate derivatization. Copyright © 2016 Elsevier B.V. All rights reserved.

A new validated analytical method for the determination of tributyltin in water samples at the quantification level set by the European Union.

PubMed

Devos, Christophe; David, Frank; Sandra, Pat

2012-10-26

According to recent directives of the European Union (EU), limits of quantification (LOQ) for the determination of tributyltin (TBT) in surface waters should be ca. 60 pg/L (ppq). This put very stringent requirements on analytical methodologies; definitely when they have to be applied in a routine environment. Stir bar sorptive extraction (SBSE), followed by thermal desorption (TD) and capillary gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) can provide accurate and precise data at the 2 ng/L level (ppt). For lower concentrations, matrix and reagent interferences together with contamination may provide too high TBT values. A two-dimensional heart-cut GC method was developed to fractionate TBT from interferences. The GC-GC-MS/MS method shows excellent linearity in the range 50 pg/L-4 ng/L, good repeatability (RSD<20% at 200 pg/L), and a limit of detection of 11 pg/L. The method performance is demonstrated with representative samples i.e. harbor water and waste water samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of hydrazine in drinking water: Development and multivariate optimization of a rapid and simple solid phase microextraction-gas chromatography-triple quadrupole mass spectrometry protocol.

PubMed

Gionfriddo, Emanuela; Naccarato, Attilio; Sindona, Giovanni; Tagarelli, Antonio

2014-07-04

In this work, the capabilities of solid phase microextraction were exploited in a fully optimized SPME-GC-QqQ-MS analytical approach for hydrazine assay. A rapid and easy method was obtained by a simple derivatization reaction with propyl chloroformate and pyridine carried out directly in water samples, followed by automated SPME analysis in the same vial without further sample handling. The affinity of the different derivatized compounds obtained towards five commercially available SPME coatings was evaluated, in order to achieve the best extraction efficiency. GC analyses were carried out using a GC-QqQ-MS instrument in selected reaction monitoring (SRM) acquisition mode which has allowed the achievement of high specificity by selecting appropriate precursor-product ion couples improving the capability in analyte identification. The multivariate approach of experimental design was crucial in order to optimize derivatization reaction, SPME process and tandem mass spectrometry parameters. Accuracy of the proposed protocol, tested at 60, 200 and 800 ng L(-1), provided satisfactory values (114.2%, 83.6% and 98.6%, respectively), whereas precision (RSD%) at the same concentration levels were of 10.9%, 7.9% and 7.7% respectively. Limit of detection and quantification of 4.4 and 8.3 ng L(-1) were obtained. The reliable application of the proposed protocol to real drinking water samples confirmed its capability to be used as analytical tool for routine analyses. Copyright © 2014 Elsevier B.V. All rights reserved.

Analysis of anabolic steroids in urine by gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry with chlorobenzene as dopant.

PubMed

Hintikka, Laura; Haapala, Markus; Kuuranne, Tiia; Leinonen, Antti; Kostiainen, Risto

2013-10-18

A gas chromatography-microchip atmospheric pressure photoionization-tandem mass spectrometry (GC-μAPPI-MS/MS) method was developed for the analysis of anabolic androgenic steroids in urine as their trimethylsilyl derivatives. The method utilizes a heated nebulizer microchip in atmospheric pressure photoionization mode (μAPPI) with chlorobenzene as dopant, which provides high ionization efficiency by producing abundant radical cations with minimal fragmentation. The performance of GC-μAPPI-MS/MS was evaluated with respect to repeatability, linearity, linear range, and limit of detection (LOD). The results confirmed the potential of the method for doping control analysis of anabolic steroids. Repeatability (RSD<10%), linearity (R(2)≥0.996) and sensitivity (LODs 0.05-0.1ng/mL) were acceptable. Quantitative performance of the method was tested and compared with that of conventional GC-electron ionization-MS, and the results were in good agreement. Copyright © 2013 Elsevier B.V. All rights reserved.

A method for rapid sampling and characterization of smokeless powder using sorbent-coated wire mesh and direct analysis in real time - mass spectrometry (DART-MS).

PubMed

Li, Frederick; Tice, Joseph; Musselman, Brian D; Hall, Adam B

2016-09-01

Improvised explosive devices (IEDs) are often used by terrorists and criminals to create public panic and destruction, necessitating rapid investigative information. However, backlogs in many forensic laboratories resulting in part from time-consuming GC-MS and LC-MS techniques prevent prompt analytical information. Direct analysis in real time - mass spectrometry (DART-MS) is a promising analytical technique that can address this challenge in the forensic science community by permitting rapid trace analysis of energetic materials. Therefore, we have designed a qualitative analytical approach that utilizes novel sorbent-coated wire mesh and dynamic headspace concentration to permit the generation of information rich chemical attribute signatures (CAS) for trace energetic materials in smokeless powder with DART-MS. Sorbent-coated wire mesh improves the overall efficiency of capturing trace energetic materials in comparison to swabbing or vacuuming. Hodgdon Lil' Gun smokeless powder was used to optimize the dynamic headspace parameters. This method was compared to traditional GC-MS methods and validated using the NIST RM 8107 smokeless powder reference standard. Additives and energetic materials, notably nitroglycerin, were rapidly and efficiently captured by the Carbopack X wire mesh, followed by detection and identification using DART-MS. This approach has demonstrated the capability of generating comparable results with significantly reduced analysis time in comparison to GC-MS. All targeted components that can be detected by GC-MS were detected by DART-MS in less than a minute. Furthermore, DART-MS offers the advantage of detecting targeted analytes that are not amenable to GC-MS. The speed and efficiency associated with both the sample collection technique and DART-MS demonstrate an attractive and viable potential alternative to conventional techniques. Copyright © 2016 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

Field-portable Gas Chromatograph Mass Spectrometer (GC-MS) Unit for Semi-volatile Compound Analysis in Groundwater

DTIC Science & Technology

2011-09-01

of interest. Lack of bias with GC-MS method ........................................................ 12 3.1.1 Data requirements...14 3.2.1 Data ...3.3.1 Data requirements ....................................................................................................... 15 3.3.2 Success

Functional Characteristics of Tumor Associated Protein Spot14 and Interacting Proteins in Mouse Mammary Epithelial and Breast Cancer Cell Lines

DTIC Science & Technology

2012-03-01

enhanced accumulation of total lipids evaluated by Bodipy staining and NMR analysis. A major finding in this report is that glycolytic and lipogenic enzyme...total lipid component using NMR Metabolomics showed significant increases in the quantity of intracellular (CH2)n and (CH3) acyl chains (i.e. fatty...Mass Spectrometry (GC-MS) methods were developed. GC-MS differs from NMR analysis of lipid fractions in that GC-MS distinguishes between fatty acids

Lipidomic analysis of glycerolipid and cholesteryl ester autooxidation products.

PubMed

Kuksis, Arnis; Suomela, Jukka-Pekka; Tarvainen, Marko; Kallio, Heikki

2009-06-01

Thin-layer chromatography (TLC), gas chromatography (GC), and liquid chromatography (LC) in combination with mass spectrometry (MS) have been adopted for the isolation and identification of oxolipids and for determining their functionality. TLC provides a rapid separation and access to most oxolipids as intact molecules and has recently been effectively interfaced with time-of-flight (TOF) MS (TOF-MS). GC with flame ionization (FI) (GC/FI) and electron impact (EI) MS (GC/EI-MS) has been extensively utilized in the analysis of isoprostanes and other low-molecular-weight oxolipids, although these methods require derivatization of the analytes. In contrast, LC with ultraviolet (UV) absorption (LC/UV) or evaporate light scattering detection (ELSD) (LC/ELSD) as well as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) MS (LC/ESI-MS) or LC/APCI-MS has proven to be well suited for the analysis of intact oxolipids and their conjugates without or with minimal derivatization. Nevertheless, kit-based colorimetric and fluorescent procedures continue to serve as sensitive indicators of the presence of hydroperoxides and aldehydes.

Rapid Quantification of N-Methyl-2-pyrrolidone in Polymer Matrices by Thermal Desorption-GC/MS.

PubMed

Kim, Young-Min; Kim, Jae Woo; Moon, Hye Mi; Lee, Min-Jin; Hosaka, Akihiko; Watanabe, Atsushi; Teramae, Norio; Park, Young-Kwon; Myung, Seung-Woon

2017-01-01

Analysis of a residual solvent in polymeric materials has become an important issue due to the increased regulations and standards for its use. N-Methyl-2-pyrrolidone (NMP) is a solvent widely used in many industries and restricted as one of the chemicals under EU REACH regulations due to its potential harmful effects. In this study, thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) is applied for the quantitative analysis of NMP with the use of a polymer-coated sample cup. By using the polymer-coated sample cup, the vaporization of NMP was prevented during waiting time before TD-GC/MS analysis. The calibration curve for the TD method showed good linearity (correlation coefficient, r 2 = 0.9998) and precision values (below 5.3% RSD). NMP recovery rates in different polymer matrices (PS, PMMA and PVC) were in the range of 98.8 to 106.6% with RSD values below 5.0%. The quantification result (600 mg NMP/kg PVC) for the blind NMP carrying sample in a PVC matrix by TD-GC/MS was higher than that (532 mg NMP/kg PVC) by solvent extraction-GC/MS method.

Use of a Deuterated Internal Standard with Pyrolysis-GC/MS Dimeric Marker Analysis to Quantify Tire Tread Particles in the Environment

PubMed Central

Unice, Kenneth M.; Kreider, Marisa L.; Panko, Julie M.

2012-01-01

Pyrolysis(pyr)-GC/MS analysis of characteristic thermal decomposition fragments has been previously used for qualitative fingerprinting of organic sources in environmental samples. A quantitative pyr-GC/MS method based on characteristic tire polymer pyrolysis products was developed for tread particle quantification in environmental matrices including soil, sediment, and air. The feasibility of quantitative pyr-GC/MS analysis of tread was confirmed in a method evaluation study using artificial soil spiked with known amounts of cryogenically generated tread. Tread concentration determined by blinded analyses was highly correlated (r2 ≥ 0.88) with the known tread spike concentration. Two critical refinements to the initial pyrolysis protocol were identified including use of an internal standard and quantification by the dimeric markers vinylcyclohexene and dipentene, which have good specificity for rubber polymer with no other appreciable environmental sources. A novel use of deuterated internal standards of similar polymeric structure was developed to correct the variable analyte recovery caused by sample size, matrix effects, and ion source variability. The resultant quantitative pyr-GC/MS protocol is reliable and transferable between laboratories. PMID:23202830

Determination of tramadol by dispersive liquid-liquid microextraction combined with GC-MS.

PubMed

Habibollahi, Saeed; Tavakkoli, Nahid; Nasirian, Vahid; Khani, Hossein

2015-01-01

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) has been developed for preconcentration and determination of tramadol, ((±)-cis-2-[(dimethylamino)methyl]-1-(3-methoxyphenyl)cyclohexanol-HCl), in aqueous and biological samples (urine, blood). DLLME is a simple, rapid and efficient method for determination of drugs in aqueous samples. Efficient factors on the DLLME process has defined and optimized for extraction of tramadol including type of extraction and disperser solvents and their volumes, pH of donor phase, time of extraction and ionic strength of donor phase. Based on the results of this study, under optimal conditions and by using 2-nitro phenol as internal standard, tramadol was determined by GC-MS, and the figures of merit of this work were evaluated. The enrichment factor, relative recovery and limit of detection were obtained 420, 99.2% and 0.08 µg L(-1), respectively. The linear range was between 0.26 and 220.00 µg L(-1) (R(2) = 0.9970). The relative standard deviation for 50.00 µg L(-1) of tramadol in aqueous samples by using 2-nitro phenol as IS was 3.6% (n = 7). Finally, the performance of DLLME was evaluated for analysis of tramadol in urine and blood. Published by Oxford University Press 2014. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Application of enhanced gas chromatography/triple quadrupole mass spectrometry for monitoring petroleum weathering and forensic source fingerprinting in samples impacted by the Deepwater Horizon oil spill.

PubMed

Adhikari, Puspa L; Wong, Roberto L; Overton, Edward B

2017-10-01

Accurate characterization of petroleum hydrocarbons in complex and weathered oil residues is analytically challenging. This is primarily due to chemical compositional complexity of both the oil residues and environmental matrices, and the lack of instrumental selectivity due to co-elution of interferences with the target analytes. To overcome these analytical selectivity issues, we used an enhanced resolution gas chromatography coupled with triple quadrupole mass spectrometry in Multiple Reaction Monitoring (MRM) mode (GC/MS/MS-MRM) to eliminate interferences within the ion chromatograms of target analytes found in environmental samples. This new GC/MS/MS-MRM method was developed and used for forensic fingerprinting of deep-water and marsh sediment samples containing oily residues from the Deepwater Horizon oil spill. The results showed that the GC/MS/MS-MRM method increases selectivity, eliminates interferences, and provides more accurate quantitation and characterization of trace levels of alkyl-PAHs and biomarker compounds, from weathered oil residues in complex sample matrices. The higher selectivity of the new method, even at low detection limits, provides greater insights on isomer and homolog compositional patterns and the extent of oil weathering under various environmental conditions. The method also provides flat chromatographic baselines for accurate and unambiguous calculation of petroleum forensic biomarker compound ratios. Thus, this GC/MS/MS-MRM method can be a reliable analytical strategy for more accurate and selective trace level analyses in petroleum forensic studies, and for tacking continuous weathering of oil residues. Copyright © 2017 Elsevier Ltd. All rights reserved.

Improvement of a headspace solid phase microextraction-gas chromatography/mass spectrometry method for the analysis of wheat bread volatile compounds.

PubMed

Raffo, Antonio; Carcea, Marina; Castagna, Claudia; Magrì, Andrea

2015-08-07

An improved method based on headspace solid phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS) was proposed for the semi-quantitative determination of wheat bread volatile compounds isolated from both whole slice and crust samples. A DVB/CAR/PDMS fibre was used to extract volatiles from the headspace of a bread powdered sample dispersed in a sodium chloride (20%) aqueous solution and kept for 60min at 50°C under controlled stirring. Thirty-nine out of all the extracted volatiles were fully identified, whereas for 95 other volatiles a tentative identification was proposed, to give a complete as possible profile of wheat bread volatile compounds. The use of an array of ten structurally and physicochemically similar internal standards allowed to markedly improve method precision with respect to previous HS-SPME/GC-MS methods for bread volatiles. Good linearity of the method was verified for a selection of volatiles from several chemical groups by calibration with matrix-matched extraction solutions. This simple, rapid, precise and sensitive method could represent a valuable tool to obtain semi-quantitative information when investigating the influence of technological factors on volatiles formation in wheat bread and other bakery products. Copyright © 2015 Elsevier B.V. All rights reserved.

Rapid determination of amino acids in neonatal blood samples based on derivatization with isobutyl chloroformate followed by solid-phase microextraction and gas chromatography/mass spectrometry.

PubMed

Deng, Chunhui; Li, Ning; Zhang, Xiangmin

2004-01-01

The purpose of this study was to develop a simple, rapid and sensitive analytical method for determination of amino acids in neonatal blood samples. The developed method involves the employment of derivatization and a solid-phase microextraction (SPME) technique together with gas chromatography/mass spectrometry (GC/MS). Amino acids in blood samples were derivatized by a mixture of isobutyl chloroformate, methanol and pyridine, and the N(O,S)-alkoxycarbonyl alkyl esters thus formed were headspace extracted by a SPME fiber. Finally, the extracted analytes on the fiber were desorbed and detected by GC/MS in electron impact (EI) mode. L-Valine, L-leucine, L-isoleucine, L-phenylanaline and L-tyrosine in blood samples were quantitatively analyzed by measurement of the corresponding N(O,S)-alkoxycarbonyl alkyl esters using an external standard method. SPME conditions were optimized, and the method was validated. The method was applied to diagnosis of neonatal phenylkenuria (PKU) and maple syrup urine disease (MSUD) by the analyses of five amino acids in blood samples. The results showed that the proposed method is a potentially powerful tool for simultaneous screening for neonatal PKU and MSUD. Copyright (c) 2004 John Wiley & Sons, Ltd.

Determination of residual solvents in bulk pharmaceuticals by thermal desorption/gas chromatography/mass spectrometry.

PubMed

Urakami, K; Saito, Y; Fujiwara, Y; Watanabe, C; Umemoto, K; Godo, M; Hashimoto, K

2000-12-01

Thermal desorption (TD) techniques followed by capillary GC/MS were applied for the analysis of residual solvents in bulk pharmaceuticals. Solvents desorbed from samples by heating were cryofocused at the head of a capillary column prior to GC/MS analysis. This method requires a very small amount of sample and no sample pretreatment. Desorption temperature was set at the point about 20 degrees C higher than the melting point of each sample individually. The relative standard deviations of this method tested by performing six consecutive analyses of 8 different samples were 1.1 to 3.1%, and analytical results of residual solvents were in agreement with those obtained by direct injection of N,N-dimethylformamide solution of the samples into the GC. This novel TD/GC/MS method was demonstrated to be very useful for the identification and quantification of residual solvents in bulk pharmaceuticals.

A solid-phase microextraction GC/MS/MS method for rapid quantitative analysis of food and beverages for the presence of legally restricted biologically active flavorings.

PubMed

Bousova, Katerina; Mittendorf, Klaus; Senyuva, Hamide

2011-01-01

A method was developed using automated headspace solid-phase microextraction coupled with GC/MS/MS to simultaneously determine the presence of seven biologically active flavoring substances whose levels of use in processed foods is controlled by statutory limits. The method can be applied to identify and quantify the presence of 1,2-benzopyrone (coumarin), beta-asarone, 1-allyl-4-methoxybenzene (estragole), menthofuran, 4-allyl-1 ,2-dimethoxybenzene (methyl eugenol), pulegone, and thujone at levels ranging from 0.5 to 3000 mg/kg. The method has been optimized and validated for three different generic food types categorized on the basis of composition and anticipated use levels of flavorings and food ingredients. The food categories are alcoholic and nonalcoholic beverages; semisolid processed foods (e.g., soups, sauces, confectionary, etc.); and solid foods (muesli, bakery products, etc.). The method is simple, inexpensive, and rapid, and eliminates the use of flammable and toxic solvents. There is no sample preparation, and using MSIMS, unequivocal confirmation of identification is achieved even in highly complex matrixes containing many potential interfering volatiles. The method precision for spiked samples ranged from 2 to 21%, with the greatest variability associated with solid matrixes. The LOD and LOQ values were well below 0.1 and 0.5 mg/kg, respectively, in all cases for individual substances, fulfilling requirements for enforcement purposes. The robustness of the method was demonstrated in a small survey of retail samples of four spirits, five flavored milks, three energy drinks, five liqueurs, five soups, 10 sauces, five herbal teas, and three breakfast cereals.

Web Server for Peak Detection, Baseline Correction, and Alignment in Two-Dimensional Gas Chromatography Mass Spectrometry-Based Metabolomics Data.

PubMed

Tian, Tze-Feng; Wang, San-Yuan; Kuo, Tien-Chueh; Tan, Cheng-En; Chen, Guan-Yuan; Kuo, Ching-Hua; Chen, Chi-Hsin Sally; Chan, Chang-Chuan; Lin, Olivia A; Tseng, Y Jane

2016-11-01

Two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC/TOF-MS) is superior for chromatographic separation and provides great sensitivity for complex biological fluid analysis in metabolomics. However, GC×GC/TOF-MS data processing is currently limited to vendor software and typically requires several preprocessing steps. In this work, we implement a web-based platform, which we call GC 2 MS, to facilitate the application of recent advances in GC×GC/TOF-MS, especially for metabolomics studies. The core processing workflow of GC 2 MS consists of blob/peak detection, baseline correction, and blob alignment. GC 2 MS treats GC×GC/TOF-MS data as pictures and clusters the pixels as blobs according to the brightness of each pixel to generate a blob table. GC 2 MS then aligns the blobs of two GC×GC/TOF-MS data sets according to their distance and similarity. The blob distance and similarity are the Euclidean distance of the first and second retention times of two blobs and the Pearson's correlation coefficient of the two mass spectra, respectively. GC 2 MS also directly corrects the raw data baseline. The analytical performance of GC 2 MS was evaluated using GC×GC/TOF-MS data sets of Angelica sinensis compounds acquired under different experimental conditions and of human plasma samples. The results show that GC 2 MS is an easy-to-use tool for detecting peaks and correcting baselines, and GC 2 MS is able to align GC×GC/TOF-MS data sets acquired under different experimental conditions. GC 2 MS is freely accessible at http://gc2ms.web.cmdm.tw .

Determination of Ethyl Carbamate in Chinese Yellow Rice Wine by Diatomaceous Earth Extraction and GC/MS Method.

PubMed

Wu, Pinggu; Zhang, Liqun; Shen, Xianghong; Wang, Liyuan; Zou, Yan; Zhang, Jing; Tan, Ying; Tang, Jun; Ma, Bingjie; Pan, Xiaodong; Jiang, Wei

2015-01-01

A sensitive and rapid analytical method based on alkaline diatomaceous earth extraction followed by GC/MS was developed for the quantitative determination of the toxic contaminant ethyl carbamate (EC) in yellow rice wines. The optimal extraction conditions were investigated. With the application of diatomaceous earth extraction, the damage of organic acids to the capillary column was greatly reduced. By using d5-EC as an internal standard for quantitative analysis of EC, the linearity of the calibration curves was good between 10 and 1000 ng/mL. The LOD and LOQ were 1.7 and 5.0 μg/kg, respectively. The spiked level of EC was 5.0-300 μg/kg, and the average recovery of the spikes was between 78.4 and 98.2%, with an RSD between 4.3 and 8.3%. Upon validation by five laboratories when spiked with 50, 100, and 300 μg/kg, the average respective recoveries were 102.9, 102.2, and 98.7% with a RSD between 0.7 and 8.1%. The validation results demonstrated that the method is fast, simple, selective, and suitable for the determination of EC in yellow rice wines.

Rapid determination of the aromatic compounds methyl-anthranilate, 2'-aminoacetophenone and furaneol by GC-MS: Method validation and characterization of grape derivatives.

PubMed

Prudêncio Dutra, Maria da Conceição; de Souza, Joyce Fagundes; Viana, Arão Cardoso; de Oliveira, Débora; Pereira, Giuliano Elias; Dos Santos Lima, Marcos

2018-05-01

A methodology for the rapid determination of the aromatic compounds methyl anthranilate (MA), 2'-aminoacetophenone (2-AAP) and furaneol by GC-MS was validated and used to characterize grape juice and wine elaborated with the new Brazilian grape varieties cultivated in northeastern Brazil, and Brazilian grape nectars. The method presented linearity (R 2  ˃ 0.9952), good accuracy (CV < 12.9%), recovery (76.6% to 106.3%), limit of detection (23 μg L -1 to 94 μg L -1 ) and limit of quantification (96 μg L -1 to 277 μg L -1 ) acceptable in only 20 min of running. The methodology was considered satisfactory for the purpose, being a simple and rapid method for the determination of these compounds in grape derivatives drinks. In the characterization of the nectars the compound that stood out was the MA, being its presence attributed to the addition of flavorings in these products. It was evidenced a significant contribution of furaneol in the aroma of grape juice and wines elaborated with the new Brazilian grape varieties. Copyright © 2018 Elsevier Ltd. All rights reserved.

Determination of acrylamide in various food matrices: evaluation of LC and GC mass spectrometric methods.

PubMed

Becalski, Adam; Lau, Benjamin P Y; Lewis, David; Seaman, Stephen W; Sun, Wing F

2005-01-01

Recent concerns surrounding the presence of acrylamide in many types of thermally processed food have brought about the need for the development of analytical methods suitable for determination of acrylamide in diverse matrices with the goals of improving overall confidence in analytical results and better understanding of method capabilities. Consequently, the results are presented of acrylamide testing in commercially available food products--potato fries, potato chips, crispbread, instant coffee, coffee beans, cocoa, chocolate and peanut butter, obtained by using the same sample extract. The results obtained by using LC-MS/MS, GC/MS (El), GC/HRMS (El)--with or without derivatization--and the use of different analytical columns, are discussed and compared with respect to matrix borne interferences, detection limits and method complexities.

Discovery and Identification of Dimethylsilanediol as a Contaminant in ISS Potable Water

NASA Technical Reports Server (NTRS)

Rutz, Jeffrey A.; Schultz, John R.; Kuo, C. Mike; Cole, Hraold E.; Manuel, Sam; Curtis, Matthew; Jones, Patrick R.; Sparkman, O. David; McCoy, J. Torin

2010-01-01

In September of 2010, analysis of ISS potable water samples was undertaken to determine the contaminant responsible for a rise in total organic carbon (TOC). As analysis of the routine target list of organic compounds did not reveal the contaminant, efforts to look for unknown compounds was initiated, resulting in an unknown peak being discovered in the gas chromatography/mass spectrometry (GC/MS) analysis for glycols. A mass spectrum of the contaminant was then generated by concentrating one of the samples by evaporation and analyzing by GC/MS in full-scan mode. Although a computer match of the compound s identity could not be obtained with the instrument s database, a search with a more up to date mass spectral library yielded a good match with dimethylsilanediol (DMSD). Inductively Coupled Plasma/Mass Spectrometry (ICP/MS) analyses showed abnormally high silicon levels in the samples, confirming that the unknown contained silicon. DMSD was then synthesized to confirm the identification and provide a standard to develop a calibration curve. Further confirmation was provided by external Direct Analysis in Real Time (DART) GC/MS analysis. A preliminary GC/MS method was then developed and archived samples from various locations on ISS were analyzed to determine the extent of the contamination and provide data for troubleshooting. This paper describes these events in more detail as well as problems encountered in routine GC/MS analyses and the subsequent development of high performance liquid chromatography and LC/MS/MS methods for quantitation of DMSD.

Freeze-thaw method improves the detection of volatile compounds in insects using Headspace Solid-Phase Microextraction (HS-SPME)

USDA-ARS?s Scientific Manuscript database

Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC-MS) is commonly used in analyzing insect volatiles. In order to improve the detection of volatiles in insects, a freeze-thaw method was applied to insect samples before the HS-SPME-GC-MS analysis. ...

METHOD 530 DETERMINATION OF SELECT SEMIVOLATILE ORGANIC CHEMICALS IN DRINKING WATER BY SOLID PHASE EXTRACTION AND GAS CHROMATOGRAPHY/ MASS SPECTROMETRY (GC/MS)

EPA Science Inventory

1.1. This is a gas chromatography/mass spectrometry (GC/MS) method for the determination of selected semivolatile organic compounds in drinking waters. Accuracy and precision data have been generated in reagent water, and in finished ground and surface waters for the compounds li...

Determination of serum cholestane-3β,5α,6β-triol by gas chromatography-mass spectrometry for identification of Niemann-Pick type C (NPC) disease.

PubMed

Kannenberg, Frank; Nofer, Jerzy-Roch; Schulte, Erhard; Reunert, Janine; Marquardt, Thorsten; Fobker, Manfred

2017-05-01

Niemann-Pick type C (NPC) is a neurological disease caused by an intracellular cholesterol accumulation. Cholesterol oxidation product cholestane-3β,5α,6β-triol (C-triol) serves as diagnostic biomarker for NPC, but its measurement in the routine laboratory remains difficult. We developed an isotope dilution gas chromatography-mass spectrometry (GC-MS) method permitting screening for NPC in plasma. 1440 plasma samples obtained from clinically suspicious patients were subjected to alkaline saponification. C-triol was extracted with carbon tetrachloride, transformed into the trimethylsilylethers, separated on a fused silica capillary column with a nonpolar silicone stationary phase, and analyzed by GC-MS. NPC diagnosis was confirmed by DNA sequencing. The method was linear over a concentration range of 0.03-200ng/mL with a mean recovery rate of 98.6%. The intra- and inter-day variation coefficients assessed at two concentrations were below 15%. Limits of quantification (LOQ) and detection (LOD) were 0.03ng/mL and 0.01ng/mL, respectively. Receiver operating characteristic (ROC) analysis estimated that the area under curve was 0.997 implying a significant discriminatory power to identify subjects with NPC. Nevertheless, 13 NPC patients and 29 control subjects confirmed by sequencing showed false negative or positive results, respectively. Two patients with cerebrotendinous xanthomatosis showed a 5-10-fold increase in C-triol levels. We developed a quick and sensitive GC-MS method for determination of C-triol, which may serve as a simple and inexpensive diagnostic tool aiding NPC diagnosis in a routine hospital laboratory. As C-triol elevation is not limited to NPC, the NPC diagnosis has to be confirmed by DNA sequencing. Copyright © 2016 Elsevier Ltd. All rights reserved.

DEVELOPMENT AND EVALUATION OF AN ENZYME-LINKED IMMUNOASSAY (ELISA) METHOD FOR THE MEASUREMENT OF 2,4-DICHLOROPHENOXYACETIC ACID IN HUMAN URINE

EPA Science Inventory

This paper describes the development of a 96-microwell high sample capacity ELISA method for measuring 2,4-D in urine; the analysis of 2,4-D in real-world urine samples by both ELISA and GC/MS methods; and compares the ELISA and GC/MS results in several key areas: accuracy, preci...

Mathematical Model Developed for Environmental Samples: Prediction of GC/MS Dioxin TEQ from XDS-CALUX Bioassay Data

PubMed Central

Brown, David J.; Orelien, Jean; Gordon, John D.; Chu, Andrew C.; Chu, Michael D.; Nakamura, Masafumi; Handa, Hiroshi; Kayama, Fujio; Denison, Michael S.; Clark, George C.

2010-01-01

Remediation of hazardous waste sites requires efficient and cost-effective methods to assess the extent of contamination by toxic substances including dioxin-like chemicals. Traditionally, dioxin-like contamination has been assessed by gas chromatography/high-resolution mass spectrometry (GC/MS) analysis for specific polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyl congeners. Toxic equivalency factors for these congeners are then used to estimate the overall dioxin toxic equivalency (TEQ) of complex mixtures found in samples. The XDS-CALUX bioassay estimates contamination by dioxin-like chemicals in a sample extract by measuring expression of a sensitive reporter gene in genetically engineered cells. The output of the XDS-CALUX assay is a CALUX-TEQ value, calibrated based on TCDD standards. Soil samples taken from a variety of hazardous waste sites were measured using the XDS-CALUX bioassay and GC/MS. TEQ and CALUX-TEQ from these methods were compared, and a mathematical model was developed describing the relationship between these two data sets: log(TEQ) = 0.654 × log(CALUX-TEQ) + 0.058-(log(CALUX-TEQ))2. Applying this equation to these samples showed that predicted and GC/MS measured TEQ values strongly correlate (R2 = 0.876) and that TEQ values predicted from CALUX-TEQ were on average nearly identical to the GC/MS-TEQ. The ability of XDS-CALUX bioassay data to predict GC/MS-derived TEQ data should make this procedure useful in risk assessment and management decisions. PMID:17626436

Vortex-homogenized matrix solid-phase dispersion for the extraction of short chain chlorinated paraffins from indoor dust samples.

PubMed

Chen, Yu-Hsuan; Chang, Chia-Yu; Ding, Wang-Hsien

2016-11-11

A simple and effective method for determining short chain chlorinated paraffins (SCCPs) in indoor dust is presented. The method employed a modified vortex-homogenized matrix solid-phase dispersion (VH-MSPD) prior to its detection by gas chromatography - electron-capture negative-ion mass spectrometry (GC-ECNI-MS) operating in the selected-ion-monitoring (SIM) mode. Under the best extraction conditions, 0.1-g of dust sample was dispersed with 0.1-g of silica gel by using vortex (2min) instead of using a mortar and pestle (3min). After that step, the blend was transferred to a glass column containing 3-g acidic silica gel, 2-g basic silica gel, and 2-g of deactivated silica gel, used as clean-up co-sorbents. Then, target analytes were eluted with 5mL of n-hexane/dichloromethane (2:1, v/v) mixture. The extract was evaporated to dryness under a gentle stream of nitrogen. The residue was then re-dissolved in n-hexane (10μL), and subjected to GC-ECNI-MS analysis. The limits of quantitation (LOQs) ranged from 0.06 to 0.25μg/g for each SCCP congener. Precision was less than 7% for both intra- and inter-day analysis. Trueness was above 89%, which was calculated by mean extraction recovery. The VH-MSPD combined with GC-ECNI-MS was successfully applied to quantitatively detect SCCPs from various indoor dust samples, and the concentrations ranged from 1.2 to 31.2μg/g. Copyright © 2016 Elsevier B.V. All rights reserved.

Preliminary study of urine metabolism in type two diabetic patients based on GC-MS

PubMed Central

Zhang, Ning; Geng, Fang; Hu, Zhong-Hua; Liu, Bin; Wang, Ye-Qiu; Liu, Jun-Cen; Qi, Yong-Hua; Li, Li-Jing

2016-01-01

Objective: Comparative study of type 2 diabetes and healthy controls by metabolomics methods to explore the pathogenesis of Type II diabetes. Methods: Gas chromatography - mass spectrometry (GC-MS) with a variety of multivariate statistical analysis methods to the healthy control group 58 cases, 68 cases of Type II diabetes group were analyzed. Chromatographic conditions: DB-5MS column; the carrier gas He; flow rate of 1 mL·min-1, the injection volume 1 uL; split ratio is 100: 1. MS conditions: electron impact (EI) ion source, an auxiliary temperature of 280°C, the ion source 230°C, quadrupole 150°C; mass scan range 30~600 mAu. Results: Established analytical method based on urine metabolomics GC-MS of Type II diabetes, determine the urine succinic acid, L-leucine, L-isoleucine, tyrosine, slanine, acetoace acid, mannose, L-isoleucine, L-threonine, Phenylalanine, fructose, D-glucose, palmi acid, oleic acid and arachidonic acid were significantly were significantly changed. Conclusion: Based on metabolomics of GC-MS detection and analysis metabolites can be found differences between type 2 diabetes and healthy control group, PCA diagram can effectively distinguish Type II diabetes and healthy control group, with load diagrams and PLS-DA VIP value metabolite screening, the resulting differences in metabolic pathways involved metabolites, including amino acid metabolism, lipid metabolism, glucose metabolism and energy metabolism. PMID:27508010

Utilization of a deuterated derivatization agent to synthesize internal standards for gas chromatography-tandem mass spectrometry quantification of silylated metabolites.

PubMed

Lien, Stina K; Kvitvang, Hans Fredrik Nyvold; Bruheim, Per

2012-07-20

GC-MS analysis of silylated metabolites is a sensitive method that covers important metabolite groups such as sugars, amino acids and non-amino organic acids, and it has become one of the most important analytical methods for exploring the metabolome. Absolute quantitative GC-MS analysis of silylated metabolites poses a challenge as different metabolites have different derivatization kinetics and as their silyl-derivates have varying stability. This report describes the development of a targeted GC-MS/MS method for quantification of metabolites. Internal standards for each individual metabolite were obtained by derivatization of a mixture of standards with deuterated N-methyl-N-trimethylsilyltrifluoroacetamide (d9-MSTFA), and spiking this solution into MSTFA derivatized samples prior to GC-MS/MS analysis. The derivatization and spiking protocol needed optimization to ensure that the behaviour of labelled compound responses in the spiked sample correctly reflected the behaviour of unlabelled compound responses. Using labelled and unlabelled MSTFA in this way enabled normalization of metabolite responses by the response of their deuterated counterpart (i.e. individual correction). Such individual correction of metabolite responses reproducibly resulted in significantly higher precision than traditional data correction strategies when tested on samples both with and without serum and urine matrices. The developed method is thus a valuable contribution to the field of absolute quantitative metabolomics. Copyright © 2012 Elsevier B.V. All rights reserved.

GC/MS determination of amines following exhaustive trifluoroacetylation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomson, J.S.; Green, J.B.; McWilliams, T.B.

An analytical method for trifluoroacetylation of aromatic amines and GC/MS of the resulting derivatives has been developed. The key feature of the method is its capability to differentiate d tertiary amines; since, using the conditions described in the report, most primary, secondary, an primary amines add two and secondary amines add one trifluoroacetyl group. In general, tertiary amines do not react. Since conventional trifluoroacetylation procedures introduce only a single trifluoroacetyl group into both primary and secondary aminess the procedure reported here improves GC/MS identification of the relatively large number of isomers of nitrogen compounds found in petroleum or similarly complexmore » mixtures. For example, using exhaustive trifluoroacetylation, it is possible to differentiate isomeric forms of C{sub 9}H{sub 11}N (e.g., cyclohexenopyridines, aminoindans, 1,2,3,4-tetrahydroquinoline and tetrahydroisoquinolines). Examples of the application of the method to petroleum and coal liquid products are provided. Because of the limited thermal stability of the derivatives of primary amines, the method is applicable only to distillates boiling below 370{degrees}C (700{degrees}F). To expedite utilization of the method by others, GC retention indices and relative GC/MS total ion current response factors for 102 trifluoroacetyl derivatives are included in the body of the report and their 70 ev mass spectra are reported in Appendix A.« less

[Study on supercritical CO2 extraction of xiaoyaosan and its GC-MS fingerprint].

PubMed

Zuo, Ya-Mei; Tian, Jun-Sheng; Guo, Xiao-Qing; Zhou, Yu-Zhi; Gao, Xiao-Xia; Qin, Xue-Mei

2014-02-01

To determine the optimum conditions of supercritical CO2 extraction of Xiaoyaosan, and establish its fingerprint by gas chromatography-mass spectrometry (GC-MS), the yield of extract were investigated, an orthogonal test was used to quantify the effects of extraction temperature, pressure, CO2 flow rate and time, and fingerprint analysis of different batches of extracts were by GC-MS. The optimal extraction conditions were determined as follows: extraction pressure 20 MPa, extraction temperature 50 degrees C, CO2 flow rate 25 kg x h(-1), extraction time 3 h, and average yield 2.2%. The GC-MS fingerprint was established and 27 common peaks were found, whose contents add up to 81.89% of the total peak area. Among them, 21 compounds were identified, accounting for 53.20% of the total extract. The extraction process is reasonable and favorable for industrial production. The GC-MS method is accurate, reliable, reproducible, and can be used for quality control of supercritical CO2 extract from Xiaoyaosan.

New criteria for the characterization of traditional East Asian papers.

PubMed

Avataneo, Chiara; Sablier, Michel

2017-01-01

We report a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method capable of analyzing traditional East Asian papers. The method proposed is based on rapid and easy single step Py-GC/MS analysis that can be carried out with a minimum amount of matter, in the few microgram range. Three reference papers manufactured from kozo (Broussonetia kazinoki Siebold & Zucc.), mitsumata (Edgeworthia chrysantha Lindl.), and gampi (Wikstroemia sikokiana Franch. & Sav.) with the traditional hand paper making processes were examined. The method allows discrimination between terpenic and steroid compounds, which were revealed as chemical markers of origin of the plant fibers. Each paper investigated was found to have characteristic pyrolysis fingerprints that were unique to the traditional handmade paper, demonstrating the potential for differentiation of these biochemical components of fiber plants on East Asian papers towards identification and conservation of cultural heritage. The investigation on Py-GC/MS was extended to liquid extraction followed by GC/MS analysis to characterize the biochemical components of fiber plants. The main contribution of this study is to provide molecular criteria for discriminating plant species used for traditional East Asian hand papermaking. Py-GC/MS complements efficiently microscope identification especially for adverse cases. A case study of archaeological Chinese paper painting artefacts was thereafter successfully investigated to address informative potential and efficiency of the criteria of identification on ancient and degraded East Asian paperworks.

Direct and simultaneous determination of representative byproducts in a lignocellulosic hydrolysate of corn stover via gas chromatography-mass spectrometry with a Deans switch.

PubMed

Zheng, Rongping; Zhang, Hongman; Zhao, Jing; Lei, Mingliu; Huang, He

2011-08-05

Pretreatment is one of the most important steps in producing fuel ethanol from lignocellulosic biomass. Simple, fast and accurate quantification of byproducts in lignocellulosic hydrolysates is critical to optimize the pretreatment procedures, but still a challenge. In this paper, a new GC-MS (SIM) method based on a Deans switch has been developed for the determination of byproducts in a corn stover hydrolysate. The Deans switch was incorporated into a hardware system that facilitated the direct aqueous injection (DAI) on GC-MS system. Simultaneous chromatographic separation and quantification of 18 byproducts including four aliphatic acids, five furan derivatives, four phenolic compounds and five others were achieved within 45 min. The detection limits of the presented method for various byproducts were in the range of 0.007-0.832 mg/L. The within-day and between-day precisions of the method were less than 6.0% (RSD, n=6). The accuracy of the method was confirmed with recoveries of 86-128%. A lignocellulosic hydrolysate sample of corn stover was successfully analyzed using this method, with aliphatic acids and furan derivatives accounting for 89.15% of the selected total byproducts. Copyright © 2011 Elsevier B.V. All rights reserved.

Online Simultaneous Hydrogen/Deuterium Exchange of Multitarget Gas-Phase Molecules by Electrospray Ionization Mass Spectrometry Coupled with Gas Chromatography.

PubMed

Jeong, Eun Sook; Cha, Eunju; Cha, Sangwon; Kim, Sunghwan; Oh, Han Bin; Kwon, Oh-Seung; Lee, Jaeick

2017-11-21

In this study, a hydrogen/deuterium (H/D) exchange method using gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) was first investigated as a novel tool for online H/D exchange of multitarget analytes. The GC and ESI source were combined with a homemade heated column transfer line. GC-ESI/MS-based H/D exchange occurs in an atmospheric pressure ion source as a result of reacting the gas-phase analyte eluted from GC with charged droplets of deuterium oxide infused as the ESI spray solvent. The consumption of the deuterated solvent at a flow rate of 2 μL min -1 was more economical than that in online H/D exchange methods reported to date. In-ESI-source H/D exchange by GC-ESI/MS was applied to 11 stimulants with secondary amino or hydroxyl groups. After H/D exchange, the spectra of the stimulants showed unexchanged, partially exchanged, and fully exchanged ions showing various degrees of exchange. The relative abundances corrected for naturally occurring isotopes of the fully exchanged ions of stimulants, except for etamivan, were in the range 24.3-85.5%. Methylephedrine and cyclazodone showed low H/D exchange efficiency under acidic, neutral, and basic spray solvent conditions and nonexchange for etamivan with an acidic phenolic OH group. The in-ESI-source H/D exchange efficiency by GC-ESI/MS was sufficient to determine the number of hydrogen by elucidation of fragmentation from the spectrum. Therefore, this online H/D exchange technique using GC-ESI/MS has potential as an alternative method for simultaneous H/D exchange of multitarget analytes.

Enzymatic digestion and selective quantification of underivatised delta-9-tetrahydrocannabinol and cocaine in human hair using gas chromatography-mass spectrometry.

PubMed

Breidi, Salah Eddine; Barker, James; Petróczi, Andrea; Naughton, Declan P

2012-01-01

Gas chromatography-mass spectrometric (GC-MS) methods for drug analysis routinely employ derivatising reagents. The aim of this paper was to develop a method for the analysis of two recreational drugs, delta-9-tetrahydrocannabinol (Δ(9)-THC) and cocaine in hair samples using GC-MS, without prior derivatisation, thus allowing the sample to be reanalysed in its original form. An enzymatic digestion technique was also developed. Ten hair samples, that were known positive for either Δ(9)-THC and/or cocaine, were enzymatically digested, extracted, and then analysed by GC-MS. All samples measured contained Δ(9)-THC and one sample contained cocaine. The limits of detection (LOD) and quantification (LOQ) were 0.02 ng/mg and 0.05 ng/mg, respectively, for cocaine and 0.015 ng/mg and 0.02 ng/mg, respectively, for Δ(9)-THC. The wide detection window, ease of direct analysis by GC-MS, lower detection limits of underivatised samples, and the stability of drugs using this technique may offer an improved method of analysis.

Enzymatic Digestion and Selective Quantification of Underivatised Delta-9-Tetrahydrocannabinol and Cocaine in Human Hair Using Gas Chromatography-Mass Spectrometry

PubMed Central

Breidi, Salah Eddine; Barker, James; Petróczi, Andrea; Naughton, Declan P.

2012-01-01

Gas chromatography-mass spectrometric (GC-MS) methods for drug analysis routinely employ derivatising reagents. The aim of this paper was to develop a method for the analysis of two recreational drugs, delta-9-tetrahydrocannabinol (Δ9-THC) and cocaine in hair samples using GC-MS, without prior derivatisation, thus allowing the sample to be reanalysed in its original form. An enzymatic digestion technique was also developed. Ten hair samples, that were known positive for either Δ9-THC and/or cocaine, were enzymatically digested, extracted, and then analysed by GC-MS. All samples measured contained Δ9-THC and one sample contained cocaine. The limits of detection (LOD) and quantification (LOQ) were 0.02 ng/mg and 0.05 ng/mg, respectively, for cocaine and 0.015 ng/mg and 0.02 ng/mg, respectively, for Δ9-THC. The wide detection window, ease of direct analysis by GC-MS, lower detection limits of underivatised samples, and the stability of drugs using this technique may offer an improved method of analysis. PMID:22567573

Analysis of residual monomers in dendritic methacrylate copolymers and composites by HPLC and headspace-GC/MS.

PubMed

Viljanen, Eeva K; Langer, Sarka; Skrifvars, Mikael; Vallittu, Pekka K

2006-09-01

The aim of this study was to analyze the residual monomer content of photopolymerized dendritic methacrylate copolymers and particulate filler composites. Headspace-gas chromatography/mass spectrometry (HS-GC/MS) was compared with high performance liquid chromatography (HPLC). The resin mixtures consisted of a dendritic methacrylate monomer, methyl methacrylate and acetoacetoxyethyl methacrylate in varied proportions. In addition, one of the composites contained 1,4-butanediol dimethacrylate. Camphorquinone and 2-(N,N-dimethylamino)ethyl methacrylate were used as the light-activated initiator system. The content of residual methyl methacrylate and acetoacetoxyethyl methacrylate after 40 s photopolymerization were analyzed with HPLC and HS-GC/MS. The content of residual methyl methacrylate decreased and residual acetoacetoxyethyl methacrylate increased with increasing concentration of acetoacetoxyethyl methacrylate in the resin mixture. The results with both methods had the same trend. The addition of acetoacetoxyethyl methacrylate enhanced the copolymerization of methyl methacrylate, but did not decrease the total residual monomer content. The HS-GC/MS method was found to be a feasible method in the analysis of low-boiling residuals in dental polymers.

Ultrasonication followed by single-drop microextraction combined with GC/MS for rapid determination of organochlorine pesticides from fish.

PubMed

Shrivas, Kamlesh; Wu, Hui-Fen

2008-02-01

A novel, rapid and simple sample pretreatment technique termed ultrasonication followed by single-drop micro-extraction (U-SDME) has been developed and combined with GC/MS for the determination of organochlorine pesticides (OCPs) in fish. In the present work, the lengthy procedures generally used in the conventional methods like, Soxhlet extraction, supercritical fluid extraction, pressurized liquid extraction and microwave assisted solvent extraction for extraction of OCPs from fish tissues are minimized by the use of two simple extraction procedures. Firstly, OCPs from fish were extracted in organic solvent with ultrasonication and then subsequently preconcentrated by single-drop micro-extraction (SDME). Extraction parameters of ultrasonication and SDME were optimized in spiked sample solution in order to obtain efficient extraction of OCPs from fish tissues. The calibration curves for OCPs were found to be linear between 10-1000 ng/g with correlation of estimations in the range 0.990-0.994. The recoveries obtained in blank fish tissues were ranged from 82.1 to 95.3%. The LOD and RSD for determination of OCPs in fish were 0.5 ng/g and 9.4-10.0%, respectively. The proposed method was applied for the determination of bioconcentration factor in fish after exposure to different concentrations of OCPs in cultured water. The present method avoids the co-extraction of lipids, long extraction steps (>12 h) and large amount of organic solvent for the separation of OCPs. The main advantages of the present method are rapid, selective, sensitive and low cost for the determination of OCPs in fish.

Chemical Composition Analysis of Extracts from Ficus Hirta Using Supercritical Fluid

NASA Astrophysics Data System (ADS)

Deng, S. B.; Chen, J. P.; Chen, Y. Z.; Yu, C. Q.; Yang, Y.; Wu, S. H.; Chen, C. Z.

2018-05-01

Ficus hirta was extracted by supercritical carbon dioxide. The volatile chemical components of extracts were analyzed using gas chromatography-mass spectrometry (GC-MS). The percentage of products extracted by Supercritical Fluid Extraction(SFE) was 2.5%. Nineteen volatile compounds were identified. The main volatile components were Elemicin, Psoralen, Palmitic acid, Bergapten, α-Linolenic acid, Medicarpin, Retinoic Acid, Maackiain, and Squalene. The method is simple and quick, and can be used for the preliminary analysis of chemical constituents of supercritical extracts of Ficus hirta.

Phenol-selective mass spectrometric analysis of jet fuel.

PubMed

Zhu, Haoxuan; Janusson, Eric; Luo, Jingwei; Piers, James; Islam, Farhana; McGarvey, G Bryce; Oliver, Allen G; Granot, Ori; McIndoe, J Scott

2017-08-21

Bromobenzyl compounds react selectively with phenols via the Williamson ether synthesis. An imidazolium charge-tagged bromobenzyl compound can be used to reveal phenol impurities in jet fuel by analysis via electrospray ionization mass spectrometry. The complex matrix as revealed by Cold EI GC/MS analysis is reduced to a few simple sets of compounds in the charge-tagged ESI mass spectrum, primarily substituted phenols and thiols. Examination of jet fuels treated by different refinery methods reveals the efficacy of these approaches in removing these contaminants.

GC-MS quantitation of fragrance compounds suspected to cause skin reactions. 1.

PubMed

Chaintreau, Alain; Joulain, Daniel; Marin, Christophe; Schmidt, Claus-Oliver; Vey, Matthias

2003-10-22

Recent changes in European legislation require monitoring of 24 volatile compounds in perfumes as they might elicit skin sensitization. This paper reports a GC-MS quantitation procedure for their determination in fragrance concentrates. GC and MS conditions were optimized for a routine use: analysis within 30 min, solvent and internal standard selection, and stock solution stability. Calibration curves were linear in the range of 2-100 mg/L with coefficients of determination in excess of 0.99. The method was tested using real perfumes spiked with known amounts of reference compounds.

Development of carbon plasma-coated multiwell plates for high-throughput mass spectrometric analysis of highly lipophilic fermentation products.

PubMed

Heinig, Uwe; Scholz, Susanne; Dahm, Pia; Grabowy, Udo; Jennewein, Stefan

2010-08-01

Classical approaches to strain improvement and metabolic engineering rely on rapid qualitative and quantitative analyses of the metabolites of interest. As an analytical tool, mass spectrometry (MS) has proven to be efficient and nearly universally applicable for timely screening of metabolites. Furthermore, gas chromatography (GC)/MS- and liquid chromatography (LC)/MS-based metabolite screens can often be adapted to high-throughput formats. We recently engineered a Saccharomyces cerevisiae strain to produce taxa-4(5),11(12)-diene, the first pathway-committing biosynthetic intermediate for the anticancer drug Taxol, through the heterologous and homologous expression of several genes related to isoprenoid biosynthesis. To date, GC/MS- and LC/MS-based high-throughput methods have been inherently difficult to adapt to the screening of isoprenoid-producing microbial strains due to the need for extensive sample preparation of these often highly lipophilic compounds. In the current work, we examined different approaches to the high-throughput analysis of taxa-4(5),11(12)-diene biosynthesizing yeast strains in a 96-deep-well format. Carbon plasma coating of standard 96-deep-well polypropylene plates allowed us to circumvent the inherent solvent instability of commonly used deep-well plates. In addition, efficient adsorption of the target isoprenoid product by the coated plates allowed rapid and simple qualitative and quantitative analyses of the individual cultures. Copyright 2010 Elsevier Inc. All rights reserved.

A gas chromatography-mass spectrometry (GC-MS) method for the detection and quantitation of monofluoroacetate in plants toxic to livestock

USDA-ARS?s Scientific Manuscript database

Monofluoroacetate (MFA) is a potent toxin that occurs in over 50 plant species in Africa, Australia, and South America and is responsible for significant livestock deaths in these regions. A gas chromatography–mass spectrometry (GC-MS) method for the analysis of MFA in plants based on the derivatiza...

A gas chromatography-mass spectrometry (GC-MS) method for the detection and quantitation of monofluoroacetate in plants toxic to livestock

USDA-ARS?s Scientific Manuscript database

Monofluoroacetate (MFA) is a potent toxin that occurs in over 50 plant species in Africa, Australia, and South America and is responsible for significant livestock deaths in these regions. A gas chromatography–mass spectrometry (GC-MS) method for the analysis of MFA in plants based on the derivatiz...

Analysis of Phenolic Antioxidants in Navy Mobility Fuels by Gas Chromatography-Mass Spectrometry

DTIC Science & Technology

2013-06-19

8.0 LITERATURE CITED .........................................................................................14 APPENDIX A: Calibration Curves for...chromatogram from an F-76 diesel fuel containing 24 ppm of the AO-37 additive package, analyzed using single column GC-MS-SIM method...sulfur diesel fuel containing 6.25 ppm of the AO-37 additive package, analyzed using dual column Deans switch GC-MS-SIM method

Method for factor analysis of GC/MS data

DOEpatents

Van Benthem, Mark H; Kotula, Paul G; Keenan, Michael R

2012-09-11

The method of the present invention provides a fast, robust, and automated multivariate statistical analysis of gas chromatography/mass spectroscopy (GC/MS) data sets. The method can involve systematic elimination of undesired, saturated peak masses to yield data that follow a linear, additive model. The cleaned data can then be subjected to a combination of PCA and orthogonal factor rotation followed by refinement with MCR-ALS to yield highly interpretable results.

Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction for determining acidic herbicides by gas chromatography/mass spectrometry.

PubMed

Wu, Jingming; Lee, Hian Kee

2006-10-15

Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction (LPME) for the trace determination of acidic herbicides (2,4-dichlorobenzoic acid, 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)propionic acid, 3,5-dichlorobenzoic acid, 2-(2,4,5-trichlorophenoxy)propionic acid) in aqueous samples by gas chromatography/mass spectrometry (GC/MS) was developed. Prior to GC injection port derivatization, acidic herbicides were converted into their ion-pair complexes with tetrabutylammonium chloride in aqueous samples and then extracted by 1-octanol impregnated in the hollow fiber. Upon injection, ion pairs of acidic herbicides were quantitatively derivatized to their butyl esters in the GC injection port. Thus, several parameters related to the derivatization process (i.e., injection temperature, purge-off time) were evaluated, and main parameters affecting the hollow fiber-protected LPME procedure such as extraction organic solvent, ion-pair reagent type, pH of aqueous medium, concentration of ion-pair reagent, sodium chloride concentration added to the aqueous medium, stirring speed, and extraction time profile, optimized. At the selected extraction and derivatization conditions, no matrix effects were observed. This method proved good repeatability (RSDs <12.3%, n = 6) and good linearity (r2 > or = 0.9939) for spiked deionized water samples for five analytes. The limits of detection were in the range of 0.51-13.7 ng x L(-1) (S/N =3) under GC/MS selected ion monitoring mode. The results demonstrated that injection port derivatization following ion-pair hollow fiber-protected LPME was a simple, rapid, and accurate method for the determination of trace acidic herbicides from aqueous samples. In addition, this method proved to be environmentally friendly since it completely avoided open derivatization with potentially hazardous reagents.

LC-MS/MS and GC-MS methods in propofol detection: Evaluation of the two analytical procedures.

PubMed

Vaiano, Fabio; Serpelloni, Giovanni; Focardi, Martina; Fioravanti, Alessia; Mari, Francesco; Bertol, Elisabetta

2015-11-01

Propofol is a short-acting hypnotic agent that is commonly used to induce and maintain anesthesia. Propofol abuse and its involvement in suicide deaths have increased in recent years, especially among healthcare personnel. An example is the suicide of a 61-year-old nurse found with a propofol drip in his left arm. We describe the postmortem concentration of propofol in various tissues (femoral and cardiac blood, bile, urine, brain, and liver) and in the drip. The toxicological analyses were performed through two analytical methods, differing in derivatization reaction and in instrumentation: silylation for gas chromatograph-mass spectrometer (GC-MS), as routinely performed in our laboratory for this kind of analyses (lower limits of quantification-LLOQ-in urine and blood: 0.3 and 5ng/ml); for liquid chromatograph-tandem mass spectrometer (LC-MS/MS) an innovative azo-coupling derivatization (LLOQ: 0.0004 and 0.1ng/ml). This latter produces an azo-derivative (molecular composition: C18H22ON2; molecular weight: 282Da) highly ionizable in electro-spray ion source, both in negative and positive ionizations. These two methods were compared to evaluate the effectiveness of this new LC-MS/MS analysis. An acidic hydrolysis (HCl 6N, 100°C, and 1h) was performed for the biological samples (1ml or 1g) irrespective of the analytical method applied. The drip content was extracted adding phosphate buffer (pH 8) and a dichloromethane/ethylacetate 8:2 (v:v) mixture. Derivatization steps were: silylation with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)+tetramethylammonium hydroxide (TMAH) for GC-MS; regarding LC-MS/MS, azo-coupling reaction with the aryl-diazonium salt (0-5°C, and 30min). The analyses were achieved in selected-ion monitoring for GC-MS (m/z, 235,250,73 propofol"; m/z, 252,267,27 propofol-d17) and in multiple reaction monitoring ([M-H](-): m/z 283→241,77, azo-propofol; m/z 299→251,77, azo-propofol-d17) for LC-MS/MS. Autopsy showed no significant findings. Propofol concentrations were (LC-MS/MS vs GC-MS, respectively): 15.1 vs 14.5mg/ml, drip content; 7.11 vs 6.07μg/ml, cardiac blood; 9.50 vs 7.19μg/ml, femoral blood; 0.64 vs 1.07μg/ml, bile; 0.042 vs 0.051μg/ml urine; 4.93 vs 5.89μg/g, brain; and 7.88 vs 6.80μg/g, liver. These values are comparable with the ones described in literature for death by acute propofol intoxication; the drip content is compatible with a diluted formulation of propofol available in Italy (20mg/ml injectable emulsion). The comparison shows an excellent fitting of the data (R(2): 0.9362). Toxicological results proved the cause of death as acute propofol intoxication. Furthermore, the new LC-MS/MS method showed an excellent effectiveness and reliability when compared to the routinely used GC-MS method. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Amino acid analysis in physiological samples by GC-MS with propyl chloroformate derivatization and iTRAQ-LC-MS/MS.

PubMed

Dettmer, Katja; Stevens, Axel P; Fagerer, Stephan R; Kaspar, Hannelore; Oefner, Peter J

2012-01-01

Two mass spectrometry-based methods for the quantitative analysis of free amino acids are described. The first method uses propyl chloroformate/propanol derivatization and gas chromatography-quadrupole mass spectrometry (GC-qMS) analysis in single-ion monitoring mode. Derivatization is carried out directly in aqueous samples, thereby allowing automation of the entire procedure, including addition of reagents, extraction, and injection into the GC-MS. The method delivers the quantification of 26 amino acids. The isobaric tagging for relative and absolute quantification (iTRAQ) method employs the labeling of amino acids with isobaric iTRAQ tags. The tags contain two different cleavable reporter ions, one for the sample and one for the standard, which are detected by fragmentation in a tandem mass spectrometer. Reversed-phase liquid chromatography of the labeled amino acids is performed prior to mass spectrometric analysis to separate isobaric amino acids. The commercial iTRAQ kit allows for the analysis of 42 physiological amino acids with a respective isotope-labeled standard for each of these 42 amino acids.

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

PubMed Central

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

2013-01-01

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

Application of gas chromatography/flame ionization detector-based metabolite fingerprinting for authentication of Asian palm civet coffee (Kopi Luwak).

PubMed

Jumhawan, Udi; Putri, Sastia Prama; Yusianto; Bamba, Takeshi; Fukusaki, Eiichiro

2015-11-01

Development of authenticity screening for Asian palm civet coffee, the world-renowned priciest coffee, was previously reported using metabolite profiling through gas chromatography/mass spectrometry (GC/MS). However, a major drawback of this approach is the high cost of the instrument and maintenance. Therefore, an alternative method is needed for quality and authenticity evaluation of civet coffee. A rapid, reliable and cost-effective analysis employing a universal detector, GC coupled with flame ionization detector (FID), and metabolite fingerprinting has been established for discrimination analysis of 37 commercial and non-commercial coffee beans extracts. gas chromatography/flame ionization detector (GC/FID) provided higher sensitivity over a similar range of detected compounds than GC/MS. In combination with multivariate analysis, GC/FID could successfully reproduce quality prediction from GC/MS for differentiation of commercial civet coffee, regular coffee and coffee blend with 50 wt % civet coffee content without prior metabolite details. Our study demonstrated that GC/FID-based metabolite fingerprinting can be effectively actualized as an alternative method for coffee authenticity screening in industries. Copyright © 2015. Published by Elsevier B.V.

Combination of solid-phase extraction with dispersive liquid-liquid microextraction followed by GC-MS for determination of pesticide residues from water, milk, honey and fruit juice.

PubMed

Shamsipur, Mojtaba; Yazdanfar, Najmeh; Ghambarian, Mahnaz

2016-08-01

In this work, an effective preconcentration method for the extraction and determination of traces of multi-residue pesticides was developed using solid-phase extraction (SPE) coupled with dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry (GC-MS). Variables affecting the performance of both extraction steps such as type and volume of elution and extraction solvents, breakthrough volume, salt addition, extraction time were thoroughly investigated. The proposed method resulted in good linearities (R(2)>0.9915) over the ranges of 1-10,000ngkg(-1), limits of detection (LODs) in the range of 0.5-1.0ngkg(-1) at S/N=3, and precision of RSD% of ⩽11.8. Under optimal conditions, the preconcentration factors were obtained in the range of 2362-10,593 for 100mL sample solutions. Comparison of the proposed method with other ones demonstrated that SPE-DLLME method provides higher extraction efficiency and larger preconcentration factor for determination of pesticides residues. Further, it is simple, inexpensive, highly sensitive, and can be successfully applied to separation, preconcentration and determination of the pesticides (and other noxious materials) in different real food samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid Screening of Ergot Alkaloids in Sclerotia by MALDI-TOF Mass Spectrometry.

PubMed

Sivagnanam, Kumaran; Komatsu, Emy; Patrick, Susan; Rampitsch, Christoph; Perreault, Hélène; Gräfenhan, Tom

2016-07-01

Ergot is a common disease of wheat and other cereal grains that is predominantly caused by Claviceps purpurea in the field, often affecting crop yield in addition to the environment. Infected grain can be contaminated with dark sclerotia, which contain fungal metabolites such as ergot alkaloids. The occurrence of ergot alkaloids in cereal grain is a major health concern for humans and livestock. Effective and rapid screening of these mycotoxins is crucial for producers, processors, and consumers of cereal-based food and feed grain. Established methods of ergot alkaloid screening based on LC-MS or GC-MS require laborious processes. A novel method using matrix-assisted laser desorption ionization (MALDI)-time-of-flight (TOF) MS was developed to identify four ergot alkaloids. Using dihydroxybenzoic acid as the matrix, ergosine, ergocornine, ergocryptine, and ergocristine were readily detected in individual sclerotia of C. purpurea. The accuracy of the identified ergot alkaloids was further confirmed by tandem MS analysis. MALDI-TOF MS is suitable for high-throughput screening of ergot alkaloids because it permits rapid and accurate identification, simple sample preparation, and no derivatization or chromatographic separation.

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

PubMed

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

2006-11-03

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

Evaluation of flavour profiles in e-cigarette refill solutions using gas chromatography-tandem mass spectrometry.

PubMed

Aszyk, Justyna; Kubica, Paweł; Woźniak, Mateusz Kacper; Namieśnik, Jacek; Wasik, Andrzej; Kot-Wasik, Agata

2018-04-27

Many flavour compounds that are present in e-liquids for e-cigarettes are responsible for specific tastes and smoking sensations for users. Data concerning content and specific types of flavours is often limited and unknown to users. The aim of the research was to define and compare flavour profiles of e-liquids with the same group taste from different manufacturers. Gas chromatography coupled with tandem mass spectrometry (GC-MS/MS) was used to separate and identify 90 popular compounds (98, including isomers) of interest. The developed method was validated in terms of accuracy (88-113%) for three spiking levels and the intra-day (0.2-13%) and inter-day precision (1-10%). Limits of quantitation were in the range of 10-816 ng/mL, while the matrix effects for 80% of the compounds were at negligible levels. The proposed method is rapid, simple and reliable and uses a green and modern GC-MS/MS technique. Twenty-five samples of five different flavours (tobacco, strawberry, cherry, menthol and apple) from five different producers were analysed, and the determined compounds were categorized and differentiated. The approach proposed in this study allowed for the evaluation of which compounds/group of compounds are responsible for taste and to distinguish common flavour compounds among the investigated brands for each flavour. Furthermore, the presented research can be considered in future toxicological studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives.

PubMed

Cunha, Sara C; Lehotay, Steven J; Mastovska, Katerina; Fernandes, José O; Beatriz, Maria; Oliveira, P P

2007-03-01

This paper describes the use of a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for extraction and cleanup of 16 pesticide residues of interest in olives and olive oil. These products contain a high lipid content, which can adversely affect pesticide recoveries and harm traditional chromatographic systems. For extraction, the main factors (oil and water content) were studied and optimized in experiments to maximize pesticide recoveries. Dispersive SPE with different sorbents was also investigated to minimize matrix coextractives and interferences. For analysis, a new automated DSI device was tested in GC-MS to avoid nonvolatile coextractives from contaminating the instrument. LC-MS/MS with positive ESI was used for those pesticides that were difficult to detect by GC-MS. The final method was validated for olives in terms of recoveries, repeatabilities, and reproducibilities using both detection techniques. The results demonstrated that the method achieved acceptable quantitative recoveries of 70-109% with RSDs < 20% for DSI-GC-MS and 88-130% with RSDs < 10% for LC-MS/MS, and LOQ at or below the regulatory maximum residue limits for the pesticides were achieved.

Comparison of gas chromatography-combustion-mass spectrometry and gas chromatography-flame ionization detector for the determination of fatty acid methyl esters in biodiesel without specific standards.

PubMed

Sobrado, Laura Alonso; Freije-Carrelo, Laura; Moldovan, Mariella; Encinar, Jorge Ruiz; Alonso, J Ignacio García

2016-07-29

GC-FID has been effectively used as a universal quantification technique for volatile organic compounds for a long time. In most cases, the use of the ECN allows for quantification by GC-FID without external calibration using only the response of a single internal standard. In this paper we compare the performance characteristics of GC-FID with those of post-column (13)C Isotope Dilution GC-Combustion-MS for the absolute quantification of organic compounds without the need for individual standards. For this comparison we have selected the quantification of FAMEs in biodiesel. The selection of the right internal standard was critical for GC-FID even when ECN were considered. On the other hand, the nature of the internal standard was not relevant when GC-Combustion-MS was employed. The proposed method was validated with the analysis of the certified reference material SRM 2772 and comparative data was obtained on real biodiesel samples. The analysis of the SRM 2772 biodiesel provided recoveries in the range 100.6-103.5% and 96.4-103.6% for GC-combustion-MS and GC-FID, respectively. The detection limit for GC-combustion-MS was found to be 4.2ng compound/g of injected sample. In conclusion, the quantitative performance of GC-Combustion-MS compared satisfactorily with that of GC-FID constituting a viable alternative for the quantification of organic compounds without the need for individual standards. Copyright © 2016 Elsevier B.V. All rights reserved.

Identification of 11-Nor-delta9-tetrahydrocannabinol-9-carboxylic acid in urine by ion trap GC-MS-MS in the context of doping analysis.

PubMed

Caballero, Gerardo M; D'Angelo, Carlos; Fraguío, Mariá Sol; Centurión, Osvaldo Teme

2004-01-01

The purpose of this study is to develop a sensitive and specific alternative to current gas chromatography (GC)-mass spectrometry (MS) selected ion monitoring confirmation methods of 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid (cTHC) in human urine samples, in the context of doping analysis. An identification procedure based on the comparison, among suspicious and control samples, of the relative abundances of cTHC selected product ions obtained by GC-tandem MS in an ion trap is presented. The method complies with the identification criteria for qualitative assays established by sports authorities; the comparison procedure is precise, reproducible, specific, and sensitive, thus indicating that it is fit for the purpose of identification accordingly to World Antidoping Agency requirements.

Full evaporation dynamic headspace in combination with selectable one-dimensional/two-dimensional gas chromatography-mass spectrometry for the determination of suspected fragrance allergens in cosmetic products.

PubMed

Devos, Christophe; Ochiai, Nobuo; Sasamoto, Kikuo; Sandra, Pat; David, Frank

2012-09-14

Suspected fragrance allergens were determined in cosmetic products using a combination of full evaporation-dynamic headspace (FEDHS) with selectable one-dimensional/two-dimensional GC-MS. The full evaporation dynamic headspace approach allows the non-discriminating extraction and injection of both apolar and polar fragrance compounds, without contamination of the analytical system by high molecular weight non-volatile matrix compounds. The method can be applied to all classes of cosmetic samples, including water containing matrices such as shower gels or body creams. In combination with selectable (1)D/(2)D GC-MS, consisting of a dedicated heart-cutting GC-MS configuration using capillary flow technology (CFT) and low thermal mass GC (LTM-GC), a highly flexible and easy-to-use analytical solution is offered. Depending on the complexity of the perfume fraction, analyses can be performed in one-dimensional GC-MS mode or in heart-cutting two-dimensional GC-MS mode, without the need of hardware reconfiguration. The two-dimensional mode with independent temperature control of the first and second dimension column is especially useful to confirm the presence of detected allergen compounds when mass spectral deconvolution is not possible. Copyright © 2012 Elsevier B.V. All rights reserved.

Introducing Students to Gas Chromatography-Mass Spectrometry Analysis and Determination of Kerosene Components in a Complex Mixture

ERIC Educational Resources Information Center

Pacot, Giselle Mae M.; Lee, Lyn May; Chin, Sung-Tong; Marriott, Philip J.

2016-01-01

Gas chromatography-mass spectrometry (GC-MS) and GC-tandem MS (GC-MS/MS) are useful in many separation and characterization procedures. GC-MS is now a common tool in industry and research, and increasingly, GC-MS/MS is applied to the measurement of trace components in complex mixtures. This report describes an upper-level undergraduate experiment…

Differentiating organically and conventionally grown oregano using ultraperformance liquid chromatography mass spectrometry (UPLC-MS), headspace gas chromatography with flame ionization detection (headspace-GC-FID), and flow injection mass spectrum (FIMS) fingerprints combined with multivariate data analysis.

PubMed

Gao, Boyan; Qin, Fang; Ding, Tingting; Chen, Yineng; Lu, Weiying; Yu, Liangli Lucy

2014-08-13

Ultraperformance liquid chromatography mass spectrometry (UPLC-MS), flow injection mass spectrometry (FIMS), and headspace gas chromatography (headspace-GC) combined with multivariate data analysis techniques were examined and compared in differentiating organically grown oregano from that grown conventionally. It is the first time that headspace-GC fingerprinting technology is reported in differentiating organically and conventionally grown spice samples. The results also indicated that UPLC-MS, FIMS, and headspace-GC-FID fingerprints with OPLS-DA were able to effectively distinguish oreganos under different growing conditions, whereas with PCA, only FIMS fingerprint could differentiate the organically and conventionally grown oregano samples. UPLC fingerprinting provided detailed information about the chemical composition of oregano with a longer analysis time, whereas FIMS finished a sample analysis within 1 min. On the other hand, headspace GC-FID fingerprinting required no sample pretreatment, suggesting its potential as a high-throughput method in distinguishing organically and conventionally grown oregano samples. In addition, chemical components in oregano were identified by their molecular weight using QTOF-MS and headspace-GC-MS.

Quantification of Neural Ethanol and Acetaldehyde Using Headspace GC-MS

PubMed Central

Heit, Claire; Eriksson, Peter; Thompson, David C; Fritz, Kristofer S; Vasiliou, Vasilis

2016-01-01

BACKGROUND There is controversy regarding the active agent responsible for alcohol addiction. The theory that ethanol itself was the agent in alcohol drinking behavior was widely accepted until acetaldehyde was found in the brain. The importance of acetaldehyde formation in the brain role is still subject to speculation due to the lack of a method to accurately assay the acetaldehyde levels directly. A highly sensitive GC-MS method to reliably determine acetaldehyde concentration with certainty is needed to address whether neural acetaldehyde is indeed responsible for increased alcohol consumption. METHODS A headspace gas chromatograph coupled to selected ion monitoring mass spectrometry was utilized to develop a quantitative assay for acetaldehyde and ethanol. Our GC-MS approach was carried out using a Bruker Scion 436-GC SQ MS. RESULTS Our approach yields limits of detection of acetaldehyde in the nanomolar range and limits of quantification in the low micromolar range. Our linear calibration includes 5 concentrations with a least square regression greater than 0.99 for both acetaldehyde and ethanol. Tissue analyses using this method revealed the capacity to quantify ethanol and acetaldehyde in blood, brain, and liver tissue from mice. CONCLUSIONS By allowing quantification of very low concentrations, this method may be used to examine the formation of ethanol metabolites, specifically acetaldehyde, in murine brain tissue in alcohol research. PMID:27501276

Identification of unknown impurity of azelaic acid in liposomal formulation assessed by HPLC-ELSD, GC-FID, and GC-MS.

PubMed

Han, Stanisław; Karłowicz-Bodalska, Katarzyna; Potaczek, Piotr; Wójcik, Adam; Ozimek, Lukasz; Szura, Dorota; Musiał, Witold

2014-02-01

The identification of new contaminants is critical in the development of new medicinal products. Many impurities, such as pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid, have been identified in samples of azelaic acid. The aim of this study was to identify impurities observed during the stability tests of a new liposomal dosage form of azelaic acid that is composed of phosphatidylcholine and a mixture of ethyl alcohol and water, using high-performance liquid chromatography with evaporative light-scattering detector (HPLC-ELSD), gas chromatography-flame ionisation detection (GC-FID), and gas chromatography-mass spectrometry (GC-MS) methods. During the research and development of a new liposomal formulation of azelaic acid, we developed a method for determining the contamination of azelaic acid using HPLC-ELSD. During our analytical tests, we identified a previously unknown impurity of a liposomal preparation of azelaic acid that appeared in the liposomal formulation of azelaic acid during preliminary stability studies. The procedure led to the conclusion that the impurity was caused by the reaction of azelaic acid with one of the excipients that was applied in the product. The impurity was finally identified as an ethyl monoester of azelaic acid. The identification procedure of this compound was carried out in a series of experiments comparing the chromatograms that were obtained via the following chromatographic methods: HPLC-ELSD, GC-FID, and GC-MS. The final identification of the compound was carried out by GC with MS.

Methods in endogenous steroid profiling - A comparison of gas chromatography mass spectrometry (GC-MS) with supercritical fluid chromatography tandem mass spectrometry (SFC-MS/MS).

PubMed

Teubel, Juliane; Wüst, Bernhard; Schipke, Carola G; Peters, Oliver; Parr, Maria Kristina

2018-06-15

In various fields of endocrinology, the determination of steroid hormones synthesised by the human body plays an important role. Research on central neurosteroids has been intensified within the last years, as they are discussed as biomarkers for various cognitive disorders. Their concentrations in cerebrospinal fluid (CSF) are considered to be regulated independently from peripheral fluids. For that reason, the challenging matrix CSF becomes a very interesting specimen for analysis. Concentrations are expected to be very low and available amount of CSF is limited. Thus, a comprehensive method for very sensitive quantification of a set of analytes as large as possible in one analytical aliquot is desired. However, high structural similarities of the selected panel of 51 steroids and steroid sulfates, including numerous isomers, challenges achievement of chromatographic selectivity. Since decades the analysis of endogenous steroids in various body fluids is mainly performed by gas chromatography (GC) coupled to (tandem) mass spectrometry (MS(/MS)). Due to the structure of the steroids of interest, derivatisation is performed to meet the analytical requirements for GC-MS(/MS). Most of the laboratories use a two-step derivatisation in multi-analyte assays that was already published in the 1980s. However, for some steroids this elaborate procedure yields multiple isomeric derivatives. Thus, some laboratories utilize (ultra) high performance liquid chromatography ((U)HPLC)-MS/MS as alternative but, even UHPLC is not able to separate some of the isomeric pairs. Supercritical fluid chromatography (SFC) as an orthogonal separation technique to GC and (U)HPLC may help to overcome these issues. Within this project the two most promising methods for endogenous steroid profiling were investigated and compared: the "gold standard" GC-MS and the orthogonal separation technique SFC-MS/MS. Different derivatisation procedures for gas chromatographic detection were explored and the formation of multiple derivatives described and confirmed. Taken together, none of the investigated derivatisation procedures provided acceptable results for further method development to meet the requirements of this project. SFC with its unique selectivity was able to overcome these issues and to distinguish all selected steroids, including (pro-)gestagens, androgens, corticoids, estrogens, and steroid sulfates with appropriate selectivity. Valued especially in the separation of enantiomeric analytes, SFC has shown its potential as alternative to GC. The successful separation of 51 steroids and steroid sulfates on different columns is presented to demonstrate the potential of SFC in endogenous steroid profiling. Copyright © 2018 Elsevier B.V. All rights reserved.

Rapid analysis of 3,4-methylenedioxymethamphetamine: a comparison of nonaqueous capillary electrophoresis/fluorescence detection with GC/MS.

PubMed

Fang, Ching; Chung, Yu-Lin; Liu, Ju-Tsung; Lin, Cheng-Huang

2002-02-18

Because of the increasing use of 3,4-methylenedioxymethamphetamine (3,4-MDMA), a rapid and sensitive analytical technique is required for its detection and determination. Using nonaqueous capillary electrophoresis/fluorescence spectroscopy (NACE/FS) detection, it is possible to determine this drug at the level 0.5 ppm without any pre-treatment in less than 5 min. After liquid-liquid extraction, the sample can be condensed and a detection limit of 3,4-MDMA in urine of 50 ppb (S/N = 3) can be achieved. The precision of the method was evaluated by measuring the repeatability and intermediate precision of migration time and the corrected peak height by comparison with a 3,4-MDMA-D5 internal standard. With the conventional GC/MS method, it is necessary to derivatize the 3,4-MDMA before injection and the GC migration time also is in excess of 20 min. Therefore, NACE/FS represents a good complementary method to GC/MS for use in forensic analysis.

Authentication of organically and conventionally grown basils by gas chromatograpy/mass spectrometry chemical profiles

USDA-ARS?s Scientific Manuscript database

Basil plants cultivated by organic and conventional farming practices were differentiated using gas chromatography/mass spectrometry (GC/MS) and chemometric methods. The two-way GC/MS data sets were baseline-corrected and retention time-aligned prior to data processing. Two self-devised fuzzy clas...

GC-MS (GAS CHROMATOGRAPHIC-MASS SPECTROMETRIC) SUITABILITY TESTING OF RCRA APPENDIX VIII AND MICHIGAN LIST ANALYTES

EPA Science Inventory

As a first step in a hierarchical scheme to demonstrate the suitability of present U.S. Environmental Protection Agency (USEPA) analysis methods and/or develop new methodology, the gas chromatographic (GC) separation and mass spectrometric (MS) detection characteristics of 328 to...

Greenhouse Gas Analysis by GC/MS

NASA Astrophysics Data System (ADS)

Bock, E. M.; Easton, Z. M.; Macek, P.

2015-12-01

Current methods to analyze greenhouse gases rely on designated complex, multiple-column, multiple-detector gas chromatographs. A novel method was developed in partnership with Shimadzu for simultaneous quantification of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in environmental gas samples. Gas bulbs were used to make custom standard mixtures by injecting small volumes of pure analyte into the nitrogen-filled bulb. Resulting calibration curves were validated using a certified gas standard. The use of GC/MS systems to perform this analysis has the potential to move the analysis of greenhouse gasses from expensive, custom GC systems to standard single-quadrupole GC/MS systems that are available in most laboratories, which wide variety of applications beyond greenhouse gas analysis. Additionally, use of mass spectrometry can provide confirmation of identity of target analytes, and will assist in the identification of unknown peaks should they be present in the chromatogram.

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

PubMed

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

2015-04-07

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

Analysis of bacterial fatty acids by flow modulated comprehensive two-dimensional gas chromatography with parallel flame ionization detector/mass spectrometry.

PubMed

Gu, Qun; David, Frank; Lynen, Frédéric; Rumpel, Klaus; Xu, Guowang; De Vos, Paul; Sandra, Pat

2010-06-25

Comprehensive two-dimensional gas chromatography (GCxGC) offers an interesting tool for profiling bacterial fatty acids. Flow modulated GCxGC using a commercially available system was evaluated, different parameters such as column flows and modulation time were optimized. The method was tested on bacterial fatty acid methyl esters (BAMEs) from Stenotrophomonas maltophilia LMG 958T by using parallel flame ionization detector (FID)/mass spectrometry (MS). The results are compared to data obtained using a thermal modulated GCxGC system. The data show that flow modulated GCxGC-FID/MS method can be applied in a routine environment and offers interesting perspectives for chemotaxonomy of bacteria.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Owens, J; Hok, S; Alcaraz, A

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 limitmore » 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.« less

Analysis of non-esterified fatty acids in human samples by solid-phase-extraction and gas chromatography/mass spectrometry.

PubMed

Kopf, Thomas; Schmitz, Gerd

2013-11-01

The determination of the fatty acid (FA) profile of lipid classes is essential for lipidomic analysis. We recently developed a GC/MS-method for the analysis of the FA profile of total FAs, i.e. the totality of bound and unbound FAs, in any given biological sample (TOFAs). Here, we present a method for the analysis of non-esterified fatty acids (NEFAs) in biological samples, i.e. the fraction that is present as extractable free fatty acids. Lipid extraction is performed according to Dole using 80/20 2-propanol/n-hexane (v/v), with 0.1% H2SO4. The fatty acid-species composition of this NEFA-fraction is determined as FAME after derivatization with our GC/MS-method on a BPX column (Shimadzu). Validation of the NEFA-method presented was performed in human plasma samples. The validated method has been used with human plasma, cells and tissues, as well as mammalian body fluids and tissue samples. The newly developed solid-phase-extraction (SPE)-GC-MS method allows the rapid separation of the NEFA-fraction from a neutral lipid extract of plasma samples. As a major advantage compared to G-FID-methods, GC-MS allows the use of stable isotope labeled fatty acid precursors to monitor fatty acid metabolism. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of trace level genotoxic impurities in small molecule drug substances using conventional headspace gas chromatography with contemporary ionic liquid diluents and electron capture detection.

PubMed

Ho, Tien D; Yehl, Peter M; Chetwyn, Nik P; Wang, Jin; Anderson, Jared L; Zhong, Qiqing

2014-09-26

Ionic liquids (ILs) were used as a new class of diluents for the analysis of two classes of genotoxic impurities (GTIs), namely, alkyl/aryl halides and nitro-aromatics, in small molecule drug substances by headspace gas chromatography (HS-GC) coupled with electron capture detection (ECD). This novel approach using ILs as contemporary diluents greatly broadens the applicability of HS-GC for the determination of high boiling (≥ 130°C) analytes including GTIs with limits of detection (LOD) ranging from 5 to 500 parts-per-billion (ppb) of analytes in a drug substance. This represents up to tens of thousands-fold improvement compared to traditional HS-GC diluents such as dimethyl sulfoxide (DMSO) and dimethylacetamide (DMAC). Various ILs were screened to determine their suitability as diluents for the HS-GC/ECD analysis. Increasing the HS oven temperatures resulted in varying responses for alkyl/aryl halides and a significant increase in response for all nitroaromatic GTIs. Linear ranges of up to five orders of magnitude were found for a number of analytes. The technique was validated on two active pharmaceutical ingredients with excellent recovery. This simple and robust methodology offers a key advantage in the ease of method transfer from development laboratories to quality control environments since conventional validated chromatographic data systems and GC instruments can be used. For many analytes, it is a cost effective alternative to more complex trace analytical methodologies like LC/MS and GC/MS, and significantly reduces the training needed for operation. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of volatile profile from ten different varieties of Chinese jujubes by HS-SPME/GC-MS coupled with E-nose.

PubMed

Chen, Qinqin; Song, Jianxin; Bi, Jinfeng; Meng, Xianjun; Wu, Xinye

2018-03-01

Volatile profile of ten different varieties of fresh jujubes was characterized by HS-SPME/GC-MS (headspace solid phase micro-extraction combined with gas chromatography-mass spectrometry) and E-nose (electronic nose). GC-MS results showed that a total of 51 aroma compounds were identified in jujubes, hexanoic acid, hexanal, (E)-2-hexenal, (Z)-2-heptenal, benzaldehyde and (E)-2-nonenal were the main aroma components with contributions that over 70%. Differentiation of jujube varieties was conducted by cluster analysis of GC-MS data and principal component analysis & linear discriminant analysis of E-nose data. Both results showed that jujubes could be mainly divided into two groups: group A (JZ, PDDZ, JSXZ and LWZZ) and group B (BZ, YZ, MZ, XZ and DZ). There were significant differences in contents of alcohols, acids and aromatic compounds between group A and B. GC-MS coupled with E-nose could be a fast and accurate method to identify the general flavor difference in different varieties of jujubes. Copyright © 2017 Elsevier Ltd. All rights reserved.

N,N-Dimethyltryptamine and dichloromethane: rearrangement of quaternary ammonium salt product during GC-EI and CI-MS-MS analysis.

PubMed

Brandt, Simon D; Martins, Cláudia P B; Freeman, Sally; Dempster, Nicola; Wainwright, Mark; Riby, Philip G; Alder, John F

2008-05-12

N,N-Dimethyltryptamine (DMT) 1 is a simple tryptamine derivative with powerful psychoactive properties. It is abundant in nature and easily accessible through a variety of synthetic routes. Most work-up procedures require the use of organic solvents and halogenated representatives are often employed. DMT was found to be reactive towards dichloromethane, either during work-up or long term storage therein, which led to the formation of the quaternary ammonium salt N-chloromethyl-DMT chloride 2. Analysis of this side-product by gas chromatography ion trap mass spectrometry (GC-MS), both in electron and chemical ionisation tandem MS modes, gave only degradation products. For example, 2 could not be detected but appeared to have rearranged to 3-(2-chloroethyl)indole 3 and 2-methyltetrahydro-beta-carboline 4, whereas HPLC analysis enabled the detection of 2. GC-MS is a standard tool for the fingerprinting of drug products. The identification of a particular synthetic route is based on the analysis of impurities, provided these side products can be established to be route-specific. The in situ detection of both 3 and 4 within a DMT sample may have led to erroneous conclusions with regards to the identification of the synthetic route.

[Toxicologic blood emergency screening].

PubMed

Cohen, Sabine; Manat, Aurélie; Dumont, Benoit; Bévalot, Fabien; Manchon, Monique; Berny, Claudette

2010-01-01

In order to overcome the stop marketing by Biorad company of automated high performance liquid chromatograph with UV detection (Remedi), we developed a gas chromatography-mass spectrometry (GC-MS) to detect and to give an approximation of the overdose of molecules frequently encountered in drug intoxications. Therefore two hundred eighty seventeen blood samples were collected over a period of one year and allowed us to evaluate and compare the performance of these two techniques. As identification, GC-MS does not identify all molecules detected by Remedi in 24.2% of cases; there is a lack of sensitivity for opiates and the systematic absence of certain molecules such as betablockers. However, in 75.8% of cases the GC-MS detects all molecules found by Remedi and other molecules such as meprobamate, paracetamol, benzodiazepines and phenobarbital. The concentrations obtained are interpreted in terms of overdose showed 15.7% of discrepancy and 84.3% of concordance between the two techniques. The GC-MS technique described here is robust, fast and relatively simple to implement; the identification is facilitated by macro commands and the semi quantification remains manual. Despite a sequence of cleaning the column after each sample, carryover of a sample to the next remains possible. This technique can be used for toxicologic screening in acute intoxications. Nevertheless it must be supplemented by a HPLC with UV detection if molecules such as betablockers are suspected.

Application of gas chromatography-tandem mass spectrometry for the determination of amphetamine-type stimulants in blood and urine.

PubMed

Woźniak, Mateusz Kacper; Wiergowski, Marek; Aszyk, Justyna; Kubica, Paweł; Namieśnik, Jacek; Biziuk, Marek

2018-01-30

Amphetamine, methamphetamine, phentermine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), and 3,4-methylenedioxy-N-ethylamphetamine (MDEA) are the most popular amphetamine-type stimulants. The use of these substances is a serious societal problem worldwide. In this study, a method based on gas chromatography-tandem mass spectrometry (GC-MS/MS) with simple and rapid liquid-liquid extraction (LLE) and derivatization was developed and validated for the simultaneous determination of the six aforementioned amphetamine derivatives in blood and urine. The detection of all compounds was based on multiple reaction monitoring (MRM) transitions. The most important advantage of the method is the minimal sample volume (as low as 200μL) required for the extraction procedure. The validation parameters, i.e., the recovery (90.5-104%), inter-day accuracy (94.2-109.1%) and precision (0.5-5.8%), showed the repeatability and sensitivity of the method for both matrices and indicated that the proposed procedure fulfils internationally established acceptance criteria for bioanalytical methods The procedure was successfully applied to the analysis of real blood and urine samples examined in 22 forensic toxicological cases. To the best of our knowledge, this is the first work presenting the use of GC-MS/MS for the determination of amphetamine-type stimulants in blood and urine. In view of the low limits of detection (0.09-0.81ng/mL), limits of quantification (0.26-2.4ng/mL), and high selectivity, the procedure can be applied for drug monitoring in both fatal and non-fatal intoxication cases in routine toxicology analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Volatile Compounds from the Different Organs of Houttuynia cordata and Litsea cubeba (L. citriodora).

PubMed

Asakawa, Yoshinori; Tomiyama, Kenichi; Sakurai, Kazutoshi; Kawakami, Yukihiro; Yaguchi, Yoshihiro

2017-08-01

The volatile compounds obtained from the different organs of Houttuynia cordata (Saururaceae) and Litsea cubeba (Lauraceae) were analyzed by Gas Chromatography/Mass Spectrometry (GC/MS), Headspace Solid Phase Micro Extraction-Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS), and GC/olfactometry (GC/O). The major component of all parts of H. cordata is assigned as 4-tridecanone. Each organ produces myrcene as the major monoterpenoid. The major monoterpene in the rhizomes and roots was β-pinene instead of myrcene. 1-Decanal which was responsible for the unpleasant odor of this plant, was the predominant polyketide in both leaves and stems. The presence of 1-decanal was very poor in flowers, stem collected in summer, rhizomes, and roots. GC/MS analyses were very simple in case of the crude extracts of flowers. The content of sesquiterpenoids was extremely poor. (8Z)-Heptadecene, geranial, and neral were detected as the major components in Litsea cubeba. Odor-contributing components by GC/O analysis of the ether extract of the fresh flowers of L. cubeba were neral and geranial which played an important role in sweet-lemon fragrance of the flowers. The role of a high content of (8Z)-heptadecene was still unknown but it might play a significant role in the dispersion of the volatile monoterpene hydrocarbons and aldehydes. The flower volatiles of the Japanese L. cubeba were chemically quite different from those of the Chinese same species.

[Determination of organotin compounds in textile auxiliaries by gas chromatography-mass spectrometry].

PubMed

Li, Yanming; Hu, Yongjie; Liu, Jinhua; Guo, Yuliang; Wang, Guiqin

2011-04-01

A gas chromatography-mass spectrometry (GC-MS) method has been developed for the determination of dibutyltin (DBT), tributyltin (TBT) and triphenyltin (TPhT) in textile auxiliaries. The sample was first extracted with n-hexane in acetate buffer solution (pH 4.0) under ultrasonication (for hydrophobic sample) or oscillation extraction (for hydrophilic sample) and then derivatized with sodium tetraethylborate in tetrahydrofuran. The derivative was determined by GC-MS in selected ion monitoring (SIM) mode. The separation and quantification were achieved using a Rxi-5 ms silica capillary column (30 m x 0.25 mm x 0.25 microm). The linear ranges were 0.1-8.0 mg/L for both DBT and TBT, and 0.1-4.0 mg/L for TPhT. There were good linear relationships between the peak area and concentration in the linear ranges and the correlation coefficients (r2) were 0.9994-0.9998. The detection limits (LOD) were from 0.003 mg/L to 0.005 mg/L. The average recoveries of these organotin compounds at the three spiked levels of 4.0, 10.0 and 40.0 mg/kg were 92.6%-108.0% with the relative standard deviations (RSDs) of 2.5%-10.2%. The method is simple and accurate for simultaneous analysis of the DBT, TBT and TPhT in textile auxiliaries.

Determination of nandrolone and metabolites in urine samples from sedentary persons and sportsmen.

PubMed

Galán Martín, A M; Mariño, J I; García de Tiedra, M P; Marabé, J J; Caballero Loscos, M J; Mariño, M M

2001-09-25

Metabolites of nandrolone were determined in the urine of several sportsmen, sedentary and post-menopausal women by capillary gas chromatography-mass spectrometry quadrupole (GC-MS) and capillary gas chromatography mass-mass spectrometry ion trap (GC-MS-MS) methods. The method employed was GC-EI-MS with 17alpha-methyltestosterone as internal standard with ethyl ether extraction prior to selected ion monitoring of the bis(trimethylsilyl) ethers at ion masses m/z 405 and 420 for the nandrolone metabolites, and 418 and 403 for nandrolone derivative. Recovery for nandrolone, 19-norandrosterone (19-NA) and 19-noretiocholanolone (19-NE) was 97.20, 94.17 and 95.54%, respectively. Detection limits for nandrolone, 19-NA and 19-NE were 0.03, 0.01 and 0.06 ng/ml. Metabolites of nandrolone (19-NA and 19-NE) were found in 12.5% (n = 40) of sportsmen and 40% (n = 10) of post-menopausal women.

Development of a Direct Headspace Collection Method from Arabidopsis Seedlings Using HS-SPME-GC-TOF-MS Analysis

PubMed Central

Kusano, Miyako; Iizuka, Yumiko; Kobayashi, Makoto; Fukushima, Atsushi; Saito, Kazuki

2013-01-01

Plants produce various volatile organic compounds (VOCs), which are thought to be a crucial factor in their interactions with harmful insects, plants and animals. Composition of VOCs may differ when plants are grown under different nutrient conditions, i.e., macronutrient-deficient conditions. However, in plants, relationships between macronutrient assimilation and VOC composition remain unclear. In order to identify the kinds of VOCs that can be emitted when plants are grown under various environmental conditions, we established a conventional method for VOC profiling in Arabidopsis thaliana (Arabidopsis) involving headspace-solid-phase microextraction-gas chromatography-time-of-flight-mass spectrometry (HS-SPME-GC-TOF-MS). We grew Arabidopsis seedlings in an HS vial to directly perform HS analysis. To maximize the analytical performance of VOCs, we optimized the extraction method and the analytical conditions of HP-SPME-GC-TOF-MS. Using the optimized method, we conducted VOC profiling of Arabidopsis seedlings, which were grown under two different nutrition conditions, nutrition-rich and nutrition-deficient conditions. The VOC profiles clearly showed a distinct pattern with respect to each condition. This study suggests that HS-SPME-GC-TOF-MS analysis has immense potential to detect changes in the levels of VOCs in not only Arabidopsis, but other plants grown under various environmental conditions. PMID:24957989

Detection of the Spermicide Nonoxynol-9 Via GC-MS

NASA Astrophysics Data System (ADS)

Musah, Rabi A.; Vuong, Angela L.; Henck, Colin; Shepard, Jason R. E.

2012-05-01

The spermicide nonoxynol-9 is actually a complex mixture of dozens of closely related amphiphilic compounds, and the chemical properties of this assortment significantly hamper its characterization by GC-MS. The inability to perform routine GC-MS testing on nonoxynol-9 has limited its evidentiary value in forensic casework, which relies heavily on this technique for analysis. A disturbing trend in sexual assault is the use of condoms by assailants, to avoid leaving behind DNA evidence that can connect a perpetrator to a victim. This observation necessitates the development of alternative methods for the analysis of trace evidence that can show causal links between a victim and a suspect. Detection of lubricants associated with sexual assault is one such way to establish this connection. The development of GC-MS methods that permit facile detection of both nonoxynol-9 alone and nonoxynol-9 extracted from other complex matrices that have potential as trace evidence in sexual assault is reported. A detection limit of 2.14 μg of nonoxynol-9 is demonstrated, and a detailed mass spectral profile that elaborates on what is known of its structure is provided.

ANTIMICROBIAL AND ANTIBIOFILM EFFECTS OF EXTRACTS FROM TRAPA NATANS L., EVALUATION OF TOTAL PHENOLIC AND FLAVONOID CONTENTS AND GC-MS ANALYSIS.

PubMed

Radojevic, Ivana D; Vasic, Sava M; Dekic, Milan S; Radulovic, Niko S; Delic, Gorica T; Durdevic, Jelena S; Comic, Ljiljana R

2016-11-01

Research conducted in this study shows the applied in vitro antimicrobial and antibiofilm activity of the four extracts isolated from Trapa natans L. leaves. In this study, different methods were used (microdilution, tissue culture plate, different colorimetric methods, GC-FID and GC-MS analysis). While the water extract didn't show antibacterial activity, the acetone extract showed the strongest one. The same activity in the case of Pseudomonas aeruginosa (MIC was 313 μg/mL) was better than the activity of controls and it matched with antibiofilm activity. The effect of extracts was better on G+ bacteria (MICs were <78-625 μg/mL). For ethanol and ethyl acetate extracts all BIC values were better than MICs. Extracts showed a significant effect on Aspergillus restrictus (MICs were < 78/156 μg/mL). The GC and GC-MS analysis of the ethyl acetate extract revealed the identification of 22 compounds with (all E)-squalene (20.2%), n-alkanes and norlignan hinokiresinol among the most abundant ones. This is the first time that T. natans was studied using these methods.

Quantitation of total homocysteine in human plasma by derivatization to its N(O,S)-propoxycarbonyl propyl ester and gas chromatography-mass spectrometry analysis.

PubMed

Sass, J O; Endres, W

1997-08-01

Much evidence supports the hypothesis that mild or moderate hyperhomocysteinaemia represents an important and independent risk factor for occlusive vascular diseases. Therefore, the accurate and reliable determination of total plasma homocysteine has gained major importance for risk assessment. Furthermore, it can help in the detection of folate and vitamin B12 deficiency. This has prompted us to develop a sensitive gas chromatography-mass spectrometry (GC-MS) method in order to quantify total homocysteine in human plasma. Prior to chromatography, reduced homocysteine was released from disulfide bonds by incubation with excess dithiothreitol and converted into its N(O,S)-propoxycarbonyl propyl ester by derivatization with n-propyl chloroformate. Aminoethylcysteine served as internal standard. The method proved to be highly linear over the entire concentration range examined (corresponding to 0-266 microM homocysteine) and showed intra-assay and inter-assay variation (relative standard deviations) of approximately 5 and 5-10%, respectively. External quality control by comparison with duplicate analysis performed on a HPLC-based system revealed satisfactory correlation. The newly developed GC-MS based method provides simple, reliable and fast quantification of total homocysteine and requires only inexpensive chemicals, which are easy to obtain.

[Determination of olive oil content in olive blend oil by headspace gas chromatography-mass spectrometry].

PubMed

Jiang, Wanfeng; Zhang, Ning; Zhang, Fengyan; Yang, Zhao

2017-07-08

A method for the determination of the content of olive oil in olive blend oil by headspace gas chromatography-mass spectrometry (SH-GC/MS) was established. The amount of the sample, the heating temperature, the heating time, the amount of injection, the injection mode and the chromatographic column were optimized. The characteristic compounds of olive oil were found by chemometric method. A sample of 1.0 g was placed in a 20 mL headspace flask, and heated at 180℃ for 2700 s. Then, 1.0 mL headspace gas was taken into the instrument. An HP-88 chromatographic column was used for the separation and the analysis was performed by GC/MS. The results showed that the linear range was 0-100%(olive oil content). The linear correlation coefficient ( r 2 ) was more than 0.995, and the limits of detection were 1.26%-2.13%. The deviations of olive oil contents in the olive blend oil were from -0.65% to 1.02%, with the relative deviations from -1.3% to 6.8% and the relative standard deviations from 1.18% to 4.26% ( n =6). The method is simple, rapid, environment friendly, sensitive and accurate. It is suitable for the determination of the content of olive oil in olive blend oil.

Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

PubMed

Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

2014-08-08

For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. Copyright © 2014 Elsevier B.V. All rights reserved.

GC-MS profile of antimicrobial and antioxidant fractions from Cordia rothii roots.

PubMed

Khan, Kehkashan; Firdous, Sadiqa; Ahmad, Aqeel; Fayyaz, Nida; Nadir, Muhammad; Rasheed, Munawwer; Faizi, Shaheen

2016-11-01

An ethnobotanical survey of Cordia rothii Roem. & Schult. (Boraginaceae) reveals it as a medicinal plant. Antimicrobial and antioxidant potential evaluation and identification of chemical constituents via GC-MS of C. rothii roots fractions. To the best of our knowledge, this is the first systematic investigation of the roots exploiting GC-MS. Extraction and fractionation of C. rothii roots furnished various fractions using solvents of varying polarity, i.e., n-hexane, chloroform, ethyl acetate, acetone and methanol. In vitro antimicrobial and antioxidant screening was performed using disk diffusion and DPPH methods, respectively. MIC of active fractions was also determined using disk diffusion method. GC-MS was used to identify constituents which may be responsible for these activities. Among various fractions from C. rothii roots, fraction KA-C showed strong antibacterial activity against 17 microorganisms tested, with MIC ranging from 250-31.25 μg/mL. Fractions KA-A, KM and KM-A exhibited significant antioxidant potential with EC 50 46.875 μg/mL, while fractions KEA-PE, KM-PE and KM-M were good with EC 50 93.750 μg/mL. Forty-five phytochemicals were identified in GC-MS studies including eight hydrocarbons, six free fatty acids, 11 fatty acids esters, two phenylpropanoids, four aromatics, four terpenoid quinones/hydroquinones, three triterpenes, four phytosterols, two hexose metabolites and a DNA base. Of these, 32 constituents have been reported for the first time from C. rothii, 24 from genus Cordia and 15 from Boraginaceae. Strong antibacterial and antioxidant potential of C. rothii roots may be due to the contribution of phytoconstituents identified through GC-MS studies.

Online analysis of chlorine stable isotopes in chlorinated ethylenes: an inter-laboratory study

NASA Astrophysics Data System (ADS)

Bernstein, Anat; Shouakar-Stash, Orfan; Hunkeler, Daniel; Sakaguchi-Söder, Kaori; Laskov, Christine; Aravena, Ramon; Elsner, Martin

2010-05-01

In the last decade, compound-specific stable isotopes analysis of groundwater pollutants became an important tool to identify different sources of the same pollutant and for tracking natural attenuating processes in the sub-surface. It has been shown that trends in the isotopic composition of the target compounds can shed light on in-situ processes that are otherwise difficult to track. Analytical methods of carbon, nitrogen and hydrogen were established and are by now frequently used for a variety of organic pollutants. Yet, the motivation of introducing analytical methods for new isotopes is emerging. This motivation is further enhanced, as advantages of using two or more stable isotopes for gaining better insight on degradation pathways are well accepted. One important element which demands the development of appropriate analytical methods is chlorine, which is found in various groups of organic pollutants, among them the chlorinated ethylenes. Chlorinated ethylenes are considered as high priority environmental pollutants, and the development of suitable chlorine isotope methods for this group of pollutants is highly desired. Ideally, stable isotope techniques should have the capability to determine the isotopic composition of and individual target compound in a non-pure mixture, without the requirement of a laborious off-line treatment. Indeed, in the last years two different concepts for on-line chlorine isotope analysis methods were introduced, by using either a standard quadrapole GC/MS (Sakaguchi-Söder et al., 2007) or by using a GC/IRMS (Shouakar-Stash et al., 2006). We present a comparison of the performances of two concepts, carried out in five different laboratories: Waterloo (GC/IRMS), Neuchâtel (GC/MS), Darmstadt (GC/MS), Tübingen (GC/MS) and Munich (GC/IRMS). This comparison was performed on pure trichloroethylene and dichloroethylene products of different manufactures, as well as trichloroethylene and dichloroethylene samples that were exposed to biodegradation. This study sets standards for further application of these techniques to distinguish sources and track degradation processes in the sub-surface.

Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

PubMed

Zhang, Cheng; Cagliero, Cecilia; Pierson, Stephen A; Anderson, Jared L

2017-01-20

A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Method for determination of methyl tert-butyl ether and its degradation products in water

USGS Publications Warehouse

Church, C.D.; Isabelle, L.M.; Pankow, J.F.; Rose, D.L.; Tratnyek, P.G.

1997-01-01

An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.

Gas chromatographic/mass spectrometric analysis of the essential oil of Houttuynia cordata Thunb by using on-column methylation with tetramethylammonium acetate.

PubMed

Ch, Muhammad Ishtiaq; Wen, Yang F; Cheng, YiYu

2007-01-01

This paper describes a simple and novel on-column derivatization procedure used with gas chromatography/mass spectrometry (GC/MS) for the analysis of essential oil of Houttuynia cordata Thunb (HCT), a traditional Chinese medicine. In the procedure, the essential oil was obtained by hydrodistillation, and the fatty acid components were derivatized with tetramethylammonium acetate (TMAA) at 250 degrees C and identified by GC/MS. Methylation improved the determination of both the fatty acids and the other components in the essential oil of HCT. To obtain optimum methylation conditions, several important factors were investigated with pentadecane as the internal standard and a GC inlet temperature of 250 degres C. Tetramethylammonium hydroxide (TMAH) and TMAA were compared as the derivatization agent, and a 2:1 ratio of TMAA to capric acid was evaluated. Fatty acid methyl esters produced good chromatographic peak shapes and did not interfere with the determination of dodecanal and caryophyllene. TMAA is a neutral methylation reagent, and it yielded no side reactions during derivatization. It was found that the fatty acid content of the essential oil was about 81%; among the methylated fatty acids found were capric acid, methyl (43.66%), methyl laurate (16.15%), methyl hexadecanoate (9.27%), undecanoic acid, methyl (5.62%), methyl oleate (1.98%), and methyl linoleate (1.40%). Other major constituents were (-)-beta-pinene (1.02%), beta-myrcene (1.62%), 1-terpinen-4-ol (1.59%), decanal (1.49%), and 2-undecanone (1.47%). The results obtained demonstrated good efficiency for the procedure. Pure chromatograms allowed quantitation, which was obtained by total volume integration. The on-column derivatization procedure was simple to perform, and it improved the sensitivity, the peak resolution, and the selectivity of the GC/MS determination.

Determination of low ppm levels of dimethyl sulfate in an aqueous soluble API intermediate using liquid-liquid extraction and GC-MS.

PubMed

Zheng, Jie; Pritts, Wayne A; Zhang, Shuhong; Wittenberger, Steve

2009-12-05

Dimethyl sulfate (DMS) is an alkylating reagent commonly used in organic syntheses and pharmaceutical manufacturing processes. Due to its potential carcinogenicity, the level of DMS in the API process needs to be carefully monitored. However, in-process testing for DMS is challenging because of its reactivity and polarity as well as complex matrix effects. In this short communication, we report a GC-MS method for determination of DMS in an API intermediate that is a methyl sulfate salt. To overcome the complex matrix interference, DMS and an internal standard, d6-DMS, were extracted from the matrix with methyl tert-butyl ether. GC separation was conducted on a DB-624 column (30 m long, 0.32 mm ID, 1.8 microm film thickness). MS detection was performed on a single-quad Agilent MSD equipped with an electron impact source while the MSD signal was acquired in selected ion monitoring mode. This GC/MS method showed a linear response for DMS equivalent from 1.0 to 60 ppm. The practical quantitation limit for DMS was 1.0 ppm and the practical detection limit was 0.3 ppm. The relative standard derivation for analyte response was found as 0.1% for six injections of a working standard equivalent to 18.6 ppm of DMS. The spike recovery was ranged from 102.1 to 108.5% for a sample of API intermediate spiked with 8.0 ppm of DMS. In summary, the GC/MS method showed adequate specificity, linearity, sensitivity, repeatability and accuracy for determination of DMS in the API intermediate. This method has been successfully applied to study the efficiency of removing DMS from the process.

Second-order standard addition for deconvolution and quantification of fatty acids of fish oil using GC-MS.

PubMed

Vosough, Maryam; Salemi, Amir

2007-08-15

In the present work two second-order calibration methods, generalized rank annihilation method (GRAM) and multivariate curve resolution-alternating least square (MCR-ALS) have been applied on standard addition data matrices obtained by gas chromatography-mass spectrometry (GC-MS) to characterize and quantify four unsaturated fatty acids cis-9-hexadecenoic acid (C16:1omega7c), cis-9-octadecenoic acid (C18:1omega9c), cis-11-eicosenoic acid (C20:1omega9) and cis-13-docosenoic acid (C22:1omega9) in fish oil considering matrix interferences. With these methods, the area does not need to be directly measured and predictions are more accurate. Because of non-trilinear conditions of GC-MS data matrices, at first MCR-ALS and GRAM have been used on uncorrected data matrices. In comparison to MCR-ALS, biased and imprecise concentrations (%R.S.D.=27.3) were obtained using GRAM without correcting the retention time-shift. As trilinearity is the essential requirement for implementing GRAM, the data need to be corrected. Multivariate rank alignment objectively corrects the run-to-run retention time variations between sample GC-MS data matrix and a standard addition GC-MS data matrix. Then, two second-order algorithms have been compared with each other. The above algorithms provided similar mean predictions, pure concentrations and spectral profiles. The results validated using standard mass spectra of target compounds. In addition, some of the quantification results were compared with the concentration values obtained using the selected mass chromatograms. As in the case of strong peak-overlap and the matrix effect, the classical univariate method of determination of the area of the peaks of the analytes will fail, the "second-order advantage" has solved this problem successfully.

Validation of a gas chromatography-triple quadrupole mass spectrometry method for confirmatory analysis of dioxins and dioxin-like polychlorobiphenyls in feed following new EU Regulation 709/2014.

PubMed

L'Homme, B; Scholl, G; Eppe, G; Focant, J-F

2015-01-09

The European Regulations laying down methods of sampling and analysis for the EU official control of levels of polychlorodibenzo-p-dioxins (PCDDs), polychloro-dibenzofurans (PCDFs), dioxin-like (DL) and non dioxin-like (NDL) PCBs in food and feed have been recently amended by EU Regulation Nos. 589/2014 and 709/2014. A major update is the recognition of gas chromatography (GC) triple quadrupole mass spectrometry (GC-QQQMS/MS) as a confirmatory tool for checking compliance with maximum levels (ML). These revisions have been initiated since this technology now exhibits similar performances to GC (magnetic sector) high resolution mass spectrometry (GC-HRMS). In this paper, we show a fully validated method for PCDD/Fs and DL-PCBs analysis in feed material of plant origin (vegetable oil) using GC-QQQMS/MS following the dedicated EU Regulation 709/2014. We show that individual analytical criteria (selectivity, linearity, quant/qual MRM transitions, accuracy around ML of 1.50ng WHO2005TEQ/kg, within-lab reproducibility, robustness, and background subtraction) meet the strict requirements set by the EU Regulation. We also propose a clear interpretation of instrumental limit of quantitation (iLOQ) as a 'performance-LOQ', defined in a specific way for GC-QQQMS/MS, and method limit of quantitation (mLOQ) as 'real-LOQ' that is used to report bound results. Eventually, the evaluation of measurement uncertainty, following a top-down approach and data produced with our method, demonstrates similar results than with GC-HRMS, thus offering a reliable alternative to the standard method for vegetable oil. Copyright © 2014 Elsevier B.V. All rights reserved.

Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel

Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that varymore » as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.« less

Annual Quality Assurance Conference Presentations by Michelle Misselwitz

EPA Pesticide Factsheets

25th Annual Quality Assurance Conference. Presentations: Tools I Can’t Live Without: Speed Up Method Development and Translation, Essentials for GC and GC/MS Users; Tricks of the Trade, Keeping Your GC System Up Longer for the Analysis of Pesticides

Application of Chemometric Methods to Devolve Co-Eluting Peaks in GC-MS of Fuels to Improve Compound Identification: Final Report

DTIC Science & Technology

2018-02-12

Unclassified Unlimited 49 Jeffrey Cramer (202) 404-3419 Fuel stability and performance problems are often due to the presence of trace levels of contaminants or...other minor changes in composition. Detailed compositional analyses of suspect fuels are often critical to the determination of the cause(s) of the...problem(s) at hand. Sensitive methods to compare fuel compositions via GC-MS methods are available, but the detailed compositional analyses of

Analysis of poly-beta-hydroxybutyrate in environmental samples by GC-MS/MS.

PubMed

Elhottová, D; Tríska, J; Petersen, S O; Santrůcková, H

2000-05-01

Application of gas chromatography-mass spectrometry (GC-MS) can significantly improve trace analyses of compounds in complex matrices from natural environments compared to gas chromatography only. A GC-MS/MS technique for determination of poly-beta-hydroxybutyrate (PHB), a bacterial storage compound, has been developed and used for analysis of two soils stored for up to 319 d, fresh samples of sewage sludge, as well as a pure culture of Bacillus megaterium. Specific derivatization of beta-hydroxybutyrate (3-OH C4:0) PHB monomer units by N-tert-butyl-dimethylsilyl-N-methyltrifluoracetamide (MTBSTFA) improved chromatographic and mass spectrometric properties of the analyte. The diagnostic fragmentation scheme of the derivates tert-butyldimethylsilyl ester and ether of beta-hydroxybutyric acid (MTBSTFA-HB) essential for the PHB identification was shown. The ion trap MS was used, therefore the scan gave the best sensitivity and with MS/MS the noise decreased, so the S/N was better and also with second fragmentation the amount of ions increased compared to SIM. The detection limit for MTBSTFA-HB by GC-MS/MS was about 10(-13) g microL(-1) of injected volume, while by GC (FID) and GC-MS (scan) it was around 10(-10) g microL(-1) of injected volume. Sensitivity of GC-MS/MS measurements of PHB in arable soil and activated sludge samples was down to 10 pg of PHB g(-1) dry matter. Comparison of MTBSTFA-HB detection in natural soil sample by GC (FID), GC-MS (scan) and by GC-MS/MS demonstrated potentials and limitations of the individual measurement techniques.

Liquid chromatography and supercritical fluid chromatography as alternative techniques to gas chromatography for the rapid screening of anabolic agents in urine.

PubMed

Desfontaine, Vincent; Nováková, Lucie; Ponzetto, Federico; Nicoli, Raul; Saugy, Martial; Veuthey, Jean-Luc; Guillarme, Davy

2016-06-17

This work describes the development of two methods involving supported liquid extraction (SLE) sample treatment followed by ultra-high performance liquid chromatography or ultra-high performance supercritical fluid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS and UHPSFC-MS/MS) for the screening of 43 anabolic agents in human urine. After evaluating different stationary phases, a polar-embedded C18 and a diol columns were selected for UHPLC-MS/MS and UHPSFC-MS/MS, respectively. Sample preparation, mobile phases and MS conditions were also finely tuned to achieve highest selectivity, chromatographic resolution and sensitivity. Then, the performance of these two methods was compared to the reference routine procedure for steroid analyses in anti-doping laboratories, which combines liquid-liquid extraction (LLE) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). For this purpose, urine samples spiked with the compounds of interest at five different concentrations were analyzed using the three analytical platforms. The retention and selectivity of the three techniques were very different, ensuring a good complementarity. However, the two new methods displayed numerous advantages. The overall procedure was much faster thanks to high throughput SLE sample treatment using 48-well plates and faster chromatographic analysis. Moreover, the highest sensitivity was attained using UHPLC-MS/MS with 98% of the doping agents detected at the lowest concentration level (0.1ng/mL), against 76% for UHPSFC-MS/MS and only 14% for GC-MS/MS. Finally, the weakest matrix effects were obtained with UHPSFC-MS/MS with 76% of the analytes displaying relative matrix effect between -20 and 20%, while the GC-MS/MS reference method displayed very strong matrix effects (over 100%) for all of the anabolic agents. Copyright © 2016 Elsevier B.V. All rights reserved.

Solid-phase microextraction with temperature-programmed desorption for the analysis of iodination disinfection byproducts.

PubMed

Frazey, P A; Barkley, R M; Sievers, R E

1998-02-01

An analytical approach for the determination of chlorination and iodination disinfection byproducts based on solid-phase microextraction (SPME) was developed. Solid-phase microextraction presents a simple, rapid, sensitive, and solvent-free approach to sample preparation in which analytes in either air or water matrixes are extracted into the polymeric coating of an optical fiber. Analytes are subsequently thermally desorbed in the injection port of a gas chromatograph for separation, detection, and quantitation. Thermal degradation of iodoform was observed during desorption from a polyacrylate fiber in initial GC/MS and GC/ECD experiments. Experiments were designed to determine SPME conditions that would allow quantification without significant degradation of analytes. Isothermal and temperature-programmed thermal desorptions were evaluated for efficacy in transferring analytes with wide-ranging volatilities and thermal stabilities into chromatographic analysis columns. A temperature-programmed desorption (TPD) (120-200 degrees C at 5 degrees C/min with an on-column injection port or 150-200 degrees C at 25 degrees C/min with a split/splitless injection port) was able to efficiently remove analytes with wide-ranging volatilities without causing thermal degradation. The SPME-TPD method was linear over 2-3 orders of magnitude with an electron capture detector and detection limits were in the submicrogram per liter range. Precision and detection limits for selected trihalomethanes were comparable to those of EPA method 551. Extraction efficiencies were not affected by the presence of 10 mg/L soap, 15 mg/L sodium iodide, and 6000 mg/L sodium thiosulfate. The SPME-TPD technique was applied to the determination of iodination disinfection byproducts from individual precursor compounds using GC/MS and to the quantitation of iodoform at trace levels in a water recycle system using GC/ECD.

Guilty by dissociation-development of gas chromatography-mass spectrometry (GC-MS) and other rapid screening methods for the analysis of 13 diphenidine-derived new psychoactive substances (NPSs).

PubMed

Geyer, Pierre M; Hulme, Matthew C; Irving, Joseph P B; Thompson, Paul D; Ashton, Ryan N; Lee, Robert J; Johnson, Lucy; Marron, Jack; Banks, Craig E; Sutcliffe, Oliver B

2016-11-01

The prevalence of new psychoactive substances (NPSs) in forensic casework has increased prominently in recent years. This has given rise to significant legal and analytical challenges in the identification of these substances. The requirement for validated, robust and rapid testing methodologies for these compounds is obvious. This study details the analysis of 13 synthesised diphenidine derivatives encountered in casework using presumptive testing, thin layer chromatography and gas chromatography-mass spectrometry (GC-MS). Specifically, the validated GC-MS method provides, for the first time, both a general screening method and quantification of the active components for seized solid samples, both in their pure form and in the presence of common adulterants. Graphical Abstract Chemical synthesis and forensic analysis of 13 diphenidine-derived new psychoactive substance(s).

Comprehensive Urine Drug Screen by Gas Chromatography/Mass Spectrometry (GC/MS).

PubMed

Ramoo, Bheemraj; Funke, Melissa; Frazee, Clint; Garg, Uttam

2016-01-01

Drug screening is an essential component of clinical toxicology laboratory service. Some laboratories use only automated chemistry analyzers for limited screening of drugs of abuse and few other drugs. Other laboratories use a combination of various techniques such as immunoassays, colorimetric tests, and mass spectrometry to provide more detailed comprehensive drug screening. Mass spectrometry, gas or liquid, can screen for hundreds of drugs and is often considered the gold standard for comprehensive drug screening. We describe an efficient and rapid gas chromatography/mass spectrometry (GC/MS) method for comprehensive drug screening in urine which utilizes a liquid-liquid extraction, sample concentration, and analysis by GC/MS.

40 CFR Appendix A to Subpart C of... - Alternative Testing Methods Approved for Analyses Under the Safe Drinking Water Act

Code of Federal Regulations, 2013 CFR

2013-07-01

... Chromatography/Mass Spectrometry (GC/MS) 525.3 24 Carbofuran High-performance liquid chromatography (HPLC) with... (HPLC) with Post-Column Derivatization and Fluorescence Detection 6651 B 6651 B 6651 B-00. Heptachlor... Spectrometry (GC/MS) 525.3 24 Oxamyl High-performance liquid chromatography (HPLC) with post-column...

GC-MS analysis of bio-active compounds in methanolic extract of Lactuca runcinata DC

PubMed Central

Kanthal, Lakshmi Kanta; Dey, Akalanka; Satyavathi, K.; Bhojaraju, P.

2014-01-01

Background: The presence of phytochemical constitutes has been reported from species of the Compositae (Asteraceae). Hitherto no reports exist on the phytochemical components and biological activity of Lactuca runcinata DC. Objective: The present study was designed to determine the bioactive compounds in the whole plant methanol extract of Lactuca runcinata. Materials and Methods: Phytochemical screening of the entire herb of Lactuca runcinata DC revealed the presence of some bio-active components. Gas chromatography-mass spectrometry (GC-MS) analysis of the whole plant methanol extract of Lactuca runcinata was performed on a GC-MS equipment (Thermo Scientific Co.) Thermo GC-TRACE ultra ver.: 5.0, Thermo MS DSQ II. Results: The phytochemical tests showed the presence of alkaloids, cardiac glycosides, flavonoids, phenols, phlobatannin, reducing sugars, saponins, steroids, tannins, terpenoids, volatile oils, carbohydrates, and protein/amino acids in methanolic extract of L. runcinata. The GC-MS analysis has shown the presence of different phytochemical compounds in the methanolic extract of Lactuca runcinata. A total of 21 compounds were identified representing 84.49% of total methanolic extract composition. Conclusion: From the results, it is evident that Lactuca runcinata contains various phytocomponents and is recommended as a plant of phytopharmaceutical importance. PMID:24497744

Extraction of pure components from overlapped signals in gas chromatography-mass spectrometry (GC-MS)

PubMed Central

Likić, Vladimir A

2009-01-01

Gas chromatography-mass spectrometry (GC-MS) is a widely used analytical technique for the identification and quantification of trace chemicals in complex mixtures. When complex samples are analyzed by GC-MS it is common to observe co-elution of two or more components, resulting in an overlap of signal peaks observed in the total ion chromatogram. In such situations manual signal analysis is often the most reliable means for the extraction of pure component signals; however, a systematic manual analysis over a number of samples is both tedious and prone to error. In the past 30 years a number of computational approaches were proposed to assist in the process of the extraction of pure signals from co-eluting GC-MS components. This includes empirical methods, comparison with library spectra, eigenvalue analysis, regression and others. However, to date no approach has been recognized as best, nor accepted as standard. This situation hampers general GC-MS capabilities, and in particular has implications for the development of robust, high-throughput GC-MS analytical protocols required in metabolic profiling and biomarker discovery. Here we first discuss the nature of GC-MS data, and then review some of the approaches proposed for the extraction of pure signals from co-eluting components. We summarize and classify different approaches to this problem, and examine why so many approaches proposed in the past have failed to live up to their full promise. Finally, we give some thoughts on the future developments in this field, and suggest that the progress in general computing capabilities attained in the past two decades has opened new horizons for tackling this important problem. PMID:19818154

Solid-phase extraction and on-disc derivatization of the major benzodiazepines in urine using enzyme hydrolysis and Toxi-Lab VC MP3 column.

PubMed

King, J W; King, L J

1996-01-01

Because of the increase in use of the newer benzodiazepines, we explored the opportunity to develop a gas chromatographic-mass spectrometric (GC-MS) method that encompasses most of the widely prescribed benzodiazepines in use today. The benzodiazepines included in our study are nordiazepam, oxazepam, temazepam, lorazepam, alpha-hydroxyalprazolam, alpha-hydroxytriazolam, desalkylflurazepam, and 2-hydroxyethylflurazepam. Using 1.0 mL of urine as the matrix, we added the enzyme Glusulase and incubated the specimens for 2 h to obtain the free drugs. The hydrolyzed samples were then loaded onto a Toxi-Lab Spec VC MP3 column containing a 15-mg disc. On-disc derivatization was accomplished by adding N-methyl-N-(t-butyldimethylsilyl) trifluroacetamide (MTBSTFA) with 1% TBDMSCI to the disc. The derivatives were then placed in a GC vial and analyzed by GC-MS in the selected ion monitoring mode. These results were then compared to confirmed positives by the traditional acid hydrolysis GC-MS method.

Method translation and full metadata transfer from thermal to differential flow modulated comprehensive two dimensional gas chromatography: Profiling of suspected fragrance allergens.

PubMed

Cordero, Chiara; Rubiolo, Patrizia; Reichenbach, Stephen E; Carretta, Andrea; Cobelli, Luigi; Giardina, Matthew; Bicchi, Carlo

2017-01-13

The possibility to transfer methods from thermal to differential-flow modulated comprehensive two-dimensional gas chromatographic (GC×GC) platforms is of high interest to improve GC×GC flexibility and increase the compatibility of results from different platforms. The principles of method translation are here applied to an original method, developed for a loop-type thermal modulated GC×GC-MS/FID system, suitable for quali-quantitative screening of suspected fragrance allergens. The analysis conditions were translated to a reverse-injection differential flow modulated platform (GC×2GC-MS/FID) with a dual-parallel secondary column and dual detection. The experimental results, for a model mixture of suspected volatile allergens and for raw fragrance mixtures of different composition, confirmed the feasibility of translating methods by preserving 1 D elution order, as well as the relative alignment of resulting 2D peak patterns. A correct translation produced several benefits including an effective transfer of metadata (compound names, MS fragmentation pattern, response factors) by automatic template transformation and matching from the original/reference method to its translated counterpart. The correct translation provided: (a) 2D pattern repeatability, (b) MS fragmentation pattern reliability for identity confirmation, and (c) comparable response factors and quantitation accuracy within a concentration range of three orders of magnitude. The adoption of a narrow bore (i.e. 0.1mm d c ) first-dimension column to operate under close-to-optimal conditions with the differential-flow modulation GC×GC platform was also advantageous in halving the total analysis under the translated conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow-switching device for comprehensive two-dimensional gas chromatography.

PubMed

Bueno, Pedro A; Seeley, John V

2004-02-20

A simple flow-switching device has been developed as a differential flow modulator for comprehensive two-dimensional gas chromatography (GC x GC). The device is assembled from tubing, four tee unions, and a solenoid valve. The solenoid valve is located outside the oven of the gas chromatograph and is not in the sample path. The modulation technique has no inherent temperature restrictions and passes 100% of the primary column effluent to the secondary column(s). Secondary peaks are produced with widths at half maximum less than 100 ms when operating in GC x 2GC mode with a 2.0 s modulation period. The efficacy of this approach is demonstrated through the analysis of a standard mixture of volatile organic compounds (VOCs) and diesel fuel.

[Clinical application of mass spectrometry in the pediatric field: current topics].

PubMed

Yamaguchi, Seiji

2013-09-01

Mass spectrometry, including tandem mass spectrometry (MS/MS) and gas chromatography-mass spectrometry (GC/MS), is becoming prominent in the diagnosis of metabolic disorders in the pediatric field. It enables biochemical diagnosis of metabolic disorders from the metabolic profiles obtained by MS/MS and/or GC/MS. In neonatal mass screening for inherited metabolic disease (IMD) using MS/MS, amino acids and acylcarnitines on dried blood spots are analyzed. The target diseases include amino acidemia, urea cycle disorder, organic acidemia, and fatty acid oxidation disorder. In the MS/MS screening, organic acid analysis using GC/MS is required for differential and/or definite diagnosis of the IMDs. GC/MS data processing, however, is difficult, and metabolic diagnosis often requires the necessary skills and expertize. We developed an automated system of GC/MS data processing and autodiagnosis, and the biochemical diagnosis using GC/MS became markedly easier and user-friendly. Mass spectrometric techniques will expand from research laboratories to clinical laboratories in the near future.

Determination of N,N-dimethyltryptamine in Mimosa tenuiflora inner barks by matrix solid-phase dispersion procedure and GC-MS.

PubMed

Gaujac, Alain; Aquino, Adriano; Navickiene, Sandro; de Andrade, Jailson Bittencourt

2012-01-15

N,N-dimethyltryptamine (DMT) is a potent hallucinogen found in beverages consumed in religion rituals and neo-shamanic practices over the world. Two of these religions, Santo Daime and União do Vegetal (UDV), are represented in countries including Australia, the United States and several European nations. In some of this countries there have been legal disputes concerning the legalization of ayahuasca consumption during religious rituals, a beverage rich in DMT. In Brazil, even children and pregnant women are legally authorized to consume ayahuasca in a religious context. A simple and low-cost method based on matrix solid-phase dispersion (MSPD) and gas chromatography with mass spectrometric detection (GC-MS) has been optimized for the determination of N,N-dimethyltryptamine in Mimosa tenuiflora inner bark. The experimental variables that affect the MSPD method, such as the amounts of solid-phase and herbal sample, solvent nature, eluate volume and NaOH concentration were optimized using an experimental design. The method showed good linearity (r = 0.9962) and repeatability (RSD < 7.4%) for DMT compound, with detection limit of 0.12 mg/g. The proposed method was used to analyze 24 samples obtained locally. The results showed that concentrations of the target compound in M. tenuiflora barks, ranged from 1.26 to 9.35 mg/g for these samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Micro-pulverized extraction pretreatment for highly sensitive analysis of 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol in hair by liquid chromatography/tandem mass spectrometry.

PubMed

Kuwayama, Kenji; Miyaguchi, Hajime; Yamamuro, Tadashi; Tsujikawa, Kenji; Kanamori, Tatsuyuki; Iwata, Yuko T; Inoue, Hiroyuki

2015-11-30

A primary metabolite of Δ(9) -tetrahydrocannabinol, 11-nor-9-carboxytetrahydrocannabinol (THC-COOH), serves as an effective indicator for cannabis intake. According to the recommendations of the Society of Hair Testing, at least 0.2 pg/mg of THC-COOH (cut-off level) must be present in a hair sample to constitute a positive result in a drug test. Typically, hair is digested with an alkaline solution and is subjected to gas chromatography/tandem mass spectrometry (GC/MS/MS) with negative ion chemical ionization (NICI). It is difficult to quantify THC-COOH at the cut-off level using liquid chromatography/tandem mass spectrometry (LC/MS/MS) without acquisition of second-generation product ions in triple quadrupole-ion trap mass spectrometers, because large amounts of matrix components in the low-mass range produced by digestion interfere with the THC-COOH peak. Using the typical pretreatment method (alkaline dissolution) and micro-pulverized extraction (MPE) with a stainless bullet, we compared the quantification of THC-COOH using GC/MS/MS and LC/MS/MS. MPE reduced the amount of matrix components in the low-mass range and enabled the quantification of THC-COOH at 0.2 pg/mg using a conventional triple quadrupole liquid chromatograph coupled to a mass spectrometer. On the other hand, the MPE pretreatment was unsuitable for GC/MS/MS, probably due to matrix components in the high-mass range. The proper combination of pretreatments and instrumental analyses was shown to be important for detecting trace amounts of THC-COOH in hair. In MPE, samples can be prepared rapidly, and LC/MS/MS is readily available, unlike GC/MS/MS with NICI. The combination of MPE and LC/MS/MS might therefore be used in the initial screening for THC-COOH in hair prior to confirmatory analysis using GC/MS/MS with NICI. Copyright © 2015 John Wiley & Sons, Ltd.

Triple quadrupole tandem mass spectrometry: A real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls.

PubMed

García-Bermejo, Ángel; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; González, María José; Gómara, Belén

2015-08-19

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1-10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3-10%, for PCDD/Fs, and 0.2-15%, for DL-PCBs) and low instrumental limits of detection, 0.07-0.75 pg μL(-1) (for dioxins) and 0.05-0.63 pg μL(-1) (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g(-1). The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g(-1), in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of carbendazim, benomyl, thiophanate methyl and 2,4-dichlorophenoxyacetic acid in fruits and vegetables after supercritical fluid extraction.

PubMed

Anastassiades, M; Schwack, W

1998-10-30

Simple methods for the analysis of carbendazim, benomyl and thiophanate methyl in fruits and vegetables and of 2,4-D in citrus fruits are presented. Sample preparation involves supercritical fluid extraction with carbon dioxide and further analysis is performed without any additional clean-up by GC-MS after derivatisation or directly by HPLC-diode array detection. The SFE methods presented are clearly faster and more cost effective than traditional solvent based approaches. The recoveries, detection limits and repeatabilities achieved, meet the needs of tolerance level monitoring of these compounds in fruits and vegetables.

Application of ethyl esters and d3-methyl esters as internal standards for the gas chromatographic quantification of transesterified fatty acid methyl esters in food.

PubMed

Thurnhofer, Saskia; Vetter, Walter

2006-05-03

Ethyl esters (FAEE) and trideuterium-labeled methyl esters (d3-FAME) of fatty acids were prepared and investigated regarding their suitability as internal standards (IS) for the determination of fatty acids as methyl esters (FAME). On CP-Sil 88, ethyl esters of odd-numbered fatty acids eluted approximately 0.5 min after the respective FAME, and only coelutions with minor FAME were observed. Depending on the problem, one or even many FAEE can be added as IS for the quantification of FAME by both GC-FID and GC-MS. By contrast, d3-FAME coeluted with FAME on the polar GC column, and the use of the former as IS requires application of GC-MS. In the SIM mode, m/z 77 and 90 are suggested for d3-methyl esters of saturated fatty acids, whereas m/z 88 and 101 are recommended for ethyl esters of saturated fatty acids. These m/z values give either no or very low response for FAME and can thus be used for the analysis of FAME in food by GC-MS in the SIM mode. Fatty acids in sunflower oil and mozzarella cheese were quantified using five saturated FAEE as IS. Gravimetric studies showed that the transesterification procedure could be carried out without of loss of fatty acids. GC-EI/MS full scan analysis was suitable for the quantitative determination of all unsaturated fatty acids in both food samples, whereas GC-EI/MS in the SIM mode was particularly valuable for quantifying minor fatty acids. The novel GC-EI/MS/SIM method using fatty acid ethyl esters as internal standards can be used to quantify individual fatty acids only, that is, without determination of all fatty acids (the common 100% method), although this is present. This was demonstrated by the exclusive quantification of selected fatty acids including methyl-branched fatty acids, erucic acid (18:1n-9trans), and polyunsaturated fatty acids in cod liver oil and goat's milk fat.

Biodiesel production from microalgal isolates of southern Pakistan and quantification of FAMEs by GC-MS/MS analysis

PubMed Central

2012-01-01

Background Microalgae have attracted major interest as a sustainable source for biodiesel production on commercial scale. This paper describes the screening of six microalgal species, Scenedesmus quadricauda, Scenedesmus acuminatus, Nannochloropsis sp., Anabaena sp., Chlorella sp. and Oscillatoria sp., isolated from fresh and marine water resources of southern Pakistan for biodiesel production and the GC-MS/MS analysis of their fatty acid methyl esters (FAMEs). Results Growth rate, biomass productivity and oil content of each algal species have been investigated under autotrophic condition. Biodiesel was produced from algal oil by acid catalyzed transesterification reaction and resulting fatty acid methyl esters (FAMEs) content was analyzed by GC/MS. Fatty acid profiling of the biodiesel, obtained from various microalgal oils showed high content of C-16:0, C-18:0, cis-Δ9C-18:1, cis-Δ11C-18:1 (except Scenedesmus quadricauda) and 10-hydroxyoctadecanoic (except Scenedesmus acuminatus). Absolute amount of C-14:0, C-16:0 and C-18:0 by a validated GC-MS/MS method were found to be 1.5-1.7, 15.0-42.5 and 4.2-18.4 mg/g, respectively, in biodiesel obtained from various microalgal oils. Biodiesel was also characterized in terms of cetane number, kinematic viscosity, density and higher heating value and compared with the standard values. Conclusion Six microalgae of local origin were screened for biodiesel production. A method for absolute quantification of three important saturated fatty acid methyl esters (C-14, C-16 and C-18) by gas chromatography-tandem mass spectrometry (GC-MS/MS), using multiple reactions monitoring (MRM) mode, was employed for the identification and quantification of biodiesels obtained from various microalgal oils. The results suggested that locally found microalgae can be sustainably harvested for the production of biodiesel. This offers the tremendous economic opportunity for an energy-deficient nation. PMID:23216896

A gas chromatography-mass spectrometry method for the determination of delta-aminolevulinic acid in plant leaves.

PubMed

Hijaz, Faraj; Killiny, Nabil

2016-05-20

Delta-aminolevulinic (δ-ALA) acid is an important intermediate for tetrapyrroles biosynthesis and it has recently received great attention in plant physiology and human toxicology. However, the colorimetric method which is the most common method for determination of δ-ALA is time consuming and is not specific. In this study, a method for determination of δ-ALA in plant tissues was developed based on the trimethylsilyl (TMS) derivative of the pyrrole formed from the reaction of δ-ALA with ethyl acetoacetate via Knorr condensation. The δ-ALA in the HCl extract was reacted with ethyl acetoacetate to form a pyrrole. Then, the pyrrole compound was extracted using ethyl acetate and the solvent was evaporated to dryness. The dried sample was derivatized to its TMS ester and analyzed using GC-MS. The concentration of δ-ALA in citrus leaves incubated with levulinic acid was also determined by the conventional colorimetric method. The linear range was 10-200ppm in the full scan mode and 0.1-20ppm in the selected ion monitoring (SIM). The limit of detection was 6ppm in the full scan and 0.05ppm in SIM mode, representing a four-fold increase in sensitivity compared to the colorimetric method. The GC-MS method developed in this study is simple, accurate, sensitive, and could also be used to measure δ-ALA in other biological samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Drop-to-drop solvent microextraction coupled with gas chromatography/mass spectrometry for rapid determination of trimeprazine in urine and blood of rats: application to pharmacokinetic studies.

PubMed

Agrawal, Kavita; Wu, Hui-Fen

2007-01-01

A simple and rapid method based on drop-to-drop solvent microextraction (DDSME) coupled with gas chromatography/mass spectrometry (GC/MS) has been successfully applied for the pharmacokinetic studies of trimeprazine in 8 microL of urine and blood samples of rats. Several factors that influenced the extraction efficiency of DDSME, such as selection of organic solvent, extraction time, exposure volume of organic phase, addition of salt and pH, were optimized. Linearity was obtained over the concentration ranges of 0.2-10, 0.25-7.0 and 0.5-6.0 microg/mL with correlation coefficients of 0.998, 0.996 and 0.993 in deionized water, urine and blood samples of rats, respectively. The limits of detection (LODs) of trimeprazine were 0.05, 0.06 and 0.1 microg/mL in deionized water, urine and blood samples. The concentrations of trimeprazine obtained in urine and blood samples of rats were 0.21-1.25 and 2.72-0.22 microg/mL, respectively, after a single intravenous administration of this drug. The enrichment factors and LOD values obtained by DDSME coupled to GC/MS were compared with those of hollow fiber liquid-phase microextraction (HF-LPME) combined with GC/MS. We believe that this novel approach can be very useful in clinical application since only one microdrop of biological samples was required to perform the pharmacokinetic studies from rats, so the sample pretreatments for animal experiments can be very easy too. Copyright (c) 2007 John Wiley & Sons, Ltd.

Sample analysis at Mars

NASA Astrophysics Data System (ADS)

Coll, P.; Cabane, M.; Mahaffy, P. R.; Brinckerhoff, W. B.; Sam Team

The next landed missions to Mars, such as the planned Mars Science Laboratory and ExoMars, will require sample analysis capabilities refined well beyond what has been flown to date. A key science objective driving this requirement is the determination of the carbon inventory of Mars, and particularly the detection of organic compounds. The Sample Analysis at Mars (SAM) suite consists of a group of tightly-integrated experiments that would analyze samples delivered directly from a coring drill or by a facility sample processing and delivery (SPAD) mechanism. SAM consists of an advanced GC/MS system and a laser desorption mass spectrometer (LDMS). The combined capabilities of these techniques can address Mars science objectives with much improved sensitivity, resolution, and analytical breadth over what has been previously possible in situ. The GC/MS system analyzes the bulk composition (both molecular and isotopic) of solid-phase and atmospheric samples. Solid samples are introduced with a highly flexible chemical derivatization/pyrolysis subsystem (Pyr/GC/MS) that is significantly more capable than the mass spectrometers on Viking. The LDMS analyzes local elemental and molecular composition in solid samples vaporized and ionized with a pulsed laser. We will describe how each of these capabilities has particular strengths that can achieve key measurement objectives at Mars. In addition, the close codevelopment of the GC/MS and LDMS along with a sample manipulation system enables the the sharing of resources, the correlation of results, and the utilization of certain approaches that would not be possible with separate instruments. For instance, the same samples could be analyzed with more than one technique, increasing efficiency and providing cross-checks for quantification. There is also the possibility of combining methods, such as by permitting TOF-MS analyses of evolved gas (Pyr/EI-TOF-MS) or GC/MS analyses of laser evaporated gas (LD-GC/MS).

Assaying Alpha-Dicarbonyl Compounds in Wine: A Complementary GC-MS, HPCL, and Visible Spectrophotometric Analysis

ERIC Educational Resources Information Center

Dwyer, Tammy J.; Fillo, Jeremiah D.

2006-01-01

The analytical system to teach the subtleties of assaying alpha-dicarbonyl compounds in wine is described. Spectrophotometry is determined to be minimally useful in the experiment where the GC-MS (methyglyoxal) method proved to be ideal to confirm that the compounds analyzed in the wine samples were indeed the glyoxals based on the formation of…

40 CFR Appendix A to Subpart C of... - Alternative Testing Methods Approved for Analyses Under the Safe Drinking Water Act

Code of Federal Regulations, 2014 CFR

2014-07-01

... Spectrometry (GC/MS) 525.3 24 Carbofuran High-performance liquid chromatography (HPLC) with post-column... (HPLC) with Post-Column Derivatization and Fluorescence Detection 6651 B 6651 B 6651 B-00, B-05... Chromatography/Mass Spectrometry (GC/MS) 525.3 24 Oxamyl High-performance liquid chromatography (HPLC) with post...

Characterization and differentiation of high energy cyclic organic peroxides by GC/FT-IR, GC-MS, FT-IR, and Raman microscopy

NASA Astrophysics Data System (ADS)

Pena, Alvaro J.; Pacheco-Londono, Leonardo; Figueroa, Javier; Rivera-Montalvo, Luis A.; Roman-Velazquez, Felix R.; Hernandez-Rivera, Samuel P.

2005-05-01

The characterization of Tetracetone Tetraperoxide (TRATRP), Triacetone Triperoxide (TATP), Diacetone Diperoxide (DADP), Tricyclohexylidene Triperoxide and Dibenzo Diperoxide using GC-MS, GC-FTIR, FTIR, FT-NMR and Raman Spectroscopy is reported. These compounds were synthesized, purified and characterized in the laboratory in order to develop methodologies for their trace detection. During this study, TATP has been synthesized by different methods obtaining high purity and good yields, even using common household products. DADP synthetic routes reported in the literature were verified. The methods described, including those that produce mixtures with TATP and other peroxides forms were also tested. This study will also focused in the preparation of other cyclic peroxides, including Hexamethelene Triperoxide Diamine (HMTD) and different forms of cyclic peroxides from ketones. This issue of thermodynamic versus kinetic control of secondary products of all syntheses and the effect of temperature in the distribution sub products of the syntheses was also addressed. A vibrational differentiation study of was carried out. Differences were found computationally in the υ(O-O), υ(C-O), δ(CH3-C) and δ(C-O) for Raman and IR bands and retention time and fragment patron for GC-MS and GC-FT-IR.

Application of the experimental design of experiments (DoE) for the determination of organotin compounds in water samples using HS-SPME and GC-MS/MS.

PubMed

Coscollà, Clara; Navarro-Olivares, Santiago; Martí, Pedro; Yusà, Vicent

2014-02-01

When attempting to discover the important factors and then optimise a response by tuning these factors, experimental design (design of experiments, DoE) gives a powerful suite of statistical methodology. DoE identify significant factors and then optimise a response with respect to them in method development. In this work, a headspace-solid-phase micro-extraction (HS-SPME) combined with gas chromatography tandem mass spectrometry (GC-MS/MS) methodology for the simultaneous determination of six important organotin compounds namely monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT) has been optimized using a statistical design of experiments (DOE). The analytical method is based on the ethylation with NaBEt4 and simultaneous headspace-solid-phase micro-extraction of the derivative compounds followed by GC-MS/MS analysis. The main experimental parameters influencing the extraction efficiency selected for optimization were pre-incubation time, incubation temperature, agitator speed, extraction time, desorption temperature, buffer (pH, concentration and volume), headspace volume, sample salinity, preparation of standards, ultrasonic time and desorption time in the injector. The main factors (excitation voltage, excitation time, ion source temperature, isolation time and electron energy) affecting the GC-IT-MS/MS response were also optimized using the same statistical design of experiments. The proposed method presented good linearity (coefficient of determination R(2)>0.99) and repeatibilty (1-25%) for all the compounds under study. The accuracy of the method measured as the average percentage recovery of the compounds in spiked surface and marine waters was higher than 70% for all compounds studied. Finally, the optimized methodology was applied to real aqueous samples enabled the simultaneous determination of all compounds under study in surface and marine water samples obtained from Valencia region (Spain). © 2013 Elsevier B.V. All rights reserved.

Discovery and Identification of Dimethylsilanediol as a Contaminant in ISS Potable Water

NASA Technical Reports Server (NTRS)

Rutz, Jeffrey A.; Schultz, John R.; Kuo, C. Mike; Curtis, Matthew; Jones, Patrick R.; Sparkman, O. David; McCoy, J. Torin

2011-01-01

In September 2010, analysis of ISS potable water samples was undertaken to determine the contaminant(s) responsible for a rise of total organic carbon (TOC) in the Water Processor Assembly (WPA) product water. As analysis of the routine target list of organic compounds did not reveal the contaminant, efforts to look for unknown compounds were initiated, resulting in discovery of an unknown peak in the gas chromatography/mass spectrometry (GC/MS) analysis for glycols. A mass spectrum of the contaminant was then generated by concentrating one of the samples and analyzing it by GC/MS in full-scan mode. Although a computer match of the compound identity could not be obtained with the instrument database, a search with a more up-to-date mass spectral library yielded a good match with dimethylsilanediol (DMSD). Inductively coupled plasma/mass spectrometry (ICP/MS) analyses showed abnormally high silicon levels in the samples, confirming that the unknown compound(s) contained silicon. DMSD was then synthesized to confirm the identification and provide a standard to develop a calibration curve. Further confirmation was provided by external direct analysis in real time time of flight (DART TOF) mass spectrometry. To routinely test for DMSD in the future, a quantitative method was needed. A preliminary GC/MS method was developed and archived samples from various locations on ISS were analyzed to determine the extent of the contamination and provide data for troubleshooting. This paper describes these events in more detail as well as problems encountered in routine GC/MS analyses and the subsequent development of high performance liquid chromatography and LC/MS/MS methods for measuring DMSD.

Metabolomic analysis using porcine skin: a pilot study of analytical techniques.

PubMed

Wu, Julie; Fiehn, Oliver; Armstrong, April W

2014-06-15

Metabolic byproducts serve as indicators of the chemical processes and can provide valuable information on pathogenesis by measuring the amplified output. Standardized techniques for metabolome extraction of skin samples serve as a critical foundation to this field but have not been developed. We sought to determine the optimal cell lysage techniques for skin sample preparation and to compare GC-TOF-MS and UHPLC-QTOF-MS for metabolomic analysis. Using porcine skin samples, we pulverized the skin via various combinations of mechanical techniques for cell lysage. After extraction, the samples were subjected to GC-TOF-MS and/or UHPLC-QTOF-MS. Signal intensities from GC-TOF-MS analysis showed that ultrasonication (2.7x107) was most effective for cell lysage when compared to mortar-and-pestle (2.6x107), ball mill followed by ultrasonication (1.6x107), mortar-and-pestle followed by ultrasonication (1.4x107), and homogenization (trial 1: 8.4x106; trial 2: 1.6x107). Due to the similar signal intensities, ultrasonication and mortar-and-pestle were applied to additional samples and subjected to GC-TOF-MS and UHPLC-QTOF-MS. Ultrasonication yielded greater signal intensities than mortar-and-pestle for 92% of detected metabolites following GC-TOF-MS and for 68% of detected metabolites following UHPLC-QTOF-MS. Overall, ultrasonication is the preferred method for efficient cell lysage of skin tissue for both metabolomic platforms. With standardized sample preparation, metabolomic analysis of skin can serve as a powerful tool in elucidating underlying biological processes in dermatological conditions.

Different methods for volatile sampling in mammals

PubMed Central

Möller, Manfred; Marcillo, Andrea; Einspanier, Almuth; Weiß, Brigitte M.

2017-01-01

Previous studies showed that olfactory cues are important for mammalian communication. However, many specific compounds that convey information between conspecifics are still unknown. To understand mechanisms and functions of olfactory cues, olfactory signals such as volatile compounds emitted from individuals need to be assessed. Sampling of animals with and without scent glands was typically conducted using cotton swabs rubbed over the skin or fur and analysed by gas chromatography-mass spectrometry (GC-MS). However, this method has various drawbacks, including a high level of contaminations. Thus, we adapted two methods of volatile sampling from other research fields and compared them to sampling with cotton swabs. To do so we assessed the body odor of common marmosets (Callithrix jacchus) using cotton swabs, thermal desorption (TD) tubes and, alternatively, a mobile GC-MS device containing a thermal desorption trap. Overall, TD tubes comprised most compounds (N = 113), with half of those compounds being volatile (N = 52). The mobile GC-MS captured the fewest compounds (N = 35), of which all were volatile. Cotton swabs contained an intermediate number of compounds (N = 55), but very few volatiles (N = 10). Almost all compounds found with the mobile GC-MS were also captured with TD tubes (94%). Hence, we recommend TD tubes for state of the art sampling of body odor of mammals or other vertebrates, particularly for field studies, as they can be easily transported, stored and analysed with high performance instruments in the lab. Nevertheless, cotton swabs capture compounds which still may contribute to the body odor, e.g. after bacterial fermentation, while profiles from mobile GC-MS include only the most abundant volatiles of the body odor. PMID:28841690

Forensic Drug Identification, Confirmation, and Quantification Using Fully Integrated Gas Chromatography with Fourier Transform Infrared and Mass Spectrometric Detection (GC-FT-IR-MS).

PubMed

Lanzarotta, Adam; Lorenz, Lisa; Voelker, Sarah; Falconer, Travis M; Batson, JaCinta S

2018-05-01

This manuscript is a continuation of a recent study that described the use of fully integrated gas chromatography with direct deposition Fourier transform infrared detection and mass spectrometric detection (GC-FT-IR-MS) to identify and confirm the presence of sibutramine and AB-FUBINACA. The purpose of the current study was to employ the GC-FT-IR portion of the same instrument to quantify these compounds, thereby demonstrating the ability to identify, confirm, and quantify drug substances using a single GC-FT-IR-MS unit. The performance of the instrument was evaluated by comparing quantitative analytical figures of merit to those measured using an established, widely employed method for quantifying drug substances, high performance liquid chromatography with ultraviolet detection (HPLC-UV). The results demonstrated that GC-FT-IR was outperformed by HPLC-UV with regard to sensitivity, precision, and linear dynamic range (LDR). However, sibutramine and AB-FUBINACA concentrations measured using GC-FT-IR were not significantly different at the 95% confidence interval compared to those measured using HPLC-UV, which demonstrates promise for using GC-FT-IR as a semi-quantitative tool at the very least. The most significant advantage of GC-FT-IR compared to HPLC-UV is selectivity; a higher level of confidence regarding the identity of the analyte being quantified is achieved using GC-FT-IR. Additional advantages of using a single GC-FT-IR-MS instrument for identification, confirmation, and quantification are efficiency, increased sample throughput, decreased consumption of laboratory resources (solvents, chemicals, consumables, etc.), and thus cost.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This interim notice covers the following: extractable organic halides in solids, total organic halides, analysis by gas chromatography/Fourier transform-infrared spectroscopy, hexadecane extracts for volatile organic compounds, GC/MS analysis of VOCs, GC/MS analysis of methanol extracts of cryogenic vapor samples, screening of semivolatile organic extracts, GPC cleanup for semivolatiles, sample preparation for GC/MS for semi-VOCs, analysis for pesticides/PCBs by GC with electron capture detection, sample preparation for pesticides/PCBs in water and soil sediment, report preparation, Florisil column cleanup for pesticide/PCBs, silica gel and acid-base partition cleanup of samples for semi-VOCs, concentrate acid wash cleanup, carbon determination in solids using Coulometrics` CO{submore » 2} coulometer, determination of total carbon/total organic carbon/total inorganic carbon in radioactive liquids/soils/sludges by hot persulfate method, analysis of solids for carbonates using Coulometrics` Model 5011 coulometer, and soxhlet extraction.« less

Identification of tamoxifen and metabolites in human male urine by GC/MS.

PubMed

Mihailescu, R; Aboul-Enein, H Y; Efstatide, M D

2000-05-01

Tamoxifen is an antiestrogenic drug which is used in the treatment of breast cancer and nonmalignant breast disorders. It also has a stimulating effect on the secretion of hypofisar gonadotropic hormones and is generally used in the treatment of infertility. In males, tamoxifen causes an increase of endogenous production of androgenic steroids, and therefore is used by athletes. A method for identification of tamoxifen and metabolites in urine, using the gas chromatography and mass spectrometry system (GC/MS) is described. This study also reports the extraction methodology of tamoxifen and metabolites in urine samples of healthy male volunteers and the GC/MS conditions used to identify tamoxifen and its metabolites.

Development and validation of a matrix solid-phase dispersion method to determine acrylamide in coffee and coffee substitutes.

PubMed

Soares, Cristina M Dias; Alves, Rita C; Casal, Susana; Oliveira, M Beatriz P P; Fernandes, José Oliveira

2010-04-01

The present study describes the development and validation of a new method based on a matrix solid-phase dispersion (MSPD) sample preparation procedure followed by GC-MS for determination of acrylamide levels in coffee (ground coffee and brewed coffee) and coffee substitute samples. Samples were dispersed in C(18) sorbent and the mixture was further packed into a preconditioned custom-made ISOLUTE bilayered SPE column (C(18)/Multimode; 1 g + 1 g). Acrylamide was subsequently eluted with water, and then derivatized with bromine and quantified by GC-MS in SIM mode. The MSPD/GC-MS method presented a LOD of 5 microg/kg and a LOQ of 10 microg/kg. Intra and interday precisions ranged from 2% to 4% and 4% to 10%, respectively. To evaluate the performance of the method, 11 samples of ground and brewed coffee and coffee substitutes were simultaneously analyzed by the developed method and also by a previously validated method based in a liquid-extraction (LE) procedure, and the results were compared showing a high correlation between them.

A method for the determination of acrylamide in a broad variety of processed foods by GC-MS using xanthydrol derivatization.

PubMed

Yamazaki, Kumiko; Isagawa, Satoshi; Kibune, Nobuyuki; Urushiyama, Tetsuo

2012-01-01

A novel GC-MS method was developed for the determination of acrylamide, which is applicable to a variety of processed foods, including potato snacks, corn snacks, biscuits, instant noodles, coffee, soy sauces and miso (fermented soy bean paste). The method involves the derivatization of acrylamide with xanthydrol instead of a bromine compound. Isotopically labelled acrylamide (d₃-acrylamide) was used as the internal standard. The aqueous extract from samples was purified using Sep-Pak™ C₁₈ and Sep-Pak™ AC-2 columns. For amino acid-rich samples, such as miso or soy sauce, an Extrelut™ column was used for purification or extraction. After reaction with xanthydrol, the resultant N-xanthyl acrylamide was determined by GC-MS. The method was validated for various food matrices and showed good linearity, precision and trueness. The limit of detection and limit of quantification ranged 0.5-5 and 5-20 µg kg⁻¹), respectively. The developed method was applied as an exploratory survey of acrylamide in Japanese foods and the method was shown to be applicable for all samples tested.

Detection of lysergic acid diethylamide (LSD) in urine by gas chromatography-ion trap tandem mass spectrometry.

PubMed

Sklerov, J H; Kalasinsky, K S; Ehorn, C A

1999-10-01

A confirmatory method for the detection and quantitation of lysergic acid diethylamide (LSD) is presented. The method employs gas chromatography-tandem mass spectrometry (GC-MS-MS) using an internal ionization ion trap detector for sensitive MS-MS-in-time measurements of LSD extracted from urine. Following a single-step solid-phase extraction of 5 mL of urine, underivatized LSD can be measured with limits of quantitation and detection of 80 and 20 pg/mL, respectively. Temperature-programmed on-column injections of urine extracts were linear over the concentration range 20-2000 pg/mL (r2 = 0.999). Intraday and interday coefficients of variation were < 6% and < 13%, respectively. This procedure has been applied to quality-control specimens and LSD-positive samples in this laboratory. Comparisons with alternate GC-MS methods and extraction procedures are discussed.

Mass Spectrometry for the Masses

ERIC Educational Resources Information Center

Persinger, Jared D.; Hoops, Geoffrey, C.; Samide, Michael J.

2004-01-01

A simple, qualitative experiment is developed for implementation, where the gas chromatography-mass spectrometry (GC-MS) plays an important role, into the laboratory curriculum of a chemistry course designed for nonscience majors. This laboratory experiment is well suited for the students as it helps them to determine the validity of their…

Chemical analysis and quality control of Ginkgo biloba leaves, extracts, and phytopharmaceuticals.

PubMed

van Beek, Teris A; Montoro, Paola

2009-03-13

The chemical analysis and quality control of Ginkgo leaves, extracts, phytopharmaceuticals and some herbal supplements is comprehensively reviewed. The review is an update of a similar, earlier review in this journal [T.A. van Beek, J. Chromatogr. A 967 (2002) 21-55]. Since 2001 over 3000 papers on Ginkgo biloba have appeared, and about 400 of them pertain to chemical analysis in a broad sense and are cited herein. The more important ones are discussed and, where relevant, compared with the best methods published prior to 2002. In the same period over 2500 patents were filed on Ginkgo and the very few related to analysis are mentioned as well. Important constituents include terpene trilactones, i.e. ginkgolide A, B, C, J and bilobalide, flavonol glycosides, biflavones, proanthocyanidins, alkylphenols, simple phenolic acids, 6-hydroxykynurenic acid, 4-O-methylpyridoxine and polyprenols. In the most common so-called "standardised" Ginkgo extracts and phytopharmaceuticals several of these classes are no longer present. About 130 new papers deal with the analysis of the terpene trilactones. They are mostly extracted with methanol or water or mixtures thereof. Supercritical fluid extraction and pressurised water extraction are also possible. Sample clean-up is mostly by liquid-liquid extraction with ethyl acetate although no sample clean-up at all in combination with LC/MS/MS is gaining in importance. Separation and detection can be routinely carried out by RP-HPLC with ELSD, RI or MS, or by GC/FID or GC/MS after silylation. Hydrolysis followed by LC/MS allows the simultaneous analysis of terpene trilactones and flavonol aglycones. No quantitative procedure for all major flavonol glycosides has yet been published because they are not commercially available. The quantitation of a few available glycosides has been carried out but does not serve a real purpose. After acidic hydrolysis to the aglycones quercetin, kaempferol and isorhamnetin and separation by HPLC, quantitation is straightforward and yields by recalculation an estimation of the original total flavonol glycoside content. A profile of the genuine flavonol glycosides can detect poor storage or adulteration. Although the toxicity of Ginkgo alkylphenols upon oral administration has never been undoubtedly proven, most suppliers limit their content in extracts to 5 ppm and dozens of papers on their analysis were published. One procedure in which a methanolic extract is directly injected on a C8 HPLC column appears superior in terms of sensitivity (<5 ppm), separation, simplicity and validation and will be incorporated in the European Pharmacopoeia. Alternatively GC/MS and ELISA methods can be used. A sharp contrast to the plethora of papers on terpene trilactones, flavonol glycosides, and ginkgolic acids forms the low number of papers on biflavones, proanthocyanidins, simple phenolics, simple acids, and other constituents that make up the remaining 70% of Ginkgo standardised extracts. More research in this direction is clearly needed. For the analysis of Ginkgo proanthocyanidins (7%) for instance, no reliable assays are yet existing. Finally the growing literature on pharmacokinetic and fingerprinting studies of Ginkgo is briefly summarised.

Evaluation of the quality of sandalwood essential oils by gas chromatography-mass spectrometry.

PubMed

Howes, Melanie-Jayne R; Simmonds, Monique S J; Kite, Geoffrey C

2004-03-05

Trade and historic oils from 'sandalwoods', labelled as Amyris balsamifera, Eremophila mitchelli, Fusanus acuminatus (= Santalum acuminatum), Santalum album, S. austrocaledonicum, S. latifolium, S. spicatum and S. yasi, were assessed using gas chromatography-mass spectrometry (GC-MS). Using GC-MS, none of the oils assessed complied with the internationally recognised standard of a 90% santalol content, and only about half of the trade sandalwood oils met with recent International Organisation for Standardisation standards. The majority of trade oils, reportedly from S. album, contained approximately 50-70% santalols (Z-alpha and Z-beta). Thus, the internationally recognised specification (90% santalols) for S. album requires re-evaluation by more efficient analysis methods. In view of the issues associated with the quality of sandalwood oils being traded, specifications of > or = 43% Z-alpha-santalol and > or = 18% Z-beta-santalol for S. album oil estimated by GC-MS are suggested. GC-MS are recommended as it assists with authentication and quality control issues associated with sandalwood oils.

Detailed study of polystyrene solubility using pyrolysis-gas chromatography-mass spectrometry and combination with size-exclusion chromatography.

PubMed

Chojnacka, Aleksandra; Janssen, Hans-Gerd; Schoenmakers, Peter

2014-01-01

Measuring polymer solubility accurately and precisely is challenging. This is especially true at unfavourable solvent compositions, when only very small amounts of polymer dissolve. In this paper, pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) is demonstrated to be much more informative and sensitive than conventional methods, such as ultraviolet spectroscopy. By using a programmed-temperature-vapourisation injector as the pyrolysis chamber, we demonstrate that Py-GC-MS can cover up to five orders of magnitude in dissolved polymer concentrations. For polystyrene, a detection limit of 1 ng mL(-1) is attained. Dissolution in poor solvents is demonstrated to be discriminating in terms of the analyte molecular weight. Py-GC-MS additionally can yield information on polymer composition (e.g. in case of copolymers). In combination with size-exclusion chromatography, Py-GC-MS allows us to estimate the molecular weight distributions of minute amounts of a dissolved polymer and variations therein as a function of time.

Analysis of volatiles in fire debris by combination of activated charcoal strips (ACS) and automated thermal desorption-gas chromatography-mass spectrometry (ATD/GC-MS).

PubMed

Martin Fabritius, Marie; Broillet, Alain; König, Stefan; Weinmann, Wolfgang

2018-06-04

Adsorption of volatiles in gaseous phase to activated charcoal strip (ACS) is one possibility for the extraction and concentration of ignitable liquid residues (ILRs) from fire debris in arson investigations. Besides liquid extraction using carbon dioxide or hexane, automated thermo-desorption can be used to transfer adsorbed residues to direct analysis by gas chromatography-mass spectrometry (GC-MS). We present a fire debris analysis work-flow with headspace adsorption of volatiles onto ACS and subsequent automated thermo-desorption (ATD) GC-MS analysis. Only a small portion of the ACS is inserted in the ATD tube for thermal desorption coupled to GC-MS, allowing for subsequent confirmation analysis with another portion of the same ACS. This approach is a promising alternative to the routinely used ACS method with solvent extraction of retained volatiles, and the application to fire debris analysis is demonstrated. Copyright © 2018 Elsevier B.V. All rights reserved.

Gas chromatography and ultra high performance liquid chromatography tandem mass spectrometry methods for the determination of selected endocrine disrupting chemicals in human breast milk after stir-bar sorptive extraction.

PubMed

Rodríguez-Gómez, R; Zafra-Gómez, A; Camino-Sánchez, F J; Ballesteros, O; Navalón, A

2014-07-04

In the present work, two specific, accurate and sensitive methods for the determination of endocrine disrupting chemicals (EDCs) in human breast milk are developed and validated. Bisphenol A and its main chlorinated derivatives, five benzophenone-UV filters and four parabens were selected as target analytes. The method involves a stir-bar sorptive extraction (SBSE) procedure followed by a solvent desorption prior to GC-MS/MS or UHPLC-MS/MS analysis. A derivatization step is also necessary when GC analysis is performed. The GC column used was a capillary HP-5MS with a run time of 26min. For UHPLC analysis, the stationary phase was a non-polar Acquity UPLC(®) BEH C18 column and the run time was 10min. In both cases, the analytes were detected and quantified using a triple quadrupole mass spectrometer (QqQ). Quality parameters such as linearity, accuracy (trueness and precision), sensitivity and selectivity were examined and yielded good results. The limits of quantification (LOQs) ranged from 0.3 to 5.0ngmL(-1) for GC and from 0.2 to 1.0ngmL(-1) for LC. The relative standard deviation (RSD) was lower than 15% and the recoveries ranged from 92 to 114% in all cases, being slightly unfavorable the results obtained with LC. The methods were satisfactorily applied for the determination of target compounds in human milk samples from 10 randomly selected women. Copyright © 2014 Elsevier B.V. All rights reserved.

[Determination of organotin compounds in plastic products by GC/MS after ethyl derivatization with sodium tetraethylborate].

PubMed

Ohno, Hiroyuki; Suzuki, Masako; Nakashima, Shigehito; Aoyama, Taiki; Mitani, Kazunori

2002-08-01

A simultaneous determination method for 9 organotin compounds in polyvinyl chloride (PVC) and silicone products used as kitchen utensils and food packages was developed using ethyl derivatization with sodium tetraethylborate (NaBEt4). Organotin compounds were extracted with acetone-hexane (3:7) from the samples after acidification and the extract was filtered and concentrated at under 40 degrees C. After centrifugal separation, these compounds were derivatized with 2% NaBEt4 solution and determined by GC/MS. This method was applicable for simple routine analysis. Recoveries of spiked compounds were 49.1-118.1% for 3 PVC products and 88.8-102.2% for a siliconized paper. Monooctyltin, dioctyltin and trioctyltin compounds were found in all PVC food containers at the levels of 123-1,380 micrograms/g, 1,770-13,200 micrograms/g and 6.6-139 micrograms/g, respectively. They also were found in 3 gloves, 5 spouts, 1 hose and 5 pipes. Some PVC products contained monomethyltin, dimethyltin, trimethyltin, monobutyltin and dibutyltin compounds at the levels of 97.3-433 micrograms/g, 96.5-5,120 micrograms/g, 8.5-24.9 micrograms/g, 1.2-852 micrograms/g and 1.2-29.4 micrograms/g, respectively.

[Determination of fatty acid esters of chloropropanediols in diet samples by gas chromatography-mass spectrometry coupled with solid-supported liquid-liquid extraction].

PubMed

Gao, Jie; Liu, Qing; Han, Feng; Miao, Hong; Zhao, Yunfeng; Wu, Yongning

2014-05-01

To establish a method for the determination of fatty acid esters of 3-monochloropropane-1, 2-diol (3-MCPD) and 2-monochloropropane-1, 3-diol (2-MCPD) in diet samples by gas chromatography-mass spectrometry (GC-MS) with solid-supported liquid-liquid extraction (SLE). Diet samples were ultrasonically extracted by hexane, followed by ester cleavage reaction with sodium methylate in methanol, and then purified by solid-supported liquid-liquid extraction. (SLE) using diatomaceous earth as the sorbent. After derivatization with heptafluorobutyrylimidazole, the analytes were detected by GC-MS and quantified by the deuterated internal standards. The limits of detection (LODs) of 3-MCPD esters and 2-MCPD esters in different diet samples were 0.002 - 0.005 mg/kg and 0.002 - 0.006 mg/kg. The average recoveries of 3-MCPD esters and 2-MCPD esters at the spiking levels of 0.05 and 0.1 mg/kg in the diet samples were in the range of 65.9% - 104.2% and 75.4% - 118.0%, respectively, with the relative standard deviations in the range of 2.2% - 14.2% and 0.8% - .13.9%. The method is simple, accurate and rugged for the determination of fatty acid esters of 3-MCPD and 2-MCPD in diet samples.

Characterization of ion processes in a GC/DMS air quality monitor by integration of the instrument to a mass spectrometer.

PubMed

Limero, T F; Nazarov, E G; Menlyadiev, M; Eiceman, G A

2015-02-07

The air quality monitor (AQM), which included a portable gas chromatograph (GC) and a detector was interfaced to a mass spectrometer (MS) by introducing flow from the GC detector to the atmospheric pressure ion source of the MS. This small GC system, with a gas recirculation loop for carrier and detector make-up gases, comprised an inlet to preconcentrate volatile organic compounds (VOCs) in air, a thermal desorber before the GC column, a differential mobility spectrometer (DMS), and another DMS as an atmospheric pressure ionization source for the MS. Return flow to the internally recirculated air system of the AQM's DMS was replenished using purified air. Although ions and unreacted neutral vapors flowed from the detector through Viton® tubing into the source of the MS, ions were not detected in the MS without the auxillary ion source, (63)Ni as in the mobility detector. The GC-DMS-MS instrument provided a 3-D measurement platform (GC, DMS, and MS analysis) to explore the gas composition inside the GC-DMS recirculation loop and provide DMS-MS measurement of the components of a complex VOC mixture with performance significantly enhanced by mass-analysis, either with mass spectral scans or with an extracted ion chromatogram. This combination of a mobility spectrometer and a mass spectrometer was possible as vapors and ions are carried together through the DMS analyzer, thereby preserving the chromatographic separation efficiency. The critical benefit of this instrument concept is that all flows in and through the thoroughly integrated GC-DMS analyzer are kept intact allowing a full measure of the ion and vapor composition in the complete system. Performance has been evaluated using a synthetic air sample and a sample of airborne vapors in a laboratory. Capabilities and performance values are described using results from AQM-MS analysis of purified air, ambient air from a research laboratory in a chemistry building, and a sample of synthetic air of known composition. Quantitative measures of a stand-alone AQM are disclosed for VOCs in the ppb to ppm levels with an average precision of 5.8% RSD and accuracy from 4% to 28% error against a standard method.

Enhanced Isotopic Ratio Outlier Analysis (IROA) Peak Detection and Identification with Ultra-High Resolution GC-Orbitrap/MS: Potential Application for Investigation of Model Organism Metabolomes.

PubMed

Qiu, Yunping; Moir, Robyn D; Willis, Ian M; Seethapathy, Suresh; Biniakewitz, Robert C; Kurland, Irwin J

2018-01-18

Identifying non-annotated peaks may have a significant impact on the understanding of biological systems. In silico methodologies have focused on ESI LC/MS/MS for identifying non-annotated MS peaks. In this study, we employed in silico methodology to develop an Isotopic Ratio Outlier Analysis (IROA) workflow using enhanced mass spectrometric data acquired with the ultra-high resolution GC-Orbitrap/MS to determine the identity of non-annotated metabolites. The higher resolution of the GC-Orbitrap/MS, together with its wide dynamic range, resulted in more IROA peak pairs detected, and increased reliability of chemical formulae generation (CFG). IROA uses two different 13 C-enriched carbon sources (randomized 95% 12 C and 95% 13 C) to produce mirror image isotopologue pairs, whose mass difference reveals the carbon chain length (n), which aids in the identification of endogenous metabolites. Accurate m/z, n, and derivatization information are obtained from our GC/MS workflow for unknown metabolite identification, and aids in silico methodologies for identifying isomeric and non-annotated metabolites. We were able to mine more mass spectral information using the same Saccharomyces cerevisiae growth protocol (Qiu et al. Anal. Chem 2016) with the ultra-high resolution GC-Orbitrap/MS, using 10% ammonia in methane as the CI reagent gas. We identified 244 IROA peaks pairs, which significantly increased IROA detection capability compared with our previous report (126 IROA peak pairs using a GC-TOF/MS machine). For 55 selected metabolites identified from matched IROA CI and EI spectra, using the GC-Orbitrap/MS vs. GC-TOF/MS, the average mass deviation for GC-Orbitrap/MS was 1.48 ppm, however, the average mass deviation was 32.2 ppm for the GC-TOF/MS machine. In summary, the higher resolution and wider dynamic range of the GC-Orbitrap/MS enabled more accurate CFG, and the coupling of accurate mass GC/MS IROA methodology with in silico fragmentation has great potential in unknown metabolite identification, with applications for characterizing model organism networks.

Multiresidue determination of pesticides in tea by gas chromatography-tandem mass spectrometry.

PubMed

Saito-Shida, Shizuka; Nemoto, Satoru; Teshima, Reiko

2015-01-01

An efficient and reliable GC-MS/MS method for the multiresidue determination of pesticides in tea was developed by modifying the Japanese official multiresidue method. Sample preparation was carefully optimized for the efficient removal of coextracted matrix components. The optimal sample preparation procedure involved swelling of the sample in water; extraction with acetonitrile; removal of water by salting-out; and sequential cleanup by ODS, graphitized carbon black/primary secondary amine (GCB/PSA) and silica gel cartridges prior to GC-MS/MS analysis. The recoveries of 162 pesticides from fortified (at 0.01 mg kg(-1)) green tea, oolong tea, black tea and matcha (powdered green tea) were mostly (95-98% of the tested pesticides) within the range of 70-120%, with relative standard deviations of <20%. Poor recovery of triazole pesticides was considered to be due to low recovery from the silica gel cartridges. The test solutions obtained by the modified method contained relatively small amounts of pigments, caffeine and other matrix components and were cleaner than those obtained by the original Japanese official multiresidue method. No interfering peaks were observed in the blank chromatograms, indicating the high selectivity of the modified method. The overall results suggest that the developed method is suitable for the quantitative analysis of GC-amenable pesticide residues in tea.

Outdoor and indoor benzene evaluation by GC-FID and GC-MS/MS.

PubMed

Sousa, José A; Domingues, Valentina F; Rosas, Mónica S; Ribeiro, Susana O; Alvim-Ferraz, Conceiçao M; Delerue-Matos, Cristina F

2011-01-01

The evaluation of benzene in different environments such as indoor (with and without tobacco smoke), a city area, countryside, gas stations and near exhaust pipes from cars running on different types of fuels was performed. The samples were analyzed using gas chromatography (GC) with flame ionization detection (FID) and tandem mass spectrometric detection (MS/MS) (to confirm the identification of benzene in the air samples). Operating conditions for the GC-MS analysis were optimized as well as the sampling and sample preparation. The results obtained in this work indicate that i) the type of fuel directly influences the benzene concentration in the air. Gasoline with additives provided the highest amount of benzene followed by unleaded gasoline and diesel; ii) the benzene concentration in the gas station was always higher than the advisable limit established by law (5 μg m⁻³) and during the unloading of gasoline the achieved concentration was 8371 μg m⁻³; iii) the data from the countryside (Taliscas) and the urban city (Matosinhos) were below 5 μg m⁻³ except 5 days after a fire on a petroleum refinery plant located near the city; iv) it was proven that in coffee shops where smoking is allowed the benzene concentration is higher (6 μg m⁻³) than in coffee shops where this is forbidden (4 μg m⁻³). This method may also be helpful for environmental analytical chemists who use GC-MS/MS for the confirmation or/and quantification of benzene.

Analysis of yohimbine alkaloid from Pausinystalia yohimbe by non-aqueous capillary electrophoresis and gas chromatography-mass spectrometry.

PubMed

Chen, Qinhua; Li, Peng; Zhang, Zhuo; Li, Kaijun; Liu, Jia; Li, Qiang

2008-07-01

In the present work, the qualitative and quantitative analysis of Pausinystalia yohimbe-type alkaloids in the barks of Rubiaceae species is presented using different analytical approaches. Extracts of P. yohimbe were first examined by GC-MS and the major alkaloids were identified. The quantitation of yohimbine was then accomplished by non-aqueous CE (NACE) with diode array detection. This approach was selected in order to use a running buffer fully compatible with samples in organic solvent. In particular, a mixture of methanol containing ammonium acetate (20 mM) and glacial acetic acid was used as a BGE. The same analytical sample was subjected to GC-MS and NACE analysis; the different selectivity displayed by these techniques allowed different separation profiles that can be useful in phytochemical characterization of the extracts. The linear calibration ranges were all 10-1000 microg/mL for yohimbine by GC-MS and NACE analysis. The recovery of yohimbine was 91.2-94.0% with RSD 1.4-4.3%. The LOD for yohimbine were 0.6 microg/mL by GC-MS and 1.0 microg/mL by NACE, respectively. The GC-MS and NACE methods were successfully validated and applied to the quantitation of yohimbine.

Bacterial biomarkers thermally released from dissolved organic matter

USGS Publications Warehouse

Greenwood, P.F.; Leenheer, J.A.; McIntyre, C.; Berwick, L.; Franzmann, P.D.

2006-01-01

Hopane biomarker products were detected using microscale sealed vessel (MSSV) pyrolysis gas chromatography-mass spectrometry (GC-MS) analysis of dissolved organic matter from natural aquatic systems colonised by bacterial populations. MSSV pyrolysis can reduce the polyhydroxylated alkyl side chain of bacteriohopanepolyols, yielding saturated hopane products which are more amenable to GC-MS detection than their functionalised precursors. This example demonstrates how the thermal conditions of MSSV pyrolysis can reduce the biologically-inherited structural functionality of naturally occurring organic matter such that additional structural fragments can be detected using GC methods. This approach complements traditional analytical pyrolysis methods by providing additional speciation information useful for establishing the structures and source inputs of recent or extant organic material. ?? 2006.

SDE and SPME Analysis of Flavor Compounds in Jin Xuan Oolong Tea.

PubMed

Sheibani, Ershad; Duncan, Susan E; Kuhn, David D; Dietrich, Andrea M; O'Keefe, Sean F

2016-02-01

Simultaneous distillation-extraction (SDE) and solid phase micro extraction (SPME) are procedures used for the isolation of flavor compounds in foods. The purpose of this study was to optimize SDE conditions (solvent and time) and to compare SDE with SPME for the isolation of flavor compounds in Jin Xuan oolong tea using GC-MS and GC-O. The concentration of volatile compounds isolated with diethyl ether was higher (P < 0.05) than for dichloromethane and concentration was higher at 40 min (P < 0.05) than 20 or 60 min extractions. For SDE, 128 volatiles were identified using GC-MS and 45 aroma active compounds using GC-O. Trans-nerolidol was the most abundant compound in oolong tea. The number of volatiles identified using GC-MS was lower in SPME than SDE. For SPME, 59 volatiles and 41 aroma active compounds were identified. The composition of the volatiles isolated by the 2 methods differed considerably but provided complementary information. © 2016 Institute of Food Technologists®

OZONATION BY-PRODUCTS 2. IMPROVEMENT OF AN AQUEOUS- PHASE DERIVITIZATION METHOD FOR THE DETECTION OF FORMALDEHYDE AND OTHER CARBONYL COMPOUNDS FORMED BY THE OZONATION OF DRINKING WATER

EPA Science Inventory

A method for the determination of low molecular weight aldehydes in water using aqueous-phase derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride has been improved by the use of high-resolution capillary GC. Detection limits with GC/ECD and GC/MS with ...

Measurement of imidacloprid in xylem fluid from eastern hemlock (Tsuga canadensis) by derivitization/GC/MS and ELISA

Treesearch

Anthony Lagalante; Peter Greenbacker; Jonathan Jones; Richard Turcotte; Bradley Onken

2007-01-01

Imidacloprid is a nonvolatile insecticide and its direct quantification is not possible by gas chromatography. In order to ascertain imidacloprid levels in soil and trunk injection treated trees, a sensitive and selective method has been developed using GC/MS to measure the imidacloprid levels in xylem fluid exudates. In May 2005, a stand of hemlock trees in West...

[The biotransformation of fenetylline].

PubMed

Rücker, G; Neugebauer, M; Heiden, P G

1988-04-01

After oral administration of 3,7-dihydro-1,3-dimethyl-7-2 [(1-methyl-2-phenylethyl)-amino-ethyl]-1H-purine-2,6-dione (fenetylline, Captagon), 7 new metabolites could be detected in urine besides 4 known substances. The metabolites were identified by gas chromatography (GC) and by comparison of the mass spectra (MS) of metabolites with those of authentic reference compounds using a combined GC/MS method.

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.

PubMed

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.

Applicability of the new 60 μm polyethylene glycol solid-phase microextraction fiber assembly for the simultaneous analysis of six pesticides in water.

PubMed

Pereira, Ana; Silva, Emília; Cerejeira, Maria J

2014-01-01

A solid-phase microextraction (SPME) method has been applied for the simultaneous analysis of six pesticides in water, with polar to moderately polar range, by gas chromatography-mass spectrometry (GC-MS). Two types of fiber coatings [60 µm polyethylene glycol (PEG) and 65 µm polydimethylsiloxane/divinylbenzene (PDMS/DVB)] and the effect of salt (addition of 10 and 25% of NaCl) were compared. The extraction efficiency was higher with PEG than with the PDMS/DVB fiber for all pesticides, with the exception of terbuthylazine and phosmet, and with addition of 25% NaCl. The optimized SPME-GC-MS method, adopting the PEG fiber and the addition of 25% NaCl, in addition to other conditions [60 min of direct dipping of the fiber into the water sample (10 mL) under agitation (250 rpm) at ambient temperature; desorption period of 5 min at 240°C] allowed the determination of all studied pesticides and showed good linearity for concentrations ranging from 0.05 to 5 µg/L. Limits of detection varied between 0.003 and 0.145 µg/L, with values below 0.025 µg/L for most of the analytes. Precision ranged from 4.2 to 12%. The proposed method is fast and simple, and was proven to be reliable for the routine analysis of pesticides in water, primarily for environmental monitoring.

“Retention Projection” Enables Reliable Use of Shared Gas Chromatographic Retention Data Across Labs, Instruments, and Methods

PubMed Central

Barnes, Brian B.; Wilson, Michael B.; Carr, Peter W.; Vitha, Mark F.; Broeckling, Corey D.; Heuberger, Adam L.; Prenni, Jessica; Janis, Gregory C.; Corcoran, Henry; Snow, Nicholas H.; Chopra, Shilpi; Dhandapani, Ramkumar; Tawfall, Amanda; Sumner, Lloyd W.; Boswell, Paul G.

2014-01-01

Gas chromatography-mass spectrometry (GC-MS) is a primary tool used to identify compounds in complex samples. Both mass spectra and GC retention times are matched to those of standards, but it is often impractical to have standards on hand for every compound of interest, so we must rely on shared databases of MS data and GC retention information. Unfortunately, retention databases (e.g. linear retention index libraries) are experimentally restrictive, notoriously unreliable, and strongly instrument dependent, relegating GC retention information to a minor, often negligible role in compound identification despite its potential power. A new methodology called “retention projection” has great potential to overcome the limitations of shared chromatographic databases. In this work, we tested the reliability of the methodology in five independent laboratories. We found that even when each lab ran nominally the same method, the methodology was 3-fold more accurate than retention indexing because it properly accounted for unintentional differences between the GC-MS systems. When the labs used different methods of their own choosing, retention projections were 4- to 165-fold more accurate. More importantly, the distribution of error in the retention projections was predictable across different methods and labs, thus enabling automatic calculation of retention time tolerance windows. Tolerance windows at 99% confidence were generally narrower than those widely used even when physical standards are on hand to measure their retention. With its high accuracy and reliability, the new retention projection methodology makes GC retention a reliable, precise tool for compound identification, even when standards are not available to the user. PMID:24205931

Cocaine and opiates use in pregnancy: detection of drugs in neonatal meconium and urine.

PubMed

López, P; Bermejo, A M; Tabernero, M J; Cabarcos, P; Alvarez, I; Fernández, P

2009-09-01

In this study, the case of a newborn with symptoms of hyperexcitability was analyzed. After it was confirmed in the hospital that the mother had consumed drugs during pregnancy using an enzyme multiplied immunoassay technique, samples of the newborn's urine and meconium were sent to our laboratory to observe the evolution in the distribution of cocaine and opiates during the days following birth. For urine analysis, screening was done with an immunoassay technique, and the confirmation was done by gas chromatography-mass spectrometry (GC-MS) according to a published method. A GC-MS method for simultaneous analysis of cocaine, benzoylecgonine, codeine, morphine, and 6-acetylmorphine in meconium is described. GC-MS confirmation of urine and meconium results showed consumption of cocaine and codeine during pregnancy and also showed the levels of drugs gradually declined, totally disappearing by the third day.

Differentiation of Volatile Profiles from Stockpiled Almonds at Varying Relative Humidity Levels Using Benchtop and Portable GC-MS.

PubMed

Beck, John J; Willett, Denis S; Gee, Wai S; Mahoney, Noreen E; Higbee, Bradley S

2016-12-14

Contamination by aflatoxin, a toxic metabolite produced by Aspergillus fungi ubiquitous in California almond and pistachio orchards, results in millions of dollars of lost product annually. Current detection of aflatoxin relies on destructive, expensive, and time-intensive laboratory-based methods. To explore an alternative method for the detection of general fungal growth, volatile emission profiles of almonds at varying humidities were sampled using both static SPME and dynamic needle-trap SPE followed by benchtop and portable GC-MS analysis. Despite the portable SPE/GC-MS system detecting fewer volatiles than the benchtop system, both systems resolved humidity treatments and identified potential fungal biomarkers at extremely low water activity levels. This ability to resolve humidity levels suggests that volatile profiles from germinating fungal spores could be used to create an early warning, nondestructive, portable detection system of fungal growth.

GC-MS determination of parabens, triclosan and methyl triclosan in water by in situ derivatisation and stir-bar sorptive extraction.

PubMed

Casas Ferreira, Ana María; Möder, Monika; Fernández Laespada, María Esther

2011-01-01

Stir-bar sorptive extraction in combination with an in situ derivatisation reaction and thermal desorption-gas chromatography-mass spectrometry was successfully applied to determine parabens (methylparaben, isopropylparaben, n-propylparaben, butylparaben and benzylparaben), triclosan and methyltriclosan in water samples. This approach improves both the extraction efficiency and the sensitivity in the GC in a simple way since the derivatisation reaction occurs at the same time as the extraction procedure. The in situ derivatisation reaction was carried out with acetic anhydride under alkaline conditions. Thermal desorption parameters (cryofocusing temperature, desorption flow, desorption time, desorption temperature) were optimised using a Box-Behnken experimental design. All the analytes gave recoveries higher than 79%, except methylparaben (22%). The method afforded detection limits between 0.64 and 4.12 ng/L, with good reproducibility and accuracy values. The feasibility of the method for the determination of analytes in water samples was checked in tap water and untreated and treated wastewater.

Metabolite profiling on apple volatile content based on solid phase microextraction and gas-chromatography time of flight mass spectrometry.

PubMed

Aprea, Eugenio; Gika, Helen; Carlin, Silvia; Theodoridis, Georgios; Vrhovsek, Urska; Mattivi, Fulvio

2011-07-15

A headspace SPME GC-TOF-MS method was developed for the acquisition of metabolite profiles of apple volatiles. As a first step, an experimental design was applied to find out the most appropriate conditions for the extraction of apple volatile compounds by SPME. The selected SPME method was applied in profiling of four different apple varieties by GC-EI-TOF-MS. Full scan GC-MS data were processed by MarkerLynx software for peak picking, normalisation, alignment and feature extraction. Advanced chemometric/statistical techniques (PCA and PLS-DA) were used to explore data and extract useful information. Characteristic markers of each variety were successively identified using the NIST library thus providing useful information for variety classification. The developed HS-SPME sampling method is fully automated and proved useful in obtaining the fingerprint of the volatile content of the fruit. The described analytical protocol can aid in further studies of the apple metabolome. Copyright © 2011 Elsevier B.V. All rights reserved.

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg, France) during agricultural application.

PubMed

Liaud, Céline; Brucher, Michel; Schummer, Claude; Coscollà, Clara; Wolff, Hélène; Schwartz, Jean-Jacques; Yusà, Vicent; Millet, Maurice

2016-10-02

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.

Direct determination of acrylamide in potato chips by using headspace solid-phase microextraction coupled with gas chromatography-flame ionization detection.

PubMed

Ghiasvand, Ali Reza; Hajipour, Somayeh

2016-01-01

Acrylamide is a potentially toxic and carcinogenic substance present in many high-consumption foods. Recently, this matter has been placed in category of "reasonably anticipated to be a human carcinogen" by National Toxicology Program (NTP). Therefore, simple and cost-effective determination of acrylamide in food samples has attracted intense interest. The most reported techniques for this purpose are GC-MS and LC-MS, which are very expensive and available in few laboratories. In this research, for the first time, a rapid, easy and low-cost method is introduced for sensitive and precise determination of acrylamide in foodstuffs, using gas chromatography-flame ionization detection (GC-FID) system after its direct trapping in the upper atmosphere of samples by headspace solid-phase microextraction (HS-SPME). The effects of main experimental variables were studied and the optimized parameters were obtained as the type of fiber, carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVB/PDMS); extraction time, 30 min; extraction temperature, 60°C; moisture content, 10 µL water per 1g of sample; desorption time, 2 min; and desorption temperature, 230°C. The linear calibration graph was obtained in the range of 0.77-50 µg g(-1), with regression coefficient of 0.998. The detection and quantification limits of the proposed method were 0.22 and 0.77 µg g(-1), respectively. The recoveries, for different food samples, were 79.6-95.7%. The repeatability of measurements, expressed as relative standard deviation (RSD), were found to be 4.1-8.0% (n=9). The proposed HS-SPME-GC-FID method was successfully carried out for quantifying of trace levels of acrylamide in some processed food products (chips and French fries), sold in open local markets. Copyright © 2015 Elsevier B.V. All rights reserved.

Multi-residue method for the determination of 450 pesticide residues in honey, fruit juice and wine by double-cartridge solid-phase extraction/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry.

PubMed

Pang, G-F; Fan, C-L; Liu, Y-M; Cao, Y-Z; Zhang, J-J; Fu, B-L; Li, X-M; Li, Z-Y; Wu, Y-P

2006-08-01

A multi-residue method was developed for the determination of 450 pesticide residues in honey, fruit juice and wine using double-cartridge solid-phase extraction (SPE), gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS). The method development was based on an appraisal of the characteristics of GC-MS and LC-MS-MS for 654 pesticides as well as the efficiency of extraction and purification from honey, fruit juice and wine. Samples were first diluted with water plus acetone, then extracted with portions of dichloromethane. The extracts were concentrated and cleaned up with graphitized carbon black and aminopropyl cartridges stacked in tandem. Pesticides were eluted with acetonitrile + toluene, and the eluates were concentrated. For 383 pesticides, the eluate was extracted with hexane twice and internal standard solution was added prior to GC-MS determination. For 67 pesticides, extraction was with methanol prior to LC-MS-MS determination. The limit of detection for the method was between 1.0 and 300 ng g(-1) depending on each pesticide analyte. At the three fortification levels of 2.0-3000 ng g(-1), the average recovery rates were between 59 and 123%, among which 413 pesticides (92% of the 450) had recovery rates of 70-120% and 35 pesticides (8% of the 450) had recovery rates of 59-70%. There were 437 pesticides (97% of the 450) with a relative standard deviation below 25%; there were 13 varieties (3% of the 450) between 25.0 and 30.4%.

Doping control analysis of trimetazidine and characterization of major metabolites using mass spectrometric approaches.

PubMed

Sigmund, Gerd; Koch, Anja; Orlovius, Anne-Katrin; Guddat, Sven; Thomas, Andreas; Schänzer, Wilhelm; Thevis, Mario

2014-01-01

Since January 2014, the anti-anginal drug trimetazidine [1-(2,3,4-trimethoxybenzyl)-piperazine] has been classified as prohibited substance by the World Anti-Doping Agency (WADA), necessitating specific and robust detection methods in sports drug testing laboratories. In the present study, the implementation of the intact therapeutic agent into two different initial testing procedures based on gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) is reported, along with the characterization of urinary metabolites by electrospray ionization-high resolution/high accuracy (tandem) mass spectrometry. For GC-MS analyses, urine samples were subjected to liquid-liquid extraction sample preparation, while LC-MS/MS analyses were conducted by established 'dilute-and-inject' approaches. Both screening methods were validated for trimetazidine concerning specificity, limits of detection (0.5-50 ng/mL), intra-day and inter-day imprecision (<20%), and recovery (41%) in case of the GC-MS-based method. In addition, major metabolites such as the desmethylated trimetazidine and the corresponding sulfoconjugate, oxo-trimetazidine, and trimetazidine-N-oxide as identified in doping control samples were used to complement the LC-MS/MS-based assay, although intact trimetazidine was found at highest abundance of the relevant trimetazidine-related analytes in all tested sports drug testing samples. Retrospective data mining regarding doping control analyses conducted between 1999 and 2013 at the Cologne Doping Control Laboratory concerning trimetazidine revealed a considerable prevalence of the drug particularly in endurance and strength sports accounting for up to 39 findings per year. Copyright © 2014 John Wiley & Sons, Ltd.

Detection and characterization of a new metabolite of 17alpha-methyltestosterone.

PubMed

Pozo, Oscar J; Van Eenoo, Peter; Deventer, Koen; Lootens, Leen; Van Thuyne, Wim; Parr, Maria K; Schänzer, Wilhelm; Sancho, Juan V; Hernández, Felix; Meuleman, Philip; Leroux-Roels, Geert; Delbeke, Frans T

2009-11-01

The misuse of the anabolic steroid methyltestosterone is currently routinely monitored in doping control laboratories by gas chromatography-mass spectrometry (GC-MS) of two of its metabolites: 17alpha-methyl-5beta-androstane-3alpha,17beta-diol and 17alpha-methyl-5alpha-androstane-3alpha,17beta-diol. Because of the absence of any easy ionizable moiety, these metabolites are poorly detectable using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI). In this study, the metabolism of methyltestosterone has been reinvestigated by the use of a precursor ion scan method in LC-ESI-MS/MS. Two metabolites have been detected using this method. Both compounds have been confirmed in postadministration urine samples of an urokinase plasminogen activator-severe combined immunodeficiency (uPA-SCID) mouse with humanized liver and were characterized by LC-MS/MS and GC-MS using both quadrupole and time of flight analyzers. From the detailed study of the fragmentation, these metabolites were proposed to be epimethyltestosterone and a dehydrogenated compound. Epimethyltestosterone has previously been described as a minor metabolite, whereas the occurrence of the oxidized metabolite has not been reported. Comparison with the synthesized reference revealed that the structure of the dehydrogenated metabolite is 6-ene-epimethyltestosterone. A selected reaction monitoring method including three transitions for each metabolite has been developed and applied to samples from an excretion study and to samples declared positive after GC-MS analysis. 6-Ene-epimethyltestosterone was found in all samples, showing its applicability in the detection of methyltestosterone misuse.

Volatile organic compounds in pesticide formulations: Methods to estimate ozone formation potential

NASA Astrophysics Data System (ADS)

Zeinali, Mazyar; McConnell, Laura L.; Hapeman, Cathleen J.; Nguyen, Anh; Schmidt, Walter F.; Howard, Cody J.

2011-05-01

The environmental fate and toxicity of active ingredients in pesticide formulations has been investigated for many decades, but relatively little research has been conducted on the fate of pesticide co-formulants or inerts. Some co-formulants are volatile organic compounds (VOCs) and can contribute to ground-level ozone pollution. Effective product assessment methods are required to reduce emissions of the most reactive VOCs. Six emulsifiable concentrate pesticide products were characterized for percent VOC by thermogravimetric analysis (TGA) and gas chromatography-mass spectrometry (GC-MS). TGA estimates exceeded GC-MS by 10-50% in all but one product, indicating that for some products a fraction of active ingredient is released during TGA or that VOC contribution was underestimated by GC-MS. VOC profiles were examined using TGA-Fourier transform infrared (FTIR) evolved gas analysis and were compared to GC-MS results. The TGA-FTIR method worked best for products with the simplest and most volatile formulations, but could be developed into an effective product screening tool. An ozone formation potential ( OFP) for each product was calculated using the chemical composition from GC-MS and published maximum incremental reactivity ( MIR) values. OFP values ranged from 0.1 to 3.1 g ozone g -1 product. A 24-h VOC emission simulation was developed for each product assuming a constant emission rate calculated from an equation relating maximum flux rate to vapor pressure. Results indicate 100% VOC loss for some products within a few hours, while other products containing less volatile components will remain in the field for several days after application. An alternate method to calculate a product OFP was investigated utilizing the fraction of the total mass of each chemical emitted at the end of the 24-h simulation. The ideal assessment approach will include: 1) unambiguous chemical composition information; 2) flexible simulation models to estimate emissions under different management practices; and 3) accurate reactivity predictions.

Determination of 48 fragrance allergens in toys using GC with ion trap MS/MS.

PubMed

Lv, Qing; Zhang, Qing; Li, Wentao; Li, Haiyu; Li, Pi; Ma, Qiang; Meng, Xianshuang; Qi, Meiling; Bai, Hua

2013-11-01

This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single-stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005-5.0 and from 0.02-20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5-109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7-10.5% and from 3.1-13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous determination of 24 polycyclic aromatic hydrocarbons in edible oil by tandem solid-phase extraction and gas chromatography coupled/tandem mass spectrometry.

PubMed

Xu, Ting; Tang, Hua; Chen, Dazhou; Dong, Haifeng; Li, Lei

2015-01-01

An efficient and fast tandem SPE method followed by GC/MS/MS has been developed for the determination and the quantification of 24 polycyclic aromatic hydrocarbons (PAHs) in edible oil. This method includes the monitoring of 15 + 1 PAHs designated as a priority by the European Union in their 2005/108/EC recommendation and 16 PAHs listed by the U. S. Environmental Protection Agency. The sample preparation procedures were based on SPE in which PAH-dedicated cartridges with molecularly imprinted polymers and graphitized carbon black were used in series. The novel tandem SPE combination of selective extraction and purification of light and heavy PAHs provided highly purified analytes. Identification and quantification of 24 target PAHs were performed using GC/MS/MS with the isotope dilution approaches using D-labeled and (13)C-labeled PAHs. The advantages of GC/MS/MS as compared to other detection methods include high sensitivity, selectivity, and interpretation ability. The method showed satisfactory linearity (R(2) > 0.998) over the range assayed (0.5-200 μg/kg); the LODs ranged from 0.03 to 0.6 μg/kg, and LOQs from 0.1 to 2.0 μg/kg. The recoveries using this method at three spiked concentration levels (2, 10, and 50 μg/kg) ranged from 56.8 to 117.7%. The RSD was lower than 12.7% in all cases. The proposed analytical method has been successfully applied for the analysis of the 24 PAHs in edible oil.

Comprehensive automation of the solid phase extraction gas chromatographic mass spectrometric analysis (SPE-GC/MS) of opioids, cocaine, and metabolites from serum and other matrices.

PubMed

Lerch, Oliver; Temme, Oliver; Daldrup, Thomas

2014-07-01

The analysis of opioids, cocaine, and metabolites from blood serum is a routine task in forensic laboratories. Commonly, the employed methods include many manual or partly automated steps like protein precipitation, dilution, solid phase extraction, evaporation, and derivatization preceding a gas chromatography (GC)/mass spectrometry (MS) or liquid chromatography (LC)/MS analysis. In this study, a comprehensively automated method was developed from a validated, partly automated routine method. This was possible by replicating method parameters on the automated system. Only marginal optimization of parameters was necessary. The automation relying on an x-y-z robot after manual protein precipitation includes the solid phase extraction, evaporation of the eluate, derivatization (silylation with N-methyl-N-trimethylsilyltrifluoroacetamide, MSTFA), and injection into a GC/MS. A quantitative analysis of almost 170 authentic serum samples and more than 50 authentic samples of other matrices like urine, different tissues, and heart blood on cocaine, benzoylecgonine, methadone, morphine, codeine, 6-monoacetylmorphine, dihydrocodeine, and 7-aminoflunitrazepam was conducted with both methods proving that the analytical results are equivalent even near the limits of quantification (low ng/ml range). To our best knowledge, this application is the first one reported in the literature employing this sample preparation system.

Determination of carbohydrates in medicinal plants--comparison between TLC, mf-MELDI-MS and GC-MS.

PubMed

Qureshi, Muhammad Nasimullah; Stecher, Guenther; Sultana, Tahira; Abel, Gudrun; Popp, Michael; Bonn, Guenther K

2011-01-01

Quality control in the pharmaceutical and phytopharmaceutical industries requires fast and reliable methods for the analysis of raw materials and final products. This study evaluates different analytical approaches in order to recognise the most suitable technique for the analysis of carbohydrates in herbal drug preparations. The specific focus of the study is on thin-layer chromatography (TLC), gas chromatography (GC), and a newly developed mass spectrometric method, i.e. matrix free material enhanced laser desorption/ionisation time of flight mass spectrometry (mf-MELDI-MS). Samples employed in the study were standards and microwave-assisted water extracts from Quercus. TLC analysis proved the presence of mono-, di- and trisaccharides within the biological sample and hinted at the existence of an unknown carbohydrate of higher oligomerisation degree. After evaluation of different derivatisation techniques, GC-MS confirmed data obtained via TLC for mono- to trisaccharides, delivering additionally quantified values under a considerable amount of time. A carbohydrate of higher oligomerisation degree could not be found. The application of mf-MELDI-MS further confirmed the presence of carbohydrates up to trisaccharides, also hinting at the presence of a form of tetrasaccharide. Besides this information, mf-MELDI-MS delivered further data about other substances present in the extract. Quantitative determination resulted in 1.750, 1.736 and 0.336 mg/mL for glucose, sucrose and raffinose respectively. Evaluation of all three techniques employed, clearly proved the heightened performance of mf-MELDI-MS for the qualitative analysis of complex mixtures, as targets do not need modification and analysis requires only a few minutes. In addition, GC-MS is suitable for quantitative analysis. Copyright © 2011 John Wiley & Sons, Ltd.

Orthogonal Comparison of GC-MS and 1H NMR Spectroscopy for Short Chain Fatty Acid Quantitation.

PubMed

Cai, Jingwei; Zhang, Jingtao; Tian, Yuan; Zhang, Limin; Hatzakis, Emmanuel; Krausz, Kristopher W; Smith, Philip B; Gonzalez, Frank J; Patterson, Andrew D

2017-08-01

Short chain fatty acids (SCFAs) are important regulators of host physiology and metabolism and may contribute to obesity and associated metabolic diseases. Interest in SCFAs has increased in part due to the recognized importance of how production of SCFAs by the microbiota may signal to the host. Therefore, reliable, reproducible, and affordable methods for SCFA profiling are required for accurate identification and quantitation. In the current study, four different methods for SCFA (acetic acid, propionic acid, and butyric acid) extraction and quantitation were compared using two independent platforms including gas chromatography coupled with mass spectrometry (GC-MS) and 1 H nuclear magnetic resonance (NMR) spectroscopy. Sensitivity, recovery, repeatability, matrix effect, and validation using mouse fecal samples were determined across all methods. The GC-MS propyl esterification method exhibited superior sensitivity for acetic acid and butyric acid measurement (LOD < 0.01 μg mL -1 , LOQ < 0.1 μg mL -1 ) and recovery accuracy (99.4%-108.3% recovery rate for 100 μg mL -1 SCFA mixed standard spike in and 97.8%-101.8% recovery rate for 250 μg mL -1 SCFAs mixed standard spike in). NMR methods by either quantitation relative to an internal standard or quantitation using a calibration curve yielded better repeatability and minimal matrix effects compared to GC-MS methods. All methods generated good calibration curve linearity (R 2 > 0.99) and comparable measurement of fecal SCFA concentration. Lastly, these methods were used to quantitate fecal SCFAs obtained from conventionally raised (CONV-R) and germ free (GF) mice. Results from global metabolomic analysis of feces generated by 1 H NMR and bomb calorimetry were used to further validate these approaches.

Rapid and Simultaneous Analysis of 360 Pesticides in Brown Rice, Spinach, Orange, and Potato Using Microbore GC-MS/MS.

PubMed

Lee, Jonghwa; Kim, Leesun; Shin, Yongho; Lee, Junghak; Lee, Jiho; Kim, Eunhye; Moon, Joon-Kwan; Kim, Jeong-Han

2017-04-26

A multiresidue method for the simultaneous and rapid analysis of 360 pesticides in representative agricultural produce (brown rice, orange, spinach, and potato) was developed using a modified QuEChERS procedure combined with gas chromatography-tandem mass spectrometry (GC-MS/MS). Selected reaction monitoring transition parameters (e.g., collision energy, precursor and product ions) in MS/MS were optimized to achieve the best selectivity and sensitivity for a wide range of GC-amenable pesticides. A short (20 m) microbore (0.18 mm i.d.) column resulted in better signal-to-noise ratio with reduced analysis time than a conventional narrowbore column (30 m × 0.25 mm i.d.). The priming injection dramatically increased peak areas by masking effect on a new GC liner. The limit of quantitation was <0.01 mg/kg, and the correlation coefficients (r 2 ) of matrix-matched standards were >0.99 within the range of 0.0025-0.1 mg/kg. Acetonitrile with 0.1% formic acid without additional buffer salts was used for pesticide extraction, whereas only primary-secondary amine (PSA) was used for dispersive solid phase extraction (dSPE) cleanup, to achieve good recoveries for most of the target analytes. The recoveries ranged from 70 to 120% with relative standard deviations of ≤20% at 0.01 and 0.05 mg/kg spiking levels (n = 6) in all samples, indicating acceptable accuracy and precision of the method. Seventeen real samples from local markets were analyzed by using the optimized method, and 14 pesticides in 11 incurred samples were found at below the maximum residue limits.

Evaluation of microtiter-plate enzyme-linked immunosorbent assay for the analysis of triazine and chloroacetanilide herbicides in rainfall

USGS Publications Warehouse

Pomes, M.L.; Thurman, E.M.; Aga, D.S.; Goolsby, D.A.

1998-01-01

Triazine and chloroacetanilide concentrations in rainfall samples collected from a 23-state region of the United States were analyzed with microtiter-plate enzyme-linked immunosorbent assay (ELISA). Thirty-six percent of rainfall samples (2072 out of 5691) were confirmed using gas chromatography/mass spectrometry (GC/MS) to evaluate the operating performance of ELISA as a screening test. Comparison of ELISA to GC/MS results showed that the two ELISA methods accurately reported GC/MS results (m = 1), but with more variability evident with the triazine than with the chloroacetanilide ELISA. Bayes's rule, a standardized method to report the results of screening tests, indicated that the two ELISA methods yielded comparable predictive values (80%), but the triazine ELISA yielded a false- positive rate of 11.8% and the chloroacetanilide ELISA yielded a false- negative rate of 23.1%. The false-positive rate for the triazine ELISA may arise from cross reactivity with an unknown triazine or metabolite. The false-negative rate of the chloroacetanilide ELISA probably resulted from a combination of low sensitivity at the reporting limit of 0.15 ??g/L and a distribution characterized by 75% of the samples at or below the reporting limit of 0.15 ??g/L.Triazine and chloroacetanilide concentrations in rainfall samples collected from a 23-state region of the United States were analyzed with microtiter-plate enzyme-linked immunosorbent assay (ELISA). Thirty-six percent of rainfall samples (2072 out of 5691) were confirmed using gas chromatography/mass spectrometry (GC/MS) to evaluate the operating performance of ELISA as a screening test. Comparison of ELISA to GC/MS results showed that the two ELISA methods accurately reported GC/MS results (m = 1), but with more variability evident with the triazine than with the chloroacetanilide ELISA. Bayes's rule, a standardized method to report the results of screening tests, indicated that the two ELISA methods yielded comparable predictive values (80%), but the triazine ELISA yielded a false-positive rate of 11.8% and the chloroacetanilide ELISA yielded a false-negative rate of 23.1%. The false-positive rate for the triazine ELISA may arise from cross reactivity with an unknown triazine or metabolite. The false-negative rate of the chloroacetanilide ELISA probably resulted from a combination of low sensitivity at the reporting limit of 0.15 ??g/L and a distribution characterized by 75% of the samples at or below the reporting limit of 0.15 ??g/L.

A selective and sensitive method for quantitation of lysergic acid diethylamide (LSD) in whole blood by gas chromatography-ion trap tandem mass spectrometry.

PubMed

Libong, Danielle; Bouchonnet, Stéphane; Ricordel, Ivan

2003-01-01

A gas chromatography-ion trap tandem mass spectrometry (GC-ion trap MS-MS) method for detection and quantitation of LSD in whole blood is presented. The sample preparation process, including a solid-phase extraction step with Bond Elut cartridges, was performed with 2 mL of whole blood. Eight microliters of the purified extract was injected with a cold on-column injection method. Positive chemical ionization was performed using acetonitrile as reagent gas; LSD was detected in the MS-MS mode. The chromatograms obtained from blood extracts showed the great selectivity of the method. GC-MS quantitation was performed using lysergic acid methylpropylamide as the internal standard. The response of the MS was linear for concentrations ranging from 0.02 ng/mL (detection threshold) to 10.0 ng/mL. Several parameters such as the choice of the capillary column, the choice of the internal standard and that of the ionization mode (positive CI vs. EI) were rationalized. Decomposition pathways under both ionization modes were studied. Within-day and between-day stability were evaluated.

Determination of Urinary PAH Metabolites Using DLLME Hyphenated to Injector Port Silylation and GC-MS-MS.

PubMed

Gupta, Manoj Kumar; Jain, Rajeev; Singh, Pratibha; Ch, Ratnasekhar; Mudiam, Mohana Krishna Reddy

2015-06-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants and well-known carcinogens. Hydroxy derivatives of PAH are considered as biomarkers of PAH exposure, and there is a need to measure these metabolites at low concentrations. So, a precise and eco-friendly analytical method has been developed for rapid determination of PAH metabolites. For the first time, a new analytical method based on coupling of dispersive liquid-liquid microextraction (DLLME) with auto-injector port silylation (auto-IPS) followed by gas chromatography-tandem mass spectrometry (GC-MS-MS) analysis is reported for the analysis of seven urinary PAH metabolites. Factors affecting DLLME and IPS, such as type and volume of extraction and disperser solvent, pH, ionic strength, injector port temperature, volume of N,O-bis(trimethylsilyl)trifluoroacetamide and type of solvent were investigated. Under optimized conditions, the limit of detection and limit of quantification were found to be in the range of 1-9 and 3-29 ng/mL, respectively. Satisfactory recoveries of metabolites in urine samples in the range of 87-95% were found. The developed method has been successfully applied for the determination of PAH metabolites in urine samples of exposed workers. DLLME-auto-IPS-GC-MS-MS method is time, labor, solvent and reagent saving, which can be routinely used for the analysis of urinary PAH metabolites. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Development of an indirect enzyme linked immunoassay for abscisic acid. [Pisum sativum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, G.S.; Elder, P.A.; McWha, J.A.

1987-09-01

AN INDIRECT METHOD OF ENZYME-LINKED-IMMUNOSORBENT-ASSAY (ELISA) IS REPORTED FOR ABSCISIC ACID (ABA), UTILIZING A THYROGLOBULIN-ABA CONJUGATE FOR COATING WELLS. THE ASSAY CAN USE COMMERCIALLY AVAILABLE MONOCLONAL ANTIBODIES, IS SENSITIVE TO AS LITTLE AS 20 PICOGRAMS ABA PER WELL, AND IS MUCH MORE CONSERVATIVE OF ANTIBODY THAN DIRECT METHODS. THE MOST DILUTE ABA STANDARDS DID NOT RETAIN THEIR ANTIGENICITY DURING STORAGE, SO ABA STANDARD SETS WERE DILUTED IMMEDIATELY PRIOR TO USE. THE INDIRECT ELISA WAS USED SUCCESSFULLY TO ESTIMATE ABA CONCENTRATIONS IN DEVELOPING COTYLEDONS OF PISUM SATIVUM L., AFTER ONLY LITTLE PRELIMINARY PURIFICATION. IT WAS VALIDATED FOR THIS TISSUE THROUGH THEmore » USE OF GAS CHROMATOGRAPHY-ELECTRON CAPTURE DETECTION (GC-EC), AND CAPILLARY GC-SELECTED ION MONITORING (GC-MS-SIM) USING LABELLED ABA AS AN INTERNAL STANDARD. FULL SPECTRUM GC-MASS SPECTROMETRY WAS ALSO USED TO VERIFY THAT ABA WAS PRESENT IN A SAMPLE ASSAYED QUANTITATIVELY BY BOTH ELISA AND GC-MS-SIM.« less

[Improvement of 2-mercaptoimidazoline analysis in rubber products containing chlorine].

PubMed

Kaneko, Reiko; Haneishi, Nahoko; Kawamura, Yoko

2012-01-01

An improved analysis method for 2-mercaptoimidazoline in rubber products containing chlorine was developed. 2-Mercaptoimidazoline (20 µg/mL) is detected by means of TLC with two developing solvents in the official method. But, this method is not quantitative. Instead, we employed HPLC using water-methanol (9 : 1) as the mobile phase. This procedure decreased interfering peaks, and the quantitation limit was 2 µg/mL of standard solution. 2-Mercaptoimidazoline was confirmed by GC-MS (5 µg/mL) and LC/MS (1 µg/mL) in the scan mode. For preparation of test solution, a soaking extraction method, in which 20 mL of methanol was added to the sample and allowed to stand overnight at about 40°C, was used. This gave similar values to the Soxhlet extraction method (official method) and was more convenient. The results indicate that our procedure is suitable for analysis of 2-mercaptoimidazoline. When 2-mercaptoimidazoline is detected, it is confirmed by either GC/MS or LC/MS.

Performance Evaluation of an Improved GC-MS Method to Quantify Methylmercury in Fish.

PubMed

Watanabe, Takahiro; Kikuchi, Hiroyuki; Matsuda, Rieko; Hayashi, Tomoko; Akaki, Koichi; Teshima, Reiko

2015-01-01

Here, we set out to improve our previously developed methylmercury analytical method, involving phenyl derivatization and gas chromatography-mass spectrometry (GC-MS). In the improved method, phenylation of methylmercury with sodium tetraphenylborate was carried out in a toluene/water two-phase system, instead of in water alone. The modification enabled derivatization at optimum pH, and the formation of by-products was dramatically reduced. In addition, adsorption of methyl phenyl mercury in the GC system was suppressed by co-injection of PEG200, enabling continuous analysis without loss of sensitivity. The performance of the improved analytical method was independently evaluated by three analysts using certified reference materials and methylmercury-spiked fresh fish samples. The present analytical method was validated as suitable for determination of compliance with the provisional regulation value for methylmercury in fish, set in the Food Sanitation haw.

Gas chromatography with flame photometric detection of 31 organophosphorus pesticide residues in Alpinia oxyphylla dried fruits.

PubMed

Zhao, Xiangsheng; Kong, Weijun; Wei, Jianhe; Yang, Meihua

2014-11-01

A simple, rapid and effective gas chromatography-flame photometric detection method was established for simultaneous multi-component determination of 31 organophosphorus pesticides (OPPs) residues in Alpinia oxyphylla, which is widely consumed as a traditional medicine and food in China. Sample preparation was completed in a single step without any clean-up procedure. All pesticides expressed good linear relationships between 0.004 and 1.0 μg/mL with correlation coefficients higher than 0.9973. The method gave satisfactory recoveries for most pesticides. The limits of detection varied from 1 to 10 ng/mL, and the limits of quantification (LOQs) were between 4 and 30 ng/mL. The proposed method was successfully applied to 55 commercial samples purchased from five different areas. Five pesticide residues were detected in four (7.27%) samples. The positive samples were confirmed by gas chromatography with tandem mass spectrometry (GC-MS/MS). Copyright © 2014 Elsevier Ltd. All rights reserved.

OPTIMIZATION OF HIGH-SPEED GC/TOFMS FOR METHOD TO-14 ANALYSIS

EPA Science Inventory

A fast GC/MS system (FGCMS) consisting of a high-speed gas chromatograph equipped with a narrow bandwidth injection accessory and a time-of-flight mass spectrometer detector is being optimized for analysis of Method TO-14 target compounds. The system consists entirely of comm...

Comprehensive and quantitative profiling of lipid species in human milk, cow milk and a phospholipid-enriched milk formula by GC and MS/MSALL.

PubMed

Sokol, Elena; Ulven, Trond; Færgeman, Nils J; Ejsing, Christer S

2015-06-01

Here we present a workflow for in-depth analysis of milk lipids that combines gas chromatography (GC) for fatty acid (FA) profiling and a shotgun lipidomics routine termed MS/MS ALL for structural characterization of molecular lipid species. To evaluate the performance of the workflow we performed a comparative lipid analysis of human milk, cow milk, and Lacprodan® PL-20, a phospholipid-enriched milk protein concentrate for infant formula. The GC analysis showed that human milk and Lacprodan have a similar FA profile with higher levels of unsaturated FAs as compared to cow milk. In-depth lipidomic analysis by MS/MS ALL revealed that each type of milk sample comprised distinct composition of molecular lipid species. Lipid class composition showed that the human and cow milk contain a higher proportion of triacylglycerols (TAGs) as compared to Lacprodan. Notably, the MS/MS ALL analysis demonstrated that the similar FA profile of human milk and Lacprodan determined by GC analysis is attributed to the composition of individual TAG species in human milk and glycerophospholipid species in Lacprodan. Moreover, the analysis of TAG molecules in Lacprodan and cow milk showed a high proportion of short-chain FAs that could not be monitored by GC analysis. The results presented here show that complementary GC and MS/MS ALL analysis is a powerful approach for characterization of molecular lipid species in milk and milk products. : Milk lipid analysis is routinely performed using gas chromatography. This method reports the total fatty acid composition of all milk lipids, but provides no structural or quantitative information about individual lipid molecules in milk or milk products. Here we present a workflow that integrates gas chromatography for fatty acid profiling and a shotgun lipidomics routine termed MS/MS ALL for structural analysis and quantification of molecular lipid species. We demonstrate the efficacy of this complementary workflow by a comparative analysis of molecular lipid species in human milk, cow milk, and a milk-based supplement used for infant formula.

Feasibility Research on Alternative Approaches for Sampling and Extraction Methods in the TO-4A Method for Pesticides in Ambient Air with Analysis by GC/MS and LC/MS/MS

EPA Science Inventory

This compilation of methods is the result of a Regional Methods project between the U.S. Environmental Protection Agency Region 4 and the EPA’s Office of Research and Development. The research leading to these methods was conducted in response to an observed need to update an EPA...

[Detection of methyl carbamate and ethyl carbamate in yellow rice wine by gas chromatography-mass spectrometry].

PubMed

Wu, Ping-gu; Ma, Bing-jie; Wang, Li-yuan; Shen, Xiang-hong; Zhang, Jing; Tan, Ying; Jiang, Wei

2013-11-01

To establish the method of simultaneous determination of methylcarbamate (MC) and ethylcarbamate (EC) in yellow rice wine by gas chromatography-mass spectrometry (GC/MS). MC and EC in yellow rice wine were derived by 9-xanthydrol, and then the derivants were detected by GC/MS; and quantitatively analyzed by D5-EC isotope internal standard method. The linearity of MC and EC ranged from 2.0 µg/L to 400.0 µg/L, with correlation coefficients at 0.998 and 0.999, respectively. The limits of quantitation (LOQ) and detection (LOD) were 0.67 and 2.0 µg/kg. When MC and EC were added in yellow rice wine at the range of 2.0-300.0 µg/kg, the intraday average recovery rate was 78.8%-102.3%, relative standard deviation was 3.2%-11.6%; interday average recovery rate was 75.4%-101.3%, relative standard deviation was 3.8%-13.4%. 20 samples of yellow rice wine from supermarket were detected using this method, the contents of MC were in the range of ND (no detected) to 1.2 µg/kg, the detection rate was 6% (3/20), the contents of EC in the range of 18.6 µg/kg to 432.3 µg/kg, with the average level at 135.2 µg/kg. The method is simple, rapid and useful for simultaneous determination of MC and EC in yellow rice wine.

Online in-tube microextractor coupled with UV-Vis spectrophotometer for bisphenol A detection.

PubMed

Poorahong, Sujittra; Thammakhet, Chongdee; Thavarungkul, Panote; Kanatharana, Proespichaya

2013-01-01

A simple and high extraction efficiency online in-tube microextractor (ITME) was developed for bisphenol A (BPA) detection in water samples. The ITME was fabricated by a stepwise electrodeposition of polyaniline, polyethylene glycol and polydimethylsiloxane composite (CPANI) inside a silico-steel tube. The obtained ITME coupled with UV-Vis detection at 278 nm was investigated. By this method, the extraction and pre-concentration of BPA in water were carried out in a single step. Under optimum conditions, the system provided a linear dynamic range of 0.1 to 100 μM with a limit of detection of 20 nM (S/N ≥3). A single in-tube microextractor had a good stability of more than 60 consecutive injections for 10.0 μM BPA with a relative standard deviation of less than 4%. Moreover, a good tube-to-tube reproducibility and precision were obtained. The system was applied to detect BPA in water samples from six brands of baby bottles and the results showed good agreement with those obtained from the conventional GC-MS method. Acceptable percentage recoveries from the spiked water samples were obtained, ranging from 83-102% for this new method compared with 73-107% for the GC-MS standard method. This new in-tube CPANI microextractor provided an excellent extraction efficiency and a good reproducibility. In addition, it can also be easily applied for the analysis of other polar organic compounds contaminated in water sample.

Comparative Analysis of Volatile Composition in Chinese Truffles via GC × GC/HR-TOF/MS and Electronic Nose

PubMed Central

Zhang, Ning; Chen, Haitao; Sun, Baoguo; Mao, Xueying; Zhang, Yuyu; Zhou, Ying

2016-01-01

To compare the volatile compounds of Chinese black truffle and white truffle from Yunnan province, this study presents the application of a direct solvent extraction/solvent-assisted flavor evaporation (DSE-SAFE) coupled with a comprehensive two-dimensional gas chromatography (GC × GC) high resolution time-of-flight mass spectrometry (HR-TOF/MS) and an electronic nose. Both of the analytical methods could distinguish the aroma profile of the two samples. In terms of the overall profile of truffle samples in this research, more kinds of acids were detected via the method of DSE-SAFE. Besides, compounds identified in black truffle (BT), but not in white truffle (WT), or vice versa, and those detected in both samples at different levels were considered to play an important role in differentiating the two samples. According to the analysis of electronic nose, the two samples could be separated, as well. PMID:27058524

An Exploration on the Suitability of Airborne Carbonyl Compounds Analysis in relation to Differences in Instrumentation (GC-MS versus HPLC-UV) and Standard Phases (Gas versus Liquid)

PubMed Central

Kim, Ki-Hyun; Szulejko, Jan E.; Kim, Yong-Hyun; Lee, Min-Hee

2014-01-01

The relative performance figure of merits was investigated for the two most common analytical methods employed for carbonyl compounds (CC), for example, between high performance liquid chromatography (HPLC)-UV detector (with 2,4-dinitrophenylhydrazine (DNPH) derivatization) and thermal desorption (TD)-gas chromatography (GC)-mass spectrometry (MS) (without derivatization). To this end, the suitability of each method is assessed by computing the relative recovery (RR) between the gas- and liquid-phase standards containing a suite of CC such as formaldehyde (FA), acetaldehyde (AA), propionaldehyde (PA), butyraldehyde (BA), isovaleraldehyde (IA), and valeraldehyde (VA) along with benzene (B) as a recovery reference for the GC method. The results confirm that a TD-GC-MS is advantageous to attain the maximum recovery for the heavier CCs (i.e., with molecular weights (MW) above BA−MW ≥ 74). On the other hand, the HPLC-UV is favorable for the lighter CCs (like FA and AA) with the least bias. Such compound-specific responses for each platform are validated by relative ordering of CCs as a function of response factor (RF), method detection limit (MDL), and recovery pattern. It is thus desirable to understand the advantages and limitations of each method to attain the CC data with the least experimental bias. PMID:24719571

Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC.

PubMed

Materić, Dušan; Lanza, Matteo; Sulzer, Philipp; Herbig, Jens; Bruhn, Dan; Turner, Claire; Mason, Nigel; Gauci, Vincent

2015-10-01

Proton transfer reaction mass spectrometry (PTR-MS) is a well-established technique for real-time analysis of volatile organic compounds (VOCs). Although it is extremely sensitive (with sensitivities of up to 4500 cps/ppbv, limits of detection <1 pptv and the response times of approximately 100 ms), the selectivity of PTR-MS is still somewhat limited, as isomers cannot be separated. Recently, selectivity-enhancing measures, such as manipulation of drift tube parameters (reduced electric field strength) and using primary ions other than H3O(+), such as NO(+) and O2 (+), have been introduced. However, monoterpenes, which belong to the most important plant VOCs, still cannot be distinguished so more traditional technologies, such as gas chromatography mass spectrometry (GC-MS), have to be utilised. GC-MS is very time consuming (up to 1 h) and cannot be used for real-time analysis. Here, we introduce a sensitive, near-to-real-time method for plant monoterpene research-PTR-MS coupled with fastGC. We successfully separated and identified six of the most abundant monoterpenes in plant studies (α- and β-pinenes, limonene, 3-carene, camphene and myrcene) in less than 80 s, using both standards and conifer branch enclosures (Norway spruce, Scots pine and black pine). Five monoterpenes usually present in Norway spruce samples with a high abundance were separated even when the compound concentrations were diluted to 20 ppbv. Thus, fastGC-PTR-ToF-MS was shown to be an adequate one-instrument solution for plant monoterpene research.

Simultaneous quantification of epoxy and hydroxy fatty acids as oxidation products of triacylglycerols in edible oils.

PubMed

Xia, Wei; Budge, Suzanne M

2018-02-16

Epoxy and hydroxy fatty acids are important intermediates during lipid oxidation; quantification of both structures may help evaluate the extent of competition among various lipid oxidation pathways. This article describes a method to simultaneously determine saturated- and unsaturated- epoxy and hydroxy fatty acids derived from oxidation of vegetable oils. The experimental procedures employed transesterification with sodium methoxide, separation of epoxy and hydroxy fatty acid methyl esters (FAME) using solid-phase extraction (SPE), and trimethylsilyl (TMS) derivatization of hydroxy groups. GC-MS was used to identify the epoxy and hydroxy FAME in two different SPE fractions, while GC-flame ionization detection (GC-FID) was used to determine their quantities. Epoxy-octadecanoate/octadecenoate and hydroxy-octadecanoate/octadecenoate/octadecadienoate were determined as lipid oxidation products generated from oxidation of sunflower and canola oils. An isomer of methyl 13-hydroxyoctadeca-9,11-dienoate (13-HODE) TMS ether co-eluted with methyl 15-hydroxyoctadeca-9,12-dienoate TMS ether, which was only present in canola oil; thus, GC-MS-selected ion monitoring (GC-MS-SIM) was used to determine the concentration of 13-HODE. The proposed method has been successfully applied to monitor epoxy and hydroxy fatty acids in sunflower oil and canola oil oxidized at 40 °C. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of Linum usitatissimum L. oil obtained from different extraction technique and in vitro antioxidant potential of supercritical fluid extract

PubMed Central

Chauhan, Rishika; Chester, Karishma; Khan, Yasmeen; Tamboli, Ennus Tajuddin; Ahmad, Sayeed

2015-01-01

Aim: Present investigation was aimed to characterize the fixed oil of Linum usitatissimum L. using five different extraction methods: Supercritical fluid extraction (SFE), ultrasound-assistance, soxhlet extraction, solvent extraction, and three phase partitioning method. Materials and Methods: The SFE conditions (temperature, pressure, and volume of CO2) were optimized prior for better yield. The extracted oils were analyzed and compared for their physiochemical parameters, high performance thin layer chromatography (HPTLC), gas chromatography-mass spectrometry (GC-MS), and Fourier-transformed infrared spectroscopy (FT-IR) fingerprinting. Antioxidant activity was also determined using 1,1-diphenyl-2-picrylhydrazyl and superoxide scavenging method. Result: The main fatty acids were α-linolenic acid, linoleic acid, palmitic acid, and stearic acid as obtained by GC-MS. HPTLC analysis revealed the presence of similar major components in chromatograms. Similarly, the pattern of peaks, as obtained in FT-IR and GC-MS spectra of same oils by different extraction methods, were superimposable. Conclusion: Analysis reported that the fixed oil of L. usitatissimum L. is a good source of n-3 fatty acid with the significant antioxidant activity of oil obtained from SFE extraction method. PMID:26681884

Rapid screening of selective serotonin re-uptake inhibitors in urine samples using solid-phase microextraction gas chromatography-mass spectrometry.

PubMed

Salgado-Petinal, Carmen; Lamas, J Pablo; Garcia-Jares, Carmen; Llompart, Maria; Cela, Rafael

2005-07-01

In this paper a solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)-venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline-in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL(-1) urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified.

Evaluation of gas chromatography-tandem quadrupole mass spectrometry for the determination of organochlorine pesticides in fats and oils.

PubMed

Patel, Katan; Fussell, Richard J; Hetmanski, Mike; Goodall, David M; Keely, Brendan J

2005-03-18

A gas chromatography-tandem quadrupole mass spectrometry multi-residue method for the analysis of 19 organochlorine pesticides in fats and oils has been developed. Gel permeation chromatography was employed to remove lipid material prior to GC-MS/MS analysis. Average recoveries of the pesticides spiked at 10 and 50 microg kg(-1) into fish oil, pork fat, olive oil and hydrogenated vegetable oil were typically in the range 70-110% with relative standard deviations generally less than 10%. Calculated limits of detection are between 0.1 and 2.0 microg kg(-1) and results obtained for the analysis of proficiency test materials are in good agreement with assigned values. The higher selectivity of the GC-MS/MS compared to electron capture detection and GC-MS in selective ion monitoring mode allowed unambiguous identification and confirmation of all the target pesticides at low microg kg(-1) levels in fats and oils in a single analysis.

Characterizing Vaccinium berry Standard Reference Materials by GC-MS using NIST spectral libraries.

PubMed

Lowenthal, Mark S; Andriamaharavo, Nirina R; Stein, Stephen E; Phinney, Karen W

2013-05-01

A gas chromatography-mass spectrometry (GC-MS)-based method was developed for qualitative characterization of metabolites found in Vaccinium fruit (berry) dietary supplement Standard Reference Materials (SRMs). Definitive identifications are provided for 98 unique metabolites determined among six Vaccinium-related SRMs. Metabolites were enriched using an organic liquid/liquid extraction, and derivatized prior to GC-MS analysis. Electron ionization (EI) fragmentation spectra were searched against EI spectra of authentic standards compiled in the National Institute of Standards and Technology's mass spectral libraries, as well as spectra selected from the literature. Metabolite identifications were further validated using a retention index match along with prior probabilities and were compared with results obtained in a previous effort using collision-induced dissociation (CID) MS/MS datasets from liquid chromatography coupled to mass spectrometry experiments. This manuscript describes a nontargeted metabolite profile of Vaccinium materials, compares results among related materials and from orthogonal experimental platforms, and discusses the feasibility and development of using mass spectral library matching for nontargeted metabolite identification.

Characterization of organic particulates present in milk factory process waters used for reuse along with aerobically digested effluent wastewater.

PubMed

Verheyen, Vincent; Cruickshank, Alicia; Wild, Karl; Heaven, Michael W; McGee, Rachel; Watkins, Mark; Nash, David

2011-01-01

Wastewater from a dairy processor is being reused and recycled both within the plant and for irrigation. Flash pyrolysis GC-MS was used to examine nitrogen and phenol containing compounds (M.W.=35 to 450 g/mol) in the particulate fraction of the milk condensate, combined clean wastewater and aerobic bioreactor effluent. For comparison, the particulates were also prepared for standard GC-MS analyses using conventional solvent extraction methods. Compounds detected by pyrolysis GC-MS were found mostly in the bioreactor with the amino acid arginine (220 mg/kg) and the amino acid derivative 1-methyl-5-oxo-L-proline methyl ester (130 mg/kg) found at the highest concentrations. In comparison, sterols detected in the effluent were found at higher concentrations when using solvent extraction indicating some degradation with pyrolysis GC-MS. However, with few exceptions, particulates were generally found not to act as passive collectors capable of concentrating less water soluble chemicals. Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

Screening of the chemical composition and bioactivity of Waldheimia glabra (Decne.) Regel essential oil.

PubMed

Manzo, Alessandra; Musso, Loana; Panseri, Sara; Iriti, Marcello; Dallavalle, Sabrina; Catalano, Enrico; Scarì, Giorgio; Giorgi, Annamaria

2016-07-01

This research aimed at improving knowledge as to the chemical composition and the antibacterial and anti-cancer activities of the essential oil of Waldheimia glabra, a wild plant from the Himalayan Mountains. The results obtained by GC-MS showed that spathulenol, 9-tetradecenol, thujopsene, α-thujone, santolina alcohol and terpinen-4-ol were the main constituents of Waldheimia glabra essential oil. These results were confirmed by HS-SPME GC-MS analysis that also reported high amounts of artemisia alcohol and camphor. Disc diffusion assay suggested a mild antibacterial activity against both Escherichia coli and Staphylococcus aureus. Finally, a dose-response correlation was observed between Waldhemia glabra essential oil concentration and viability of human breast adenocarcinoma cells MDA-MB-231 and MCF-7. Together with the GC-MS method, HS-SPME GC-MS proved to be a reliable technique to characterise the chemical composition of essential oil obtained from aromatic plants. Further studies will focus on W. glabra phytochemicals and their biological activity, in order to support traditional uses of the plant. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

EIA and GC/MS analysis of 8-isoprostane in EBC of children with problematic asthma.

PubMed

Carraro, S; Cogo, P E; Isak, I; Simonato, M; Corradi, M; Carnielli, V P; Baraldi, E

2010-06-01

Asthmatic airways are characterised by enhanced oxidative stress, which can be studied by measuring biomarkers, such as 8-isoprostane. The aims of the present study were: 1) to measure the concentrations of 8-isoprostane in exhaled breath condensate (EBC) and urine of children with problematic and well-controlled asthma; 2) to compare the concentrations of 8-isoprostane measured by gas chromatographic/negative ion chemical ionisation mass spectrometry (GC/NICI-MS) and by an enzymatic immunoassay (EIA). We recruited 20 asthmatic allergic children, 13 with well-controlled asthma and seven with problematic asthma. They underwent exhaled nitric oxide measurements and spirometry, and both EBC and urine samples were collected. 8-isoprostane was measured in EBC by GC/NICI-MS and EIA. 8-isoprostane concentrations in EBC were significantly higher in children with problematic asthma than in children with well-controlled asthma (p = 0.01). An acceptable reproducibility emerged between GC/NICI-MS and EIA (coefficient of reproducibility 11.5 pg x mL(-1)). 8-isoprostane levels measured in urine did not correlate with those measured in EBC. We showed that 8-isoprostane in EBC was significantly increased in children with problematic asthma, suggesting a role for oxidative stress in this asthma phenotype. In addition we found an acceptable reproducibility of EIA compared to GC/NICI-MS, even if the latter method had higher accuracy.

Eucalyptus essential oil as a natural food preservative: in vivo and in vitro antiyeast potential.

PubMed

Tyagi, Amit Kumar; Bukvicki, Danka; Gottardi, Davide; Tabanelli, Giulia; Montanari, Chiara; Malik, Anushree; Guerzoni, Maria Elisabetta

2014-01-01

In this study, the application of eucalyptus essential oil/vapour as beverages preservative is reported. The chemical composition of eucalyptus oil was determined by gas chromatography-mass spectrometry (GC-MS) and solid phase microextraction GC-MS (SPME/GC-MS) analyses. GC-MS revealed that the major constituents were 1,8-cineole (80.5%), limonene (6.5%), α-pinene (5%), and γ-terpinene (2.9%) while SPME/GC-MS showed a relative reduction of 1,8-cineole (63.9%) and an increase of limonene (13.8%), α-pinene (8.87%), and γ-terpinene (3.98%). Antimicrobial potential of essential oil was initially determined in vitro against 8 different food spoilage yeasts by disc diffusion, disc volatilization, and microdilution method. The activity of eucalyptus vapours was significantly higher than the eucalyptus oil. Minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) varied from 0.56 to 4.50 mg/mL and from 1.13 to 9 mg/mL, respectively. Subsequently, the combined efficacy of essential oil and thermal treatment were used to evaluate the preservation of a mixed fruit juice in a time-dependent manner. These results suggest eucalyptus oil as a potent inhibitor of food spoilage yeasts not only in vitro but also in a real food system. Currently, this is the first report that uses eucalyptus essential oil for fruit juice preservation against food spoiling yeast.

Eucalyptus Essential Oil as a Natural Food Preservative: In Vivo and In Vitro Antiyeast Potential

PubMed Central

Bukvicki, Danka; Gottardi, Davide; Malik, Anushree; Guerzoni, Maria Elisabetta

2014-01-01

In this study, the application of eucalyptus essential oil/vapour as beverages preservative is reported. The chemical composition of eucalyptus oil was determined by gas chromatography-mass spectrometry (GC-MS) and solid phase microextraction GC-MS (SPME/GC-MS) analyses. GC-MS revealed that the major constituents were 1,8-cineole (80.5%), limonene (6.5%), α-pinene (5%), and γ-terpinene (2.9%) while SPME/GC-MS showed a relative reduction of 1,8-cineole (63.9%) and an increase of limonene (13.8%), α-pinene (8.87%), and γ-terpinene (3.98%). Antimicrobial potential of essential oil was initially determined in vitro against 8 different food spoilage yeasts by disc diffusion, disc volatilization, and microdilution method. The activity of eucalyptus vapours was significantly higher than the eucalyptus oil. Minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) varied from 0.56 to 4.50 mg/mL and from 1.13 to 9 mg/mL, respectively. Subsequently, the combined efficacy of essential oil and thermal treatment were used to evaluate the preservation of a mixed fruit juice in a time-dependent manner. These results suggest eucalyptus oil as a potent inhibitor of food spoilage yeasts not only in vitro but also in a real food system. Currently, this is the first report that uses eucalyptus essential oil for fruit juice preservation against food spoiling yeast. PMID:25177704

Glucocorticoid Induction of Occludin Expression and Endothelial Barrier Requires Transcription Factor p54 NONO

PubMed Central

Keil, Jason M.; Liu, Xuwen; Antonetti, David A.

2013-01-01

Purpose. Glucocorticoids (GCs) effectively reduce retinal edema and induce vascular barrier properties but possess unwanted side effects. Understanding GC induction of barrier properties may lead to more effective and specific therapies. Previous work identified the occludin enhancer element (OEE) as a GC-responsive cis-element in the promoters of multiple junctional genes, including occludin, claudin-5, and cadherin-9. Here, we identify two OEE-binding factors and determine their contribution to GC induction of tight junction (TJ) gene expression and endothelial barrier properties. Methods. OEE-binding factors were isolated from human retinal endothelial cells (HREC) using DNA affinity purification followed by MALDI-TOF MS/MS. Chromatin immunoprecipitation (ChIP) assays determined in situ binding. siRNA was used to evaluate the role of trans-acting factors in transcription of TJ genes in response to GC stimulation. Paracellular permeability was determined by quantifying flux through a cell monolayer, whereas transendothelial electrical resistance (TER) was measured using the ECIS system. Results. MS/MS analysis of HREC nuclear extracts identified the heterodimer of transcription factors p54/NONO (p54) and polypyrimidine tract-binding protein-associated splicing factor (PSF) as OEE-binding factors, which was confirmed by ChIP assay from GC-treated endothelial cells and rat retina. siRNA knockdown of p54 demonstrated that this factor is necessary for GC induction of occludin and claudin-5 expression. Further, p54 knockdown ablated the pro-barrier effects of GC treatment. Conclusions. p54 is essential for GC-mediated expression of occludin, claudin-5, and barrier induction, and the p54/PSF heterodimer may contribute to normal blood-retinal barrier (BRB) induction in vivo. Understanding the mechanism of GC induction of BRB properties may provide novel therapies for macular edema. PMID:23640037

Validation of the analytical method for the simultaneous determination of selected polybrominated diphenyl ethers, polychlorinated biphenyls and organochlorine pesticides in human blood serum by gas chromatography with microelectron capture detector.

PubMed

Matuszak, Małgorzata; Minorczyk, Maria; Góralczyk, Katarzyna; Hernik, Agnieszka; Struciński, Paweł; Liszewska, Monika; Czaja, Katarzyna; Korcz, Wojciech; Łyczewska, Monika; Ludwicki, Jan K

2016-01-01

Polybrominated diphenyl ethers (PBDEs) as other persistent organic pollutants like polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) pose a significant hazard to human health, mainly due to interference with the endocrine system and carcinogenetic effects. Humans are exposed to these substances mainly through a food of animal origin. These pollutants are globally detected in human matrices which requires to dispose reliable and simple analytical method that would enable further studies to assess the exposure of specific human populations to these compounds. The purpose of this study was to modify and validate of the analytical procedure for the simultaneous determination of selected PBDEs, PCBs and OCPs in human blood serum samples. The analytical measurement was performed by GC-µECD following preparation of serum samples (denaturation, multiple extraction, lipid removal). Identity of the compounds was confirmed by GC-MS. The method was characterised by the appropriate linearity, good repeatability (CV below 20%). The recoveries ranged from 52.9 to 125.0% depending on compound and level of fortification. The limit of quantification was set at 0.03 ng mL(-1) of serum. The modified analytical method proved to be suitable for the simultaneous determination of selected PBDEs, PCBs and OCPs in human blood serum by GC-µECD with good precision.

Fast determination of 3-ethenylpyridine as a marker of environmental tobacco smoke at trace level using direct atmospheric pressure chemical ionization tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Jiang, Cheng-Yong; Sun, Shi-Hao; Zhang, Qi-Dong; Liu, Jun-Hui; Zhang, Jian-Xun; Zong, Yong-Li; Xie, Jian-Ping

2013-03-01

A method with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) was developed and applied to direct analysis of Environmental Tobacco Smoke (ETS), using 3-ethenylpyridine (3-EP) as a vapour-phase marker. In this study, the ion source of APCI-MS/MS was modified and direct analysis of gas sample was achieved by the modified instrument. ETS samples were directly introduced, via an atmospheric pressure inlet, into the APCI source. Ionization was carried out in positive-ion APCI mode and 3-EP was identified by both full scan mode and daughter scan mode. Quantification of 3-EP was performed by multiple reaction monitoring (MRM) mode. The calibration curve was obtained in the range of 1-250 ng L-1 with a satisfactory regression coefficient of 0.999. The limit of detection (LOD) and the limit of quantification (LOQ) were 0.5 ng L-1 and 1.6 ng L-1, respectively. The precision of the method, calculated as relative standard deviation (RSD), was characterized by repeatability (RSD 3.92%) and reproducibility (RSD 4.81%), respectively. In real-world ETS samples analysis, compared with the conventional GC-MS method, the direct APCI-MS/MS has shown better reliability and practicability in the determination of 3-EP at trace level. The developed method is simple, fast, sensitive and repeatable; furthermore, it could provide an alternative way for the determination of other volatile pollutants in ambient air at low levels.

Qualitative Analysis of E-Liquid Emissions as a Function of Flavor Additives Using Two Aerosol Capture Methods.

PubMed

Eddingsaas, Nathan; Pagano, Todd; Cummings, Cody; Rahman, Irfan; Robinson, Risa; Hensel, Edward

2018-02-13

This work investigates emissions sampling methods employed for qualitative identification of compounds in e-liquids and their resultant aerosols to assess what capture methods may be sufficient to identify harmful and potentially harmful constituents present. Three popular e-liquid flavors (cinnamon, mango, vanilla) were analyzed using qualitative gas chromatography-mass spectrometry (GC-MS) in the un-puffed state. Each liquid was also machine-puffed under realistic-use flow rate conditions and emissions were captured using two techniques: filter pads and methanol impingers. GC-MS analysis was conducted on the emissions captured using both techniques from all three e-liquids. The e-liquid GC-MS analysis resulted in positive identification of 13 compounds from the cinnamon flavor e-liquid, 31 from mango, and 19 from vanilla, including a number of compounds observed in all e-liquid experiments. Nineteen compounds were observed in emissions which were not present in the un-puffed e-liquid. Qualitative GC-MS analysis of the emissions samples identify compounds observed in all three samples: e-liquid, impinge, and filter pads, and each subset thereof. A limited number of compounds were observed in emissions captured with impingers, but were not observed in emissions captured using filter pads; a larger number of compounds were observed on emissions collected from the filter pads, but not those captured with impingers. It is demonstrated that sampling methods have different sampling efficiencies and some compounds might be missed using only one method. It is recommended to investigate filter pads, impingers, thermal desorption tubes, and solvent extraction resins to establish robust sampling methods for emissions testing of e-cigarette emissions.

Qualitative Analysis of E-Liquid Emissions as a Function of Flavor Additives Using Two Aerosol Capture Methods

PubMed Central

Eddingsaas, Nathan; Pagano, Todd; Cummings, Cody; Rahman, Irfan; Robinson, Risa

2018-01-01

This work investigates emissions sampling methods employed for qualitative identification of compounds in e-liquids and their resultant aerosols to assess what capture methods may be sufficient to identify harmful and potentially harmful constituents present. Three popular e-liquid flavors (cinnamon, mango, vanilla) were analyzed using qualitative gas chromatography-mass spectrometry (GC-MS) in the un-puffed state. Each liquid was also machine-puffed under realistic-use flow rate conditions and emissions were captured using two techniques: filter pads and methanol impingers. GC-MS analysis was conducted on the emissions captured using both techniques from all three e-liquids. The e-liquid GC-MS analysis resulted in positive identification of 13 compounds from the cinnamon flavor e-liquid, 31 from mango, and 19 from vanilla, including a number of compounds observed in all e-liquid experiments. Nineteen compounds were observed in emissions which were not present in the un-puffed e-liquid. Qualitative GC-MS analysis of the emissions samples identify compounds observed in all three samples: e-liquid, impinge, and filter pads, and each subset thereof. A limited number of compounds were observed in emissions captured with impingers, but were not observed in emissions captured using filter pads; a larger number of compounds were observed on emissions collected from the filter pads, but not those captured with impingers. It is demonstrated that sampling methods have different sampling efficiencies and some compounds might be missed using only one method. It is recommended to investigate filter pads, impingers, thermal desorption tubes, and solvent extraction resins to establish robust sampling methods for emissions testing of e-cigarette emissions. PMID:29438289

Application of mass spectrometry based electronic nose and chemometrics for fingerprinting radiation treatment

NASA Astrophysics Data System (ADS)

Gupta, Sumit; Variyar, Prasad S.; Sharma, Arun

2015-01-01

Volatile compounds were isolated from apples and grapes employing solid phase micro extraction (SPME) and subsequently analyzed by GC/MS equipped with a transfer line without stationary phase. Single peak obtained was integrated to obtain total mass spectrum of the volatile fraction of samples. A data matrix having relative abundance of all mass-to-charge ratios was subjected to principal component analysis (PCA) and linear discriminant analysis (LDA) to identify radiation treatment. PCA results suggested that there is sufficient variability between control and irradiated samples to build classification models based on supervised techniques. LDA successfully aided in segregating control from irradiated samples at all doses (0.1, 0.25, 0.5, 1.0, 1.5, 2.0 kGy). SPME-MS with chemometrics was successfully demonstrated as simple screening method for radiation treatment.

In-tube extraction and GC-MS analysis of volatile components from wild and cultivated sea buckthorn (Hippophae rhamnoides L. ssp. Carpatica) berry varieties and juice.

PubMed

Socaci, Sonia A; Socaciu, Carmen; Tofană, Maria; Raţi, Ioan V; Pintea, Adela

2013-01-01

The health benefits of sea buckthorn (Hippophae rhamnoides L.) are well documented due to its rich content in bioactive phytochemicals (pigments, phenolics and vitamins) as well as volatiles responsible for specific flavours and bacteriostatic action. The volatile compounds are good biomarkers of berry freshness, quality and authenticity. To develop a fast and efficient GC-MS method including a minimal sample preparation technique (in-tube extraction, ITEX) for the discrimination of sea buckthorn varieties based on their chromatographic volatile fingerprint. Twelve sea buckthorn varieties (wild and cultivated) were collected from forestry departments and experimental fields, respectively. The extraction of volatile compounds was performed using the ITEX technique whereas separation and identification was performed using a GC-MS QP-2010. Principal component analysis (PCA) was applied to discriminate the differences among sample composition. Using GC-MS analysis, from the headspace of sea buckthorn samples, 46 volatile compounds were separated with 43 being identified. The most abundant derivatives were ethyl esters of 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, octanoic acid and butanoic acid, as well as 3-methylbutyl 3-methylbutanoate, 3-methylbutyl 2-methylbutanoate and benzoic acid ethyl ester (over 80% of all volatile compounds). Principal component analysis showed that the first two components explain 79% of data variance, demonstrating a good discrimination between samples. A reliable, fast and eco-friendly ITEX/GC-MS method was applied to fingerprint the volatile profile and to discriminate between wild and cultivated sea buckthorn berries originating from the Carpathians, with relevance to food science and technology. Copyright © 2013 John Wiley & Sons, Ltd.

TargetSearch--a Bioconductor package for the efficient preprocessing of GC-MS metabolite profiling data.

PubMed

Cuadros-Inostroza, Alvaro; Caldana, Camila; Redestig, Henning; Kusano, Miyako; Lisec, Jan; Peña-Cortés, Hugo; Willmitzer, Lothar; Hannah, Matthew A

2009-12-16

Metabolite profiling, the simultaneous quantification of multiple metabolites in an experiment, is becoming increasingly popular, particularly with the rise of systems-level biology. The workhorse in this field is gas-chromatography hyphenated with mass spectrometry (GC-MS). The high-throughput of this technology coupled with a demand for large experiments has led to data pre-processing, i.e. the quantification of metabolites across samples, becoming a major bottleneck. Existing software has several limitations, including restricted maximum sample size, systematic errors and low flexibility. However, the biggest limitation is that the resulting data usually require extensive hand-curation, which is subjective and can typically take several days to weeks. We introduce the TargetSearch package, an open source tool which is a flexible and accurate method for pre-processing even very large numbers of GC-MS samples within hours. We developed a novel strategy to iteratively correct and update retention time indices for searching and identifying metabolites. The package is written in the R programming language with computationally intensive functions written in C for speed and performance. The package includes a graphical user interface to allow easy use by those unfamiliar with R. TargetSearch allows fast and accurate data pre-processing for GC-MS experiments and overcomes the sample number limitations and manual curation requirements of existing software. We validate our method by carrying out an analysis against both a set of known chemical standard mixtures and of a biological experiment. In addition we demonstrate its capabilities and speed by comparing it with other GC-MS pre-processing tools. We believe this package will greatly ease current bottlenecks and facilitate the analysis of metabolic profiling data.

TargetSearch - a Bioconductor package for the efficient preprocessing of GC-MS metabolite profiling data

PubMed Central

2009-01-01

Background Metabolite profiling, the simultaneous quantification of multiple metabolites in an experiment, is becoming increasingly popular, particularly with the rise of systems-level biology. The workhorse in this field is gas-chromatography hyphenated with mass spectrometry (GC-MS). The high-throughput of this technology coupled with a demand for large experiments has led to data pre-processing, i.e. the quantification of metabolites across samples, becoming a major bottleneck. Existing software has several limitations, including restricted maximum sample size, systematic errors and low flexibility. However, the biggest limitation is that the resulting data usually require extensive hand-curation, which is subjective and can typically take several days to weeks. Results We introduce the TargetSearch package, an open source tool which is a flexible and accurate method for pre-processing even very large numbers of GC-MS samples within hours. We developed a novel strategy to iteratively correct and update retention time indices for searching and identifying metabolites. The package is written in the R programming language with computationally intensive functions written in C for speed and performance. The package includes a graphical user interface to allow easy use by those unfamiliar with R. Conclusions TargetSearch allows fast and accurate data pre-processing for GC-MS experiments and overcomes the sample number limitations and manual curation requirements of existing software. We validate our method by carrying out an analysis against both a set of known chemical standard mixtures and of a biological experiment. In addition we demonstrate its capabilities and speed by comparing it with other GC-MS pre-processing tools. We believe this package will greatly ease current bottlenecks and facilitate the analysis of metabolic profiling data. PMID:20015393

Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis.

PubMed

van der Veen, Ike; de Boer, Jacob

2012-08-01

Since the ban on some brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), which were responsible for 20% of the flame retardant (FR) consumption in 2006 in Europe, are often proposed as alternatives for BFRs. PFRs can be divided in three main groups, inorganic, organic and halogen containing PFRs. Most of the PFRs have a mechanism of action in the solid phase of burning materials (char formation), but some may also be active in the gas phase. Some PFRs are reactive FRs, which means they are chemically bound to a polymer, whereas others are additive and mixed into the polymer. The focus of this report is limited to the PFRs mentioned in the literature as potential substitutes for BFRs. The physico-chemical properties, applications and production volumes of PFRs are given. Non-halogenated PFRs are often used as plasticisers as well. Limited information is available on the occurrence of PFRs in the environment. For triphenyl phosphate (TPhP), tricresylphosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(chloropropyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), and tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6) a number of studies have been performed on their occurrence in air, water and sediment, but limited data were found on their occurrence in biota. Concentrations found for these PFRs in air were up to 47 μg m(-3), in sediment levels up to 24 mg kg(-1) were found, and in surface water concentrations up to 379 ng L(-1). In all these matrices TCPP was dominant. Concentrations found in dust were up to 67 mg kg(-1), with TDCPP being the dominant PFR. PFR concentrations reported were often higher than polybrominated diphenylether (PBDE) concentrations, and the human exposure due to PFR concentrations in indoor air appears to be higher than exposure due to PBDE concentrations in indoor air. Only the Cl-containing PFRs are carcinogenic. Other negative human health effects were found for Cl-containing PFRs as well as for TCP, which suggest that those PFRs would not be suitable alternatives for BFRs. TPhP, diphenylcresylphosphate (DCP) and TCP would not be suitable alternatives either, because they are considered to be toxic to (aquatic) organisms. Diethylphosphinic acid is, just like TCEP, considered to be very persistent. From an environmental perspective, resorcinol-bis(diphenylphosphate) (RDP), bisphenol-A diphenyl phosphate (BADP) and melamine polyphosphate, may be suitable good substitutes for BFRs. Information on PFR analysis in air, water and sediment is limited to TCEP, TCPP, TPhP, TCP and some other organophosphate esters. For air sampling passive samplers have been used as well as solid phase extraction (SPE) membranes, SPE cartridges, and solid phase micro-extraction (SPME). For extraction of PFRs from water SPE is recommended, because this method gives good recoveries (67-105%) and acceptable relative standard deviations (RSDs) (<20%), and offers the option of on-line coupling with a detection system. For the extraction of PFRs from sediment microwave-assisted extraction (MAE) is recommended. The recoveries (78-105%) and RSDs (3-8%) are good and the method is faster and requires less solvent compared to other methods. For the final instrumental analysis of PFRs, gas chromatography-flame photometric detection (GC-FPD), GC-nitrogen-phosphorus detection (NPD), GC-atomic emission detection (AED), GC-mass spectrometry (MS) as well as liquid chromatography (LC)-MS/MS and GC-Inductively-coupled plasma-MS (ICP-MS) are used. GC-ICP-MS is a promising method, because it provides much less complex chromatograms while offering the same recoveries and limits of detection (LOD) (instrumental LOD is 5-10 ng mL(-1)) compared to GC-NPD and GC-MS, which are frequently used methods for PFR analysis. GC-MS offers a higher selectivity than GC-NPD and the possibility of using isotopically labeled compounds for quantification. Copyright © 2012 Elsevier Ltd. All rights reserved.

Validation of an Analytical Method for Determination of Benzo[a]pyrene Bread using QuEChERS Method by GC-MS

PubMed Central

Eslamizad, Samira; Yazdanpanah, Hassan; Javidnia, Katayon; Sadeghi, Ramezan; Bayat, Mitra; Shahabipour, Sara; Khalighian, Najmeh; Kobarfard, Farzad

2016-01-01

A fast and simple modified QuEChERS (quick, easy, cheap, rugged and safe) extraction method based on spiked calibration curves and direct sample introduction was developed for determination of Benzo [a] pyrene (BaP) in bread by gas chromatography-mass spectrometry single quadrupole selected ion monitoring (GC/MS-SQ-SIM). Sample preparation includes: extraction of BaP into acetone followed by cleanup with dispersive solid phase extraction. The use of spiked samples for constructing the calibration curve substantially reduced adverse matrix-related effects. The average recovery of BaP at 6 concentration levels was in range of 95-120%. The method was proved to be reproducible with relative standard deviation less than 14.5% for all of the concentration levels. The limit of detection and limit of quantification were 0.3 ng/g and 0.5 ng/g, respectively. Correlation coefficient of 0.997 was obtained for spiked calibration standards over the concentration range of 0.5-20 ng/g. To the best of our knowledge, this is the first time that a QuEChERS method is used for the analysis of BaP in breads. The developed method was used for determination of BaP in 29 traditional (Sangak) and industrial (Senan) bread samples collected from Tehran in 2014. These results showed that two Sangak samples were contaminated with BaP. Therefore, a comprehensive survey for monitoring of BaP in Sangak bread samples seems to be needed. This is the first report concerning contamination of bread samples with BaP in Iran. PMID:27642317

Simple and accurate quantification of BTEX in ambient air by SPME and GC-MS.

PubMed

Baimatova, Nassiba; Kenessov, Bulat; Koziel, Jacek A; Carlsen, Lars; Bektassov, Marat; Demyanenko, Olga P

2016-07-01

Benzene, toluene, ethylbenzene and xylenes (BTEX) comprise one of the most ubiquitous and hazardous groups of ambient air pollutants of concern. Application of standard analytical methods for quantification of BTEX is limited by the complexity of sampling and sample preparation equipment, and budget requirements. Methods based on SPME represent simpler alternative, but still require complex calibration procedures. The objective of this research was to develop a simpler, low-budget, and accurate method for quantification of BTEX in ambient air based on SPME and GC-MS. Standard 20-mL headspace vials were used for field air sampling and calibration. To avoid challenges with obtaining and working with 'zero' air, slope factors of external standard calibration were determined using standard addition and inherently polluted lab air. For polydimethylsiloxane (PDMS) fiber, differences between the slope factors of calibration plots obtained using lab and outdoor air were below 14%. PDMS fiber provided higher precision during calibration while the use of Carboxen/PDMS fiber resulted in lower detection limits for benzene and toluene. To provide sufficient accuracy, the use of 20mL vials requires triplicate sampling and analysis. The method was successfully applied for analysis of 108 ambient air samples from Almaty, Kazakhstan. Average concentrations of benzene, toluene, ethylbenzene and o-xylene were 53, 57, 11 and 14µgm(-3), respectively. The developed method can be modified for further quantification of a wider range of volatile organic compounds in air. In addition, the new method is amenable to automation. Copyright © 2016 Elsevier B.V. All rights reserved.

Preliminary phytochemical screening, Antibacterial potential and GC-MS analysis of two medicinal plant extracts.

PubMed

Vijayaram, Seerangaraj; Kannan, Suruli; Saravanan, Konda Mani; Vasantharaj, Seerangaraj; Sathiyavimal, Selvam; P, Palanisamy Senthilkumar

2016-05-01

The presence study was aimed to catalyze the primary metabolites and their confirmation by using GC-MS analysis and antibacterial potential of leaf extract of two important medicinal plant viz., Eucalyptus and Azadirachta indica. The antibacterial potential of the methanol leaf extract of the studied species was tested against Escherichia coli, Pseudomonas aeruginosa, Klebsiellap neumoniae, Streptococcus pyogens, Staphylococcus aureus using by agar well diffusion method. The higher zone of inhibition (16mm) was observed against the bacterium Pseudomonas aeruginosa at 100μl concentration of methanol leaf extract. Preliminary phytochemical analysis of studied species shows that presence of phytochemical compounds like steroids, phenolic compounds and flavonoids. GC-MS analysis confirms the occurrence of 20 different compounds in the methanol leaf extract of the both studied species.

Method development for mass spectrometry based molecular characterization of fossil fuels and biological samples

NASA Astrophysics Data System (ADS)

Mahat, Rajendra K.

In an analytical (chemical) method development process, the sample preparation step usually determines the throughput and overall success of the analysis. Both targeted and non-targeted methods were developed for the mass spectrometry (MS) based analyses of fossil fuels (coal) and lipidomic analyses of a unique micro-organism, Gemmata obscuriglobus. In the non-targeted coal analysis using GC-MS, a microwave-assisted pressurized sample extraction method was compared with the traditional extraction method, such as Soxhlet. On the other hand, methods were developed to establish a comprehensive lipidomic profile and to confirm the presence of endotoxins (a.k.a. lipopolysaccharides, LPS) in Gemmata.. The performance of pressurized heating techniques employing hot-air oven and microwave irradiation were compared with that of Soxhlet method in terms of percentage extraction efficiency and extracted analyte profiles (via GC-MS). Sub-bituminous (Powder River Range, Wyoming, USA) and bituminous (Fruitland formation, Colorado, USA) coal samples were tested. Overall 30-40% higher extraction efficiencies (by weight) were obtained with a 4 hour hot-air oven and a 20 min microwave-heating extraction in a pressurized container when compared to a 72 hour Soxhlet extraction. The pressurized methods are 25 times more economic in terms of solvent/sample amount used and are 216 times faster in term of time invested for the extraction process. Additionally, same sets of compounds were identified by GC-MS for all the extraction methods used: n-alkanes and diterpanes in the sub-bituminous sample, and n-alkanes and alkyl aromatic compounds in the bituminous coal sample. G. obscuriglobus, a nucleated bacterium, is a micro-organism of high significances from evolutionary, cell and environmental biology standpoints. Although lipidomics is an essential tool in microbiological systematics and chemotaxonomy, complete lipid profile of this bacterium is still lacking. In addition, the presence of LPS and thus outer membrane (OM) in Gemmata is unknown. Global lipidomic analysis of G. obscuriglobus showed fatty acids (FAs) in the range C14 - C22, with octadecanoic and cis-9 hexadecenoic acids (C18:0 and ωc9 C16:1) being the two most abundant FAs. Thirteen different Gram-negative specific 3-hydroxy fatty acids (3-HOFAs) and eukaryote specific sterols (C30; four in number) were identified. Additionally, like a eukaryotic cell, a polyunsaturated fatty acid (PUFA; tent. ω3 C27:3) has also been discovered. The targeted lipidomic study found a series of novel biomarkers in G. obscuriglobus. Compositional analysis of LPS confirmed eight different 3-HOFAs and a sugar-acid, 2-keto 3-deoxy-D-manno -octulosonic acid (Kdo). These two groups of compounds, being unique to a Gram-negative LPS, confirmed the presence of OM in G. obscuriglobus. Moreover, compositional analyses by GC-MS also confirmed glucosamine and hexose and heptose sugars in the LPS. These compositional information obtained from GC-MS analyses were combined with molecular/structural information collected from Matrix-assisted laser desorption and ionization-time of flight (MALDI-TOF) MS. The MALDI-TOF MS showed a cluster of ions separated by 14 u, from m/z 2017.16 to 2143.28. For the most intense ion at m/z 2087.22, a tentative hexa-acylated lipid A structure has been proposed. Identifications of multiple 3-HOFAs by GC-MS and a cluster of ions in MALDI suggest presence of multiple lipid A species, i.e., heterogeneous lipid A molecule, in G. obscuriglobus..

Efficacy of head space solid-phase microextraction coupled to gas chromatography-mass spectrometry method for determination of the trace extracellular hydrocarbons of cyanobacteria.

PubMed

Guan, Wenna; Zhu, Tao; Wang, Yuejie; Zhang, Zhongyi; Jin, Zhao; Wang, Cong; Bai, Fali

2016-09-01

Hydrocarbons are widespread in cyanobacteria, and the biochemical synthetic pathways were recently identified. Intracellular fatty alka(e)nes of cyanobacteria have been detected by liquid-liquid extraction (LLE) coupled to gas chromatography-mass spectrometry (GC/MS). However, whether fatty alka(e)nes can be released to cyanobacterial culture media remains to be clarified. This work develops a sensitive method for analyzing the trace level of extracellular hydrocarbons in cyanobacterial culture media by head space solid-phase microextraction (HS-SPME) coupled to GC/MS. Headspace (HS) extraction mode using polydimethylsiloxane fiber to extract for 30min at 50°C was employed as the optimal extraction conditions. Five cyanobacterial fatty alka(e)nes analogs including pentadecene (C15:1), pentadecane (C15:0), heptadecene (C17:1), heptadecane (C17:0), nonadecane (C19:0) were analyzed, and the data obtained from HS-SPME-GC/MS method were quantified using internal standard peak area comparisons. Limits of detection (LOD), limits of quantitation (LOQ), linear dynamic range, precisions (RSD) and recovery for the analysis of extracellular fatty alka(e)nes of cyanobacteria by HS-SPME-GC/MS were evaluated. The LODs limits of detection (S/N = 3) varied from 10 to 21 ng L-1. The correlation coefficients (r) of the calibration curves ranged from 0.9873 to 0.9977 with a linearity from 0.1 to 50 μg L-1. The RSD values were ranging from 7.8 to 14.0% and from 4.0 to 8.8% at 1.0 μg L-1 and 10.0 μg L-1 standard solutions, respectively. Comparative analysis of extracellular fatty alka(e)nes in the culture media of model cyanobacteria Synechocystis sp. PCC 6803 demonstrated that sensitivity of HS-SPME-GC/MS method was significantly higher than LLE method. Finally, we found that heptadecane can be released into the culture media of Synechocystis sp. PCC 6803 at the later growth period. Copyright © 2016 Elsevier B.V. All rights reserved.

GCALIGNER 1.0: an alignment program to compute a multiple sample comparison data matrix from large eco-chemical datasets obtained by GC.

PubMed

Dellicour, Simon; Lecocq, Thomas

2013-10-01

GCALIGNER 1.0 is a computer program designed to perform a preliminary data comparison matrix of chemical data obtained by GC without MS information. The alignment algorithm is based on the comparison between the retention times of each detected compound in a sample. In this paper, we test the GCALIGNER efficiency on three datasets of the chemical secretions of bumble bees. The algorithm performs the alignment with a low error rate (<3%). GCALIGNER 1.0 is a useful, simple and free program based on an algorithm that enables the alignment of table-type data from GC. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Avoiding hard chromatographic segmentation: A moving window approach for the automated resolution of gas chromatography-mass spectrometry-based metabolomics signals by multivariate methods.

PubMed

Domingo-Almenara, Xavier; Perera, Alexandre; Brezmes, Jesus

2016-11-25

Gas chromatography-mass spectrometry (GC-MS) produces large and complex datasets characterized by co-eluted compounds and at trace levels, and with a distinct compound ion-redundancy as a result of the high fragmentation by the electron impact ionization. Compounds in GC-MS can be resolved by taking advantage of the multivariate nature of GC-MS data by applying multivariate resolution methods. However, multivariate methods have to be applied in small regions of the chromatogram, and therefore chromatograms are segmented prior to the application of the algorithms. The automation of this segmentation process is a challenging task as it implies separating between informative data and noise from the chromatogram. This study demonstrates the capabilities of independent component analysis-orthogonal signal deconvolution (ICA-OSD) and multivariate curve resolution-alternating least squares (MCR-ALS) with an overlapping moving window implementation to avoid the typical hard chromatographic segmentation. Also, after being resolved, compounds are aligned across samples by an automated alignment algorithm. We evaluated the proposed methods through a quantitative analysis of GC-qTOF MS data from 25 serum samples. The quantitative performance of both moving window ICA-OSD and MCR-ALS-based implementations was compared with the quantification of 33 compounds by the XCMS package. Results shown that most of the R 2 coefficients of determination exhibited a high correlation (R 2 >0.90) in both ICA-OSD and MCR-ALS moving window-based approaches. Copyright © 2016 Elsevier B.V. All rights reserved.

Optimisation of a simple and reliable method based on headspace solid-phase microextraction for the determination of volatile phenols in beer.

PubMed

Pizarro, C; Pérez-del-Notario, N; González-Sáiz, J M

2010-09-24

A simple, accurate and sensitive method based on headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the analysis of 4-ethylguaiacol, 4-ethylphenol, 4-vinylguaiacol and 4-vinylphenol in beer. The effect of the presence of CO2 in the sample on the extraction of analytes was examined. The influence on extraction efficiency of different fibre coatings, of salt addition and stirring was also evaluated. Divinylbenzene/carboxen/polydimethylsiloxane was selected as extraction fibre and was used to evaluate the influence of exposure time, extraction temperature and sample volume/total volume ratio (Vs/Vt) by means of a central composite design (CCD). The optimal conditions identified were 80 degrees C for extraction temperature, 55 min for extraction time and 6 mL of beer (Vs/Vt 0.30). Under optimal conditions, the proposed method showed satisfactory linearity (correlation coefficients between 0.993 and 0.999), precision (between 6.3% and 9.7%) and detection limits (lower than those previously reported for volatile phenols in beers). The method was applied successfully to the analysis of beer samples. To our knowledge, this is the first time that a HS-SPME based method has been developed to determine simultaneously these four volatile phenols in beers. Copyright 2010 Elsevier B.V. All rights reserved.

Multiresidue method for pesticide residue analysis in food of animal and plant origin based on GC or LC and MS or MS/MS.

PubMed

Muñoz, Eva; Muñoz, Gloria; Pineda, Laura; Serrahima, Eulalia; Centrich, Francesc

2012-01-01

A multiresidue method based on GC or LC and MS or MS/MS for the determination of 204 pesticides in diverse food matrixes of animal and plant origin is described. The method can include different stages of cleanup according to the chemical characteristics of each sample. Samples were extracted using accelerated solvent extraction. Those with a high fat content or that contained chlorophyll required further purification by gel permeation chromatography and/or SPE (ENVI-Carb). The methodology developed here was fully validated; the LOQs for the 204 pesticides are presented. The LOQ values lie between 0.01 to 0.02 mg/kg. However, in some cases, mainly in baby food, they were as low as 0.003 mg/kg, thereby meeting European Union requirements on maximum residue levels for pesticides, as outlined in European regulation 396/2005 and the Commission Directive 2003/13/EC. The procedure has been accredited for a wide scope of pesticides and matrixes by the Spanish Accreditation Body (ENAC) following ISO/IEC 17025:2005, as outlined in ENAC technical note NT-19.

Metabolomic and elemental analysis of camel and bovine urine by GC-MS and ICP-MS.

PubMed

Ahamad, Syed Rizwan; Alhaider, Abdul Qader; Raish, Mohammad; Shakeel, Faiyaz

2017-01-01

Recent studies from the author's laboratory indicated that camel urine possesses antiplatelet activity and anti-cancer activity which is not present in bovine urine. The objective of this study is to compare the volatile and elemental components of bovine and camel urine using GC-MS and ICP-MS analysis. We are interested to know the component that performs these biological activities. The freeze dried urine was dissolved in dichloromethane and then derivatization process followed by using BSTFA for GC-MS analysis. Thirty different compounds were analyzed by the derivatization process in full scan mode. For ICP-MS analysis twenty eight important elements were analyzed in both bovine and camel urine. The results of GC-MS and ICP-MS analysis showed marked difference in the urinary metabolites. GC-MS evaluation of camel urine finds a lot of products of metabolism like benzene propanoic acid derivatives, fatty acid derivatives, amino acid derivatives, sugars, prostaglandins and canavanine. Several research reports reveal the metabolomics studies on camel urine but none of them completely reported the pharmacology related metabolomics. The present data of GC-MS suggest and support the previous studies and activities related to camel urine.

A new method for total OH reactivity measurements using a fast Gas Chromatographic Photo-Ionization Detector (GC-PID)

NASA Astrophysics Data System (ADS)

Nölscher, A. C.; Sinha, V.; Bockisch, S.; Klüpfel, T.; Williams, J.

2012-05-01

The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date direct measurements of total OH reactivity have been either performed using a Laser Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton Transfer Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photo-Ionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60-70 s), sensitivity (LOD 3-6 s-1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were equivalent to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.

MS-Electronic Nose Performance Improvement Using GC Retention Times And 2-Way And 3-Way Data Processing Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burian, Cosmin; Llobet, Eduard; Vilanova, Xavier

We have designed a challenging experimental sample set in the form of 20 solutions with a high degree of similarity in order to study whether the addition of chromatographic separation information improves the performance of regular MS based electronic noses. In order to make an initial study of the approach, two different chromatographic methods were used. By processing the data of these experiments with 2 and 3-way algorithms, we have shown that the addition of chromatographic separation information improves the results compared to the 2-way analysis of mass spectra or total ion chromatogram treated separately. Our findings show that whenmore » the chromatographic peaks are resolved (longer measurement times), 2-way methods work better than 3-way methods, whereas in the case of a more challenging measurement (more coeluted chromatograms, much faster GC-MS measurements) 3-way methods work better.« less

Acrylamide: formation, occurrence in food products, detection methods, and legislation.

PubMed

Arvanitoyannis, Ioannis S; Dionisopoulou, Niki

2014-01-01

This review aims at summarizing the most recent updates in the field of acrylamide (AA) formation (mechanism, conditions) and the determination of AA in a number of foods (fried or baked potatoes, chips, coffee, bread, etc). The methods applied for AA detection [Capillary Electrophoresis-Mass Spectrometry (CE-MS), Liquid Chromatography-Mass Spectrometry (LC-MS), Non-Aqueous Capillary Electrophoresis (NACE), High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS), Pressurized Fluid Extraction (PFE), Matrix Solid-Phase Dispersion (MSPD), Gas Chromatography-Mass Spectrometry (GC-MS), Solid-Phase MicroExtraction-Gas Chromatography (SPME-GC), Enzyme Linked Immunosorbent Assay (ELISA), and MicroEmulsion ElectroKinetic Chromatography (MEEKC) are presented and commented. Several informative figures and tables are included to show the effect of conditions (temperature, time) on the AA formation. A section is also included related to AA legislation in EU and US.

Regional water-quality analysis of 2,4-D and dicamba in river water using gas chromatography-isotope dilution mass spectrometry

USGS Publications Warehouse

Thurman, E.M.; Zimmerman, L.R.; Aga, D.S.; Gilliom, R.J.

2001-01-01

Gas chromatography with isotope dilution mass spectrometry (GC-MS) and enzyme-linked immunosorbent assay (ELISA) were used in regional National Water Quality Assessment studies of the herbicides, 2,4-D and dicamba, in river water across the United States. The GC-MS method involved solid-phase extraction, derivatized with deutemted 2,4-D, and analysis by selected ion monitoring. The ELISA method was applied after preconcentration with solid-phase extraction. The ELISA method was unreliable because of interference from humic substances that were also isolated by solid-phase extraction. Therefore, GC-MS was used to analyzed 80 samples from river water from 14 basins. The frequency of detection of dicamba (28%) was higher than that for 2,4-D (16%). Concentrations were higher for dicamba than for 2,4-D, ranging from less than the detection limit (<0.05 ??g/L) to 3.77 ??g/L, in spite of 5 times more annual use of 2,4-D as compared to dicamba. These results suggest that 2,4-D degrades more rapidly in the environment than dicamba.

Recommendations for Improving Identification and Quantification in Non-Targeted, GC-MS-Based Metabolomic Profiling of Human Plasma

PubMed Central

Wang, Hanghang; Muehlbauer, Michael J.; O’Neal, Sara K.; Newgard, Christopher B.; Hauser, Elizabeth R.; Shah, Svati H.

2017-01-01

The field of metabolomics as applied to human disease and health is rapidly expanding. In recent efforts of metabolomics research, greater emphasis has been placed on quality control and method validation. In this study, we report an experience with quality control and a practical application of method validation. Specifically, we sought to identify and modify steps in gas chromatography-mass spectrometry (GC-MS)-based, non-targeted metabolomic profiling of human plasma that could influence metabolite identification and quantification. Our experimental design included two studies: (1) a limiting-dilution study, which investigated the effects of dilution on analyte identification and quantification; and (2) a concentration-specific study, which compared the optimal plasma extract volume established in the first study with the volume used in the current institutional protocol. We confirmed that contaminants, concentration, repeatability and intermediate precision are major factors influencing metabolite identification and quantification. In addition, we established methods for improved metabolite identification and quantification, which were summarized to provide recommendations for experimental design of GC-MS-based non-targeted profiling of human plasma. PMID:28841195

The Hydroxyl Radical Reaction Rate Constant and Products of Dimethyl Succinate

DTIC Science & Technology

2008-03-01

phase reaction of OH + DMS, 10 liters of chamber content were flowed over 2,4- dinitrophenylhydrazine (DNPH) impregnated cartridges. Hydrazones formed... dinitrophenylhydrazine (DNPH) derivatization (method described in experimental methods), and GC/MS/MS (where samples were directly introduced into the mass

Trace-Level Automated Mercury Speciation Analysis

PubMed Central

Taylor, Vivien F.; Carter, Annie; Davies, Colin; Jackson, Brian P.

2011-01-01

An automated system for methyl Hg analysis by purge and trap gas chromatography (GC) was evaluated, with comparison of several different instrument configurations including chromatography columns (packed column or capillary), detector (atomic fluorescence, AFS, or inductively coupled plasma mass spectrometry, ICP-MS, using quadrupole and sector field ICP- MS instruments). Method detection limits (MDL) of 0.042 pg and 0.030 pg for CH3Hg+ were achieved with the automated Hg analysis system configured with AFS and ICPMS detection, respectively. Capillary GC with temperature programming was effective in improving resolution and decreasing retention times of heavier Hg species (in this case C3H7Hg+) although carryover between samples was increased. With capillary GC, the MDL for CH3Hg+ was 0.25 pg for AFS detection and 0.060 pg for ICP-MS detection. The automated system was demonstrated to have high throughput (72 samples analyzed in 8 hours) requiring considerably less analyst time than the manual method for methyl mercury analysis described in EPA 1630. PMID:21572543

Normal-Gamma-Bernoulli Peak Detection for Analysis of Comprehensive Two-Dimensional Gas Chromatography Mass Spectrometry Data.

PubMed

Kim, Seongho; Jang, Hyejeong; Koo, Imhoi; Lee, Joohyoung; Zhang, Xiang

2017-01-01

Compared to other analytical platforms, comprehensive two-dimensional gas chromatography coupled with mass spectrometry (GC×GC-MS) has much increased separation power for analysis of complex samples and thus is increasingly used in metabolomics for biomarker discovery. However, accurate peak detection remains a bottleneck for wide applications of GC×GC-MS. Therefore, the normal-exponential-Bernoulli (NEB) model is generalized by gamma distribution and a new peak detection algorithm using the normal-gamma-Bernoulli (NGB) model is developed. Unlike the NEB model, the NGB model has no closed-form analytical solution, hampering its practical use in peak detection. To circumvent this difficulty, three numerical approaches, which are fast Fourier transform (FFT), the first-order and the second-order delta methods (D1 and D2), are introduced. The applications to simulated data and two real GC×GC-MS data sets show that the NGB-D1 method performs the best in terms of both computational expense and peak detection performance.

[Comparison of essential oil enriched with ultrafiltration method and extraction method respectively from essential oil-in-water emulsion of Citri Reticulatae Pericarpium Viride by GC-MS].

PubMed

Yin, Ailing; Han, Zhifeng; Shen, Jie; Guo, Liwei; Cao, Guiping

2011-10-01

To study on the separation from essential oil-in-water emulsion of Citri Reticulatae Pericarpium Viride by ultrafiltration and acetoacetate extraction methods respectively, and the comparison of the oil yields and chemical compositions. Essential oil-in-water emulsion of Citri Reticulatae Pericarpium Viride was separated by ultrafiltration and acetoacetate extraction methods respectively, and the chemical compositions were analyzed and compared by GC-MS. Ultrafiltration method could enrich essential oil more and its chemical compositions were more similar to the essential oil prepared by steam distillation method. Ultrafiltration method is a good medium to separate essential oil from essential oil-in-water emulsion of Citri Reticulatae Pericarpium Viride.

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.

PubMed

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.

Hair analysis for delta(9)-THC, delta(9)-THC-COOH, CBN and CBD, by GC/MS-EI. Comparison with GC/MS-NCI for delta(9)-THC-COOH.

PubMed

Baptista, Maria João; Monsanto, Paula Verâncio; Pinho Marques, Estela Gouveia; Bermejo, Ana; Avila, Sofia; Castanheira, Alice Martelo; Margalho, Cláudia; Barroso, Mário; Vieira, Duarte Nuno

2002-08-14

A sensitive analytical method was developed for quantitative analysis of delta(9)-tetrahydrocannabinol (delta(9)-THC), 11-nor-delta(9)-tetrahydrocannabinol-carboxylic acid (delta(9)-THC-COOH), cannabinol (CBN) and cannabidiol (CBD) in human hair. The identification of delta(9)-THC-COOH in hair would document Cannabis use more effectively than the detection of parent drug (delta(9)-THC) which might have come from environmental exposure. Ketamine was added to hair samples as internal standard for CBN and CBD. Ketoprofen was added to hair samples as internal standard for the other compounds. Samples were hydrolyzed with beta-glucuronidase/arylsulfatase for 2h at 40 degrees C. After cooling, samples were extracted with a liquid-liquid extraction procedure (with chloroform/isopropyl alcohol, after alkalinization, and n-hexane/ethyl acetate, after acidification), which was developed in our laboratory. The extracts were analysed before and after derivatization with pentafluoropropionic anhydride (PFPA) and pentafluoropropanol (PFPOH) using a Hewlett Packard gas chromatographer/mass spectrometer detector, in electron impact mode (GC/MS-EI). Derivatized delta(9)-THC-COOH was also analysed using a Hewlett Packard gas chromatographer/mass spectrometer detector, in negative ion chemical ionization mode (GC/MS-NCI) using methane as the reagent gas. Responses were linear ranging from 0.10 to 5.00 ng/mg hair for delta(9)-THC and CBN, 0.10-10.00 ng/mg hair for CBD, 0.01-5.00 ng/mg for delta(9)-THC-COOH (r(2)>0.99). The intra-assay precisions ranged from <0.01 to 12.40%. Extraction recoveries ranged from 80.9 to 104.0% for delta(9)-THC, 85.9-100.0% for delta(9)-THC-COOH, 76.7-95.8% for CBN and 71.0-94.0% for CBD. The analytical method was applied to 87 human hair samples, obtained from individuals who testified in court of having committed drug related crimes. Quantification of delta(9)-THC-COOH using GC/MS-NCI was found to be more convenient than GC/MS-EI. The latter may give rise to false negatives due to the detection limit.

Microextraction with polyethersulfone for bisphenol-A, alkylphenols and hormones determination in water samples by means of gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry analysis.

PubMed

Ros, O; Vallejo, A; Blanco-Zubiaguirre, L; Olivares, M; Delgado, A; Etxebarria, N; Prieto, A

2015-03-01

In the present work, the suitability of polyethersulfone (PES) tube was assessed for the simultaneous sorptive microextraction of commonly found endocrine disrupting compounds in natural waters such as bisphenol-A (BPA), nonylphenol technical mixture (NP mix), 4-tert-octylphenol (4tOP), 4-n-octylphenol (4-nOP), 17β-estradiol (E2) and 17α-ethynilestradiol (EE2). After the concentration of target compounds in the PES polymer, the analytes were recovered soaking the polymer with a suitable solvent (ethyl acetate or methanol), derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane (BSTFA+1% TMCS) and determined by gas chromatography-mass spectrometry (GC-MS). The analysis was also performed without derivatization step by means of liquid chromatography-tandem mass spectrometry (LC-MS/MS). Extraction parameters (addition of MeOH, ionic strength, extraction speed and time and desorption time) were evaluated and the optimum conditions were fixed as follows: 150 mL water samples containing a 10% (w/v) of sodium chloride and using 5 tubular PES sorbent fibers (1.5 cm length×0.7 mm o.d.). Equilibrium conditions were achieved after 9 h, with absolute extraction efficiencies ranging from 27 to 56%. On the whole, good apparent recoveries were achieved (68-103% and 81-122% for GC-MS and LC-MS/MS, respectively) using deuterated analogues as surrogates. Achieved quantification limits (LOQs) varied between 2-154 ng/L and 2-63 ng/L for all the compounds using GC-MS and LC-MS/MS, respectively. The effect of organic matter was evaluated previous to apply the final method to the analysis of estuarine and wastewater real samples. The comparison of both methods showed that overall, PES-LC-MS/MS provided shorter sample preparation time and better LODs, but PES-silylation-GC-MS allowed the simultaneous determination of all the studied compounds with adequate repeatability and accuracy. Copyright © 2014 Elsevier B.V. All rights reserved.

Analytical Methodologies for Detection of Gamma-Valerolactone, Delta-Valerolactone, Acephate and Azinphos Methyl and Their Associated Metabolites in Complex Biological Matrices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zink, E.; Clark, R.; Grant, K.

2005-01-01

Non-invasive biomonitoring for chemicals of interest in law enforcement and similar monitoring of pesticides, together with their metabolites, can not only save money but can lead to faster medical attention for individuals exposed to these chemicals. This study describes methods developed for the analysis of gamma-valerolactone (GVL), delta-valerolactone (DVL), acephate, and azinphos methyl in saliva and serum. Liquid chromatography/mass spectrometry (LC/MS) operated in the negative and positive ion mode and gas chromatography/mass spectrometry (GC/MS) were used to analyze GVL and DVL. Although both analytical techniques worked well, lower detection limits were obtained with GC/MS. The lactones and their corresponding sodiummore » salts were spiked into both saliva and serum. The lactones were isolated from saliva or serum using newly developed extraction techniques and then subsequently analyzed using GC/MS. The sodium salts of the lactones are nonvolatile and require derivatization prior to analysis by this method. N-methyl-N-(t-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) was ultimately selected as the reagent for derivatization because the acidic conditions required for reactions with diazomethane caused the salts to undergo intramolecular cyclization to the corresponding lactones. In vitro studies were conducted using rat liver microsomes to determine other metabolites associated with these compounds. Azinphos methyl and acephate are classified as organophosphate pesticides, and are known to be cholinesterase inhibitors in humans and insects, causing neurotoxicity. For this reason they have both exposure and environmental impact implications. These compounds were spiked into serum and saliva and prepared for analysis by GC/MS. Continuation of this research would include analysis by GC/MS under positive ion mode to determine the parent ions of the unknown metabolites. Further research is planned through an in vivo analysis of the lactones and pesticides. These methodologies could be extended for further analysis of other similar compounds.« less

Analytical Methodologies for Detection of Gamma-valerolactone, Delta-valerolactone, Acephate, and Azinphos Methyl and their Associated Metabolites in Complex Biological Matrices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zink, Erika M.; Clark, Ryan J.; Grant, Karen E.

2005-01-01

Non-invasive biomonitoring for chemicals of interest in law enforcement and similar monitoring of pesticides together with their metabolites can not only save money but can lead to faster medical attention for individuals exposed to these chemicals. This study describes methods developed for the analysis of gamma-valerolactone (GVL), delta-valerolactone (DVL), acephate, and azinphos methyl in saliva and serum. Liquid chromatography/mass spectrometry (LC/MS) operated in the negative ion mode and in the positive ion mode and gas chromatography/mass spectrometry (GC/MS) were used to analyze GVL and DVL. Although both analytical techniques worked well, lower detection limits were obtained with GC/MS. The lactonesmore » and their corresponding sodium salts were spiked into both saliva and serum. The lactones were isolated from saliva or serum using newly developed extraction techniques and then subsequently analyzed using GC/MS. The sodium salts of the lactones are nonvolatile and require derivatization prior to analysis by this method. N-methyl-N-(t-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) was ultimately selected as the reagent for derivatization because the acidic conditions required for reactions with diazomethane caused the salts to undergo intramolecular cyclization to the corresponding lactones. In vitro studies were conducted using rat liver microsomes to determine other metabolites associated with these compounds. Azinphos methyl and acephate are classified as organophosphate pesticides, and are known to be cholinesterase inhibitors in humans and insects, causing neurotoxicity. For this reason they have both exposure and environmental impact implications. These compounds were spiked into serum and saliva and prepared for analysis by GC/MS. Continuation of this research would include analysis by GC/MS under positive ion mode to determine the parent ions of the unknown metabolites. Further research is planned through an in vivo analysis of the lactones and pesticides. These methodologies could be extended for further analysis of other similar compounds as well as chemical and biological warfare agents.« less

[Determination of 21 fragrance allergens in toys by gas chromatography-ion trap mass spectrometry].

PubMed

Lü, Qing; Zang, Qing; Bai, Hua; Li, Haiyu; Kang, Suyuan; Wang, Chao

2012-05-01

A method of gas chromatography-ion trap mass spectrometry (GC-IT-MS) was developed for the determination of 21 fragrance allergens in sticker toys, plush toys and plastic toys. The experimental conditions, such as sample pretreatment conditions, and the analytical conditions of GC-IT-MS, were optimized. The sticker toy samples and plush toy samples were extracted with acetone by ultrasonic wave, and the extracts were separated on an Agilent HP-1 MS column (50 m x 0.2 mm x 0.5 microm), then determined by IT-MS and quantified by external standard method. The plastic toy samples were extracted by the dissolution-precipitation approach, cleaned up with an Envi-carb solid phase extraction column and concentrated by rotary evaporation and nitrogen blowing, then determined by GC-IT-MS and quantified by external standard method. The calibration curves showed good linearity in the range of 0.002-50 mg/L with the correlation coefficients greater than 0.996 8. The limits of quantification (LOQ, S/N > 10) were 0.02-40 mg/kg. The average recoveries of the target compounds spiked in the sample at three concentration levels were in the range of 82.2%-110.8% with the relative standard deviations (RSDs) of 0.6%-10.5%. These results show that this method is accurate and sensitive for the qualitative and quantitative determination of the 21 fragrance allergens in the 3 types of toys.

Sterol Profile for Natural Juices Authentification by GC-MS

NASA Astrophysics Data System (ADS)

Culea, M.

2007-04-01

A GC-MS analytical method is described for some natural juices analysis. The fingerprint of sterols was used to characterize the natural juice. A rapid liquid-liquid extraction method was used. The sterols were separated on a Rtx-5MS capillary column, 15m×0.25mm, 0.25μm film thickness, in a temperature program from 50°C for 1 min, then ramped at 15°C/min to 300°C and held for 15 min. Identification of sterols and their patterns were used for juice characterization. The sterol profile is a useful approach for confirming the presence of juices of orange, grapefruit, pineapple and passion fruit in compounded beverages and for detecting of adulteration of fruit juices.

Sol-gel titania-coated needles for solid phase dynamic extraction-GC/MS analysis of desomorphine and desocodeine.

PubMed

Su, Chi-Ju; Srimurugan, Sankarewaran; Chen, Chinpiao; Shu, Hun-Chi

2011-01-01

Novel sol-gel titania film coated needles for solid-phase dynamic extraction (SPDE)-GC/MS analysis of desomorphine and desocodeine are described. The high thermal stability of titania film permits efficient extraction and analysis of poorly volatile opiate drugs. The influences of sol-gel reaction time, coating layer, extraction and desorption time and temperature on the SPDE needle performance were investigated. The deuterium labeled internal standard was introduced either during the extraction of analyte or directly injected to GC after the extraction process. The latter method was shown to be more sensitive for the analysis of water and urine samples containing opiate drugs. The proposed conditions provided a wide linear range (from 5-5000 ppb), and satisfactory linearity, with R(2) values from 0.9958 to 0.9999, and prominent sensitivity, LOQs (1.0-5.0 ng/g). The sol-gel titania film coated needle with SPDE-GC/MS will be a promising technique for desomorphine and desocodeine analysis in urine.

[Determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry].

PubMed

Xia, Guanghui; Shen, Weijian; Yu, Keyao; Wu, Bin; Zhang, Rui; Shen, Chongyu; Zhao, Zengyun; Bian, Xiaohong; Xu, Jiyang

2014-07-01

A method was developed for the determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The honey and royal jelly samples were treated with different preparation methods as the result of the different components. The honey sample was extracted with ethyl acetate and cleaned up with primary second amine, and the royal jelly sample was extracted with acetonitrile-water (1:1, v/v), and cleaned up with a C18 solid-phase extraction column. Finally, the extracts of the honey and royal jelly were analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode separately. External standard calibration method was used for quantification. The linearities of calibration curves of the four insecticides were good with the correlation coefficients greater than 0.99 in the range of 50-500 microg/L. The limits of the detection (LODs) of the four insecticides were in the range of 0.12- 5.0 microg/kg, and the limits of the quantification (LOQs) were in the range of 0.40-16.5 microg/kg. The recoveries of the four insecticides spiked in honey and royal jelly at three spiked levels (10, 15 and 20 microg/kg) were in the range of 78.2 -110.0%, and the relative standard deviations (RSDs) were all below 14%. The sensitivity and selectivity of this method were good with no interfering peaks. The proposed method is simple quick and effective to analyze the four insecticide residues in honey and royal jelly.

GC-TOF/MS-based metabolomic profiling of estrogen deficiency-induced obesity in ovariectomized rats

PubMed Central

Ma, Bo; Zhang, Qi; Wang, Guang-ji; A, Ji-ye; Wu, Di; Liu, Ying; Cao, Bei; Liu, Lin-sheng; Hu, Ying-ying; Wang, Yong-lu; Zheng, Ya-ya

2011-01-01

Aim: To explore the alteration of endogenous metabolites and identify potential biomarkers using metabolomic profiling with gas chromatography coupled a time-of-flight mass analyzer (GC/TOF-MS) in a rat model of estrogen-deficiency-induced obesity. Methods: Twelve female Sprague-Dawley rats six month of age were either sham-operated or ovariectomized (OVX). Rat blood was collected, and serum was analyzed for biomarkers using standard colorimetric methods with commercial assay kits and a metabolomic approach with GC/TOF-MS. The data were analyzed using multivariate statistical techniques. Results: A high body weight and body mass index inversely correlated with serum estradiol (E2) in the OVX rats compared to the sham rats. Estrogen deficiency also significantly increased serum total cholesterol, triglycerides, and low-density lipoprotein cholesterol. Utilizing GC/TOF-MS-based metabolomic analysis and the partial least-squares discriminant analysis, the OVX samples were discriminated from the shams. Elevated levels of cholesterol, glycerol, glucose, arachidonic acid, glutamic acid, glycine, and cystine and reduced alanine levels were observed. Serum glucose metabolism, energy metabolism, lipid metabolism, and amino acid metabolism were involved in estrogen-deficiency-induced obesity in OVX rats. Conclusion: The series of potential biomarkers identified in the present study provided fingerprints of rat metabolomic changes during obesity and an overview of multiple metabolic pathways during the progression of obesity involving glucose metabolism, lipid metabolism, and amino acid metabolism. PMID:21293480

Phentermine interference and high L-methamphetamine concentration problems in GC-EI-MS SIM Analyses of R-(-)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride-derivatized amphetamines and methamphetamines†.

PubMed

Hamilton, Theron J; Qui, Harry Z; Dozier, Katherine V R; Fuller, Zachary J

2014-09-01

In order to achieve chromatographic separation, urine samples shown to be initially positive for amphetamines and methamphetamines in US Department of Defense immunoassays are derivatized with R-(-)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride (R-(-)-MTPA) prior to gas chromatography-electron impact-mass spectrometry (GC-EI-MS) analysis. Phentermine, a member of the phenethylamine class of drugs and a common appetite suppressant, interferes with GC-EI-MS assays of R-(-)-MTPA-derivatized d-amphetamine, degrading the chromatography of the internal standard and analyte ions and skewing concentration calculations. Additionally, when specimens with high concentrations of l-methamphetamine are derivatized with R-(-)-MTPA, signal peaks have the potential to be misidentified by integration software as d-methamphetamine. We have found that replacing R-(-) MTPA with (S)-(+)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride reduces phentermine interference problems related to internal standard chromatography, reduces the possibility of concentrated l-methamphetamine peaks being misidentified by integration software, improves resolution of d-methamphetamine in the presence of high l-methamphetamine concentrations, and is a cost-neutral change that can be applied to current amphetamines GC-EI-MS methods without the need for method modification. Published by Oxford University Press 2014. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Simultaneous detection of seventeen drugs of abuse and metabolites in hair using solid phase micro extraction (SPME) with GC/MS.

PubMed

Aleksa, Katarina; Walasek, Paula; Fulga, Netta; Kapur, Bhushan; Gareri, Joey; Koren, Gideon

2012-05-10

The analysis of pediatric and adult hair is a useful non-invasive biomarker to effectively detect long term exposure to various xenobiotics, specifically drugs of abuse such as cocaine, opiates and amphetamines. Very often individuals are using, or are exposed to multiple drugs simultaneously and therefore it is important to be able to detect them in the same analysis. We have developed a sensitive and specific solid phase micro extraction (SPME) coupled with gas chromatography mass spectrometry (GC/MS) to detect 17 different analytes in hair using a single extraction method. Five milligrams of hair is extracted overnight, subjected to solid phase extraction (SPE) and then to SPME-GC/MS. The aimed analytes include amphetamine, methamphetamine, MDA, MDMA, cocaine, benzoylecognine, norcocaine, cocaethylene, methadone, codeine, morphine, 6-AM, oxycodone, oxymorphone, hydrocodone, hydromorphone and meperidone. The following are the LOD of the various drugs: 0.2ng/mg hair for amphetamine, methamphetamine, MDA, MDMA, morphine, codeine, 6-AM, oxycodone, oxymorphone, hydromorphone, hydrocodone, meperidine and 0.13ng/mg hair for cocaine, benzoylecognine, cocaethylene, norcocaine and methadone. This GC/MS method is sensitive and specific to detect the presence of these 17 analytes in as little as 5mg of hair and is especially useful for newborn and child hair analysis where the amount of hair is often very limited. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Elimination of chromatographic and mass spectrometric problems in GC-MS analysis of Lavender essential oil by multivariate curve resolution techniques: Improving the peak purity assessment by variable size moving window-evolving factor analysis.

PubMed

Jalali-Heravi, Mehdi; Moazeni-Pourasil, Roudabeh Sadat; Sereshti, Hassan

2015-03-01

In analysis of complex natural matrices by gas chromatography-mass spectrometry (GC-MS), many disturbing factors such as baseline drift, spectral background, homoscedastic and heteroscedastic noise, peak shape deformation (non-Gaussian peaks), low S/N ratio and co-elution (overlapped and/or embedded peaks) lead the researchers to handle them to serve time, money and experimental efforts. This study aimed to improve the GC-MS analysis of complex natural matrices utilizing multivariate curve resolution (MCR) methods. In addition, to assess the peak purity of the two-dimensional data, a method called variable size moving window-evolving factor analysis (VSMW-EFA) is introduced and examined. The proposed methodology was applied to the GC-MS analysis of Iranian Lavender essential oil, which resulted in extending the number of identified constituents from 56 to 143 components. It was found that the most abundant constituents of the Iranian Lavender essential oil are α-pinene (16.51%), camphor (10.20%), 1,8-cineole (9.50%), bornyl acetate (8.11%) and camphene (6.50%). This indicates that the Iranian type Lavender contains a relatively high percentage of α-pinene. Comparison of different types of Lavender essential oils showed the composition similarity between Iranian and Italian (Sardinia Island) Lavenders. Published by Elsevier B.V.

Detection of Stimulants and Narcotics by Liquid Chromatography-Tandem Mass Spectrometry and Gas Chromatography-Mass Spectrometry for Sports Doping Control.

PubMed

Ahrens, Brian D; Kucherova, Yulia; Butch, Anthony W

2016-01-01

Sports drug testing laboratories are required to detect several classes of compounds that are prohibited at all times, which include anabolic agents, peptide hormones, growth factors, beta-2 agonists, hormones and metabolic modulators, and diuretics/masking agents. Other classes of compounds such as stimulants, narcotics, cannabinoids, and glucocorticoids are also prohibited, but only when an athlete is in competition. A single class of compounds can contain a large number of prohibited substances and all of the compounds should be detected by the testing procedure. Since there are almost 70 stimulants on the prohibited list it can be a challenge to develop a single screening method that will optimally detect all the compounds. We describe a combined liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) testing method for detection of all the stimulants and narcotics on the World Anti-Doping Agency prohibited list. Urine for LC-MS/MS testing does not require sample pretreatment and is a direct dilute and shoot method. Urine samples for the GC-MS method require a liquid-liquid extraction followed by derivatization with trifluoroacetic anhydride.

Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction.

PubMed

Camino-Sánchez, F J; Zafra-Gómez, Alberto; Pérez-Trujillo, J P; Conde-González, J E; Marques, J C; Vílchez, José Luis

2011-08-01

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K(ow) values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g(-1), with detection limits below pg g(-1) levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain). Copyright © 2011 Elsevier Ltd. All rights reserved.

Simultaneous determination of nineteen hallucinogenic tryptamines/beta-calbolines and phenethylamines using gas chromatography-mass spectrometry and liquid chromatography-electrospray ionisation-mass spectrometry.

PubMed

Kikura-Hanajiri, R; Hayashi, M; Saisho, K; Goda, Y

2005-10-15

To investigate the trend of non-controlled drugs of abuse, simultaneous analytical methods were developed using GC-MS and LC-ESI-MS for 8 tryptamines/beta-carbolines, 6 phenethylamines of typically non-controlled substances in Japan, and, additionally, five legally controlled tryptamines and phenethylamines originally found in fungi or plants. Moreover, the proposed methods were applied to analyses of these drugs in 99 kinds of products (a total number of 123 products purchased at adult shops or via the Internet over the past 2 years in Japan), which potentially advertised psychotropic/psychoactive effects. The samples were extracted with methanol under ultrasonication. After centrifugation, the extracts were filtered prior to injections. GC-MS analysis was performed using a DB-5MS capillary column. Regarding the LC-ESI-MS analysis; the separation of the target drugs was optimized on an ODS column in acetonitrile/MeOH (7:3)-10 mM ammonium formate buffer (pH 3.5)/acetonitrile (95:5) by a linear gradient program and a quantitative analysis was carried out by the monitoring of each [M+H]+ in the positive ion mode of ESI-MS. As a result of the analyses using GC-MS and LC-ESI-MS, 5-MeO-DIPT (the synthetic substance known by the street name "Foxy") was found in 8 out of the 99 kinds of products. Additionally, AMT (from brown powder), DMT (from dried plant), harmine and harmaline (from dried plant) were also found in some of the 99 products. These analytical methods could be useful for the investigation of the distribution of the non-controlled psychotropic tryptamines/beta-carbolines and phenethylamines in the market.

SW-846 Test Method 8276: Toxaphene and Toxaphene Congeners By Gas Chromatography/Negative Ion Chemical Ionization Mass Spectrometry (GC-NICI/MS)

EPA Pesticide Factsheets

determine the concentrations of various toxaphene congeners and technical toxaphene (with other toxaphene congeners and compounds from Method 8081) in extracts from solidliquid matrices, using fused-silica, open-tubular capillary columns with (NICI/MS).

Quantification of methionine and selenomethionine in biological samples using multiple reaction monitoring high performance liquid chromatography tandem mass spectrometry (MRM-HPLC-MS/MS).

PubMed

Vu, Dai Long; Ranglová, Karolína; Hájek, Jan; Hrouzek, Pavel

2018-05-01

Quantification of selenated amino-acids currently relies on methods employing inductively coupled plasma mass spectrometry (ICP-MS). Although very accurate, these methods do not allow the simultaneous determination of standard amino-acids, hampering the comparison of the content of selenated versus non-selenated species such as methionine (Met) and selenomethionine (SeMet). This paper reports two approaches for the simultaneous quantification of Met and SeMet. In the first approach, standard enzymatic hydrolysis employing Protease XIV was applied for the preparation of samples. The second approach utilized methanesulfonic acid (MA) for the hydrolysis of samples, either in a reflux system or in a microwave oven, followed by derivatization with diethyl ethoxymethylenemalonate. The prepared samples were then analyzed by multiple reaction monitoring high performance liquid chromatography tandem mass spectrometry (MRM-HPLC-MS/MS). Both approaches provided platforms for the accurate determination of selenium/sulfur substitution rate in Met. Moreover the second approach also provided accurate simultaneous quantification of Met and SeMet with a low limit of detection, low limit of quantification and wide linearity range, comparable to the commonly used gas chromatography mass spectrometry (GC-MS) method or ICP-MS. The novel method was validated using certified reference material in conjunction with the GC-MS reference method. Copyright © 2018. Published by Elsevier B.V.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): review.

PubMed

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. Copyright © 2015. Published by Elsevier B.V.

Alkaloids Profiling of Fumaria capreolata by Analytical Platforms Based on the Hyphenation of Gas Chromatography and Liquid Chromatography with Quadrupole-Time-of-Flight Mass Spectrometry.

PubMed

Contreras, María Del Mar; Bribi, Noureddine; Gómez-Caravaca, Ana María; Gálvez, Julio; Segura-Carretero, Antonio

2017-01-01

Two analytical platforms, gas chromatography (GC) coupled to quadrupole-time-of-flight (QTOF) mass spectrometry (MS) and reversed-phase ultrahigh performance liquid chromatography (UHPLC) coupled to diode array (DAD) and QTOF detection, were applied in order to study the alkaloid profile of Fumaria capreolata . The use of these mass analyzers enabled tentatively identifying the alkaloids by matching their accurate mass signals and suggested molecular formulae with those previously reported in libraries and databases. Moreover, the proposed structures were corroborated by studying their fragmentation pattern obtained by both platforms. In this way, 8 and 26 isoquinoline alkaloids were characterized using GC-QTOF-MS and RP-UHPLC-DAD-QTOF-MS, respectively, and they belonged to the following subclasses: protoberberine, protopine, aporphine, benzophenanthridine, spirobenzylisoquinoline, morphinandienone, and benzylisoquinoline. Moreover, the latter analytical method was selected to determine at 280 nm the concentration of protopine (9.6 ± 0.7 mg/g), a potential active compound of the extract. In conclusion, although GC-MS has been commonly used for the analysis of this type of phytochemicals, RP-UHPLC-DAD-QTOF-MS provided essential complementary information. This analytical method can be applied for the quality control of phytopharmaceuticals containing Fumaria extracts currently found in the market.

Alkaloids Profiling of Fumaria capreolata by Analytical Platforms Based on the Hyphenation of Gas Chromatography and Liquid Chromatography with Quadrupole-Time-of-Flight Mass Spectrometry

PubMed Central

Bribi, Noureddine; Gómez-Caravaca, Ana María

2017-01-01

Two analytical platforms, gas chromatography (GC) coupled to quadrupole-time-of-flight (QTOF) mass spectrometry (MS) and reversed-phase ultrahigh performance liquid chromatography (UHPLC) coupled to diode array (DAD) and QTOF detection, were applied in order to study the alkaloid profile of Fumaria capreolata. The use of these mass analyzers enabled tentatively identifying the alkaloids by matching their accurate mass signals and suggested molecular formulae with those previously reported in libraries and databases. Moreover, the proposed structures were corroborated by studying their fragmentation pattern obtained by both platforms. In this way, 8 and 26 isoquinoline alkaloids were characterized using GC-QTOF-MS and RP-UHPLC-DAD-QTOF-MS, respectively, and they belonged to the following subclasses: protoberberine, protopine, aporphine, benzophenanthridine, spirobenzylisoquinoline, morphinandienone, and benzylisoquinoline. Moreover, the latter analytical method was selected to determine at 280 nm the concentration of protopine (9.6 ± 0.7 mg/g), a potential active compound of the extract. In conclusion, although GC-MS has been commonly used for the analysis of this type of phytochemicals, RP-UHPLC-DAD-QTOF-MS provided essential complementary information. This analytical method can be applied for the quality control of phytopharmaceuticals containing Fumaria extracts currently found in the market. PMID:29348751

Multidimensional gas chromatography in combination with accurate mass, tandem mass spectrometry, and element-specific detection for identification of sulfur compounds in tobacco smoke.

PubMed

Ochiai, Nobuo; Mitsui, Kazuhisa; Sasamoto, Kikuo; Yoshimura, Yuta; David, Frank; Sandra, Pat

2014-09-05

A method is developed for identification of sulfur compounds in tobacco smoke extract. The method is based on large volume injection (LVI) of 10μL of tobacco smoke extract followed by selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography (GC) coupled to a hybrid quadrupole time-of-flight mass spectrometer (Q-TOF-MS) using electron ionization (EI) and positive chemical ionization (PCI), with parallel sulfur chemiluminescence detection (SCD). In order to identify each individual sulfur compound, sequential heart-cuts of 28 sulfur fractions from (1)D GC to (2)D GC were performed with the three MS detection modes (SCD/EI-TOF-MS, SCD/PCI-TOF-MS, and SCD/PCI-Q-TOF-MS). Thirty sulfur compounds were positively identified by MS library search, linear retention indices (LRI), molecular mass determination using PCI accurate mass spectra, formula calculation using EI and PCI accurate mass spectra, and structure elucidation using collision activated dissociation (CAD) of the protonated molecule. Additionally, 11 molecular formulas were obtained for unknown sulfur compounds. The determined values of the identified and unknown sulfur compounds were in the range of 10-740ngmg total particulate matter (TPM) (RSD: 1.2-12%, n=3). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Investigations into the chemistry and insecticidal activity of euonymus europaeus seed oil and methanol extract

USDA-ARS?s Scientific Manuscript database

Euonymus europaeus seeds and seed oil were investigated for their volatiles using GC-MS-FID, Headspace-SPME/GC-MS-FID, and derivative GC-MS-FID for their volatiles and HPLC-DAD-CAD/MS for their non-volatile compounds. The seeds contain about 30% of fatty oil, mainly glyceryl trioleate, small amounts...

Multiresidue method for the determination of pesticides in Oolong tea using QuEChERS by gas chromatography-triple quadrupole tandem mass spectrometry.

PubMed

Wu, Chia-Chang

2017-08-15

We propose a simple, rapid analytical method for determination of 89 pesticides in Oolong tea by GC/MS/MS. Samples were extracted via QuEChERS. The limits of detection and quantification range of the 89 pesticides were 1-25μgL -1 and 10-50μgL -1 , respectively. Good separation was attained in less than 36min. A wide linear range of 1-250μgL -1 was observed with r 2 values from 0.9955 to 0.9998. Pesticide-free tea powder spiked at 50 and 100μgL -1 . Recovery ranges of the 86 (50μgL -1 ) and 83 (100μgL -1 ) pesticides were from 60% to 120%. Relative standard deviations were less than 20%. The laboratory proficiency test (FAPAS, 2014) shows satisfactory (|z|<2) z-score values. The proposed monitoring technique rapidly and efficiently screens, multiple pesticides in Oolong tea. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of Endocrine Disrupting Pesticides by Capillary GC with Mass Spectrometric Detection

PubMed Central

Matisová, Eva; Hrouzková, Svetlana

2012-01-01

Endocrine disrupting chemicals, among them many pesticides, alter the normal functioning of the endocrine system of both wildlife and humans at very low concentration levels. Therefore, the importance of method development for their analysis in food and the environment is increasing. This also covers contributions in the field of ultra-trace analysis of multicomponent mixtures of organic pollutants in complex matrices. With this fact conventional capillary gas chromatography (CGC) and fast CGC with mass spectrometric detection (MS) has acquired a real importance in the analysis of endocrine disrupting pesticide (EDP) residues. This paper provides an overview of GC methods, including sample preparation steps, for analysis of EDPs in a variety of matrices at ultra-trace concentration levels. Emphasis is put on separation method, mode of MS detection and ionization and obtained limits of detection and quantification. Analysis time is one of the most important aspects that should be considered in the choice of analytical methods for routine analysis. Therefore, the benefits of developed fast GC methods are important. PMID:23202677

Application of infrared spectroscopy and pyrolysis gas chromatography for characterisation of adhesive tapes

NASA Astrophysics Data System (ADS)

Zięba-Palus, Janina; Nowińska, Sabina; Kowalski, Rafał

2016-12-01

Infrared spectroscopy and pyrolysis GC/MS were applied in the comparative analysis of adhesive tapes. By providing information about the polymer composition, it was possible to classify both backings and adhesives of tapes into defined chemical classes. It was found that samples of the same type (of backings and adhesives) and similar infrared spectra can in most cases be effectively differentiated using Py-GC/MS, sometimes based only on the presence of peaks of very low intensity originating from minor components. The results obtained enabled us to draw the conclusion that Py-GC/MS appears to be a valuable analytical technique for examining tapes, which is complementary to infrared spectroscopy. Identification of pyrolysis products enables discrimination of samples. Both methods also provide crucial information that is useful for identification of adhesive tapes found at the crime scene.

Study of the rice straw biodegradation in mixed culture of Trichoderma viride and Aspergillus niger by GC-MS and FTIR.

PubMed

Chen, Yaoning; Huang, Jingxia; Li, Yuanping; Zeng, Guangming; Zhang, Jiachao; Huang, Aizhi; Zhang, Jie; Ma, Shuang; Tan, Xuebin; Xu, Wei; Zhou, Wei

2015-07-01

This study was conducted to investigate the biodegradation ability of the mixed culture of Trichoderma viride and Aspergillus niger through the study of the organic matter extracted from rice straw and the lignocellulose structure by using gas chromatography-mass spectrometer (GC-MS) and Fourier transform infrared spectroscopy (FTIR). The results of the GC-MS showed that the mixed culture possessed shorter alkane (heptane) at the end of the incubation and more kinds of organic matter (except the alkanes, 29 kinds of organic matter were detected) than the pure cultures. It could be deduced that the organic matter could indicate the degradation degree of the lignocellulose to some extent. Moreover, pinene was detected in the mixed culture on days 5 and 10, which might represent the antagonistic relationship between T. viride and A. niger. The analysis of FTIR spectrums which indirectly verified the GC-MS results showed that the mixed culture possessed a better degradation of rice straw compared with the pure culture. Therefore, the methods used in this research could be considered as effective ones to investigate the lignocellulose degradation mechanism in mixed culture.

Methods, applications and concepts of metabolite profiling: primary metabolism.

PubMed

Steinhauser, Dirk; Kopka, Joachim

2007-01-01

In the 1990s the concept of a comprehensive analysis of the metabolic complement in biological systems, termed metabolomics or alternately metabonomics, was established as the last of four cornerstones for phenotypic studies in the post-genomic era. With genomic, transcriptomic, and proteomic technologies in place and metabolomic phenotyping under rapid development all necessary tools appear to be available today for a fully functional assessment of biological phenomena at all major system levels of life. This chapter attempts to describe and discuss crucial steps of establishing and maintaining a gas chromatography/electron impact ionization/ mass spectrometry (GC-EI-MS)-based metabolite profiling platform. GC-EI-MS can be perceived as the first and exemplary profiling technology aimed at simultaneous and non-biased analysis of primary metabolites from biological samples. The potential and constraints of this profiling technology are among the best understood. Most problems are solved as well as pitfalls identified. Thus GC-EI-MS serves as an ideal example for students and scientists who intend to enter the field of metabolomics. This chapter will be biased towards GC-EI-MS analyses but aims at discussing general topics, such as experimental design, metabolite identification, quantification and data mining.

Discrimination of honeys using colorimetric sensor arrays, sensory analysis and gas chromatography techniques.

PubMed

Tahir, Haroon Elrasheid; Xiaobo, Zou; Xiaowei, Huang; Jiyong, Shi; Mariod, Abdalbasit Adam

2016-09-01

Aroma profiles of six honey varieties of different botanical origins were investigated using colorimetric sensor array, gas chromatography-mass spectrometry (GC-MS) and descriptive sensory analysis. Fifty-eight aroma compounds were identified, including 2 norisoprenoids, 5 hydrocarbons, 4 terpenes, 6 phenols, 7 ketones, 9 acids, 12 aldehydes and 13 alcohols. Twenty abundant or active compounds were chosen as key compounds to characterize honey aroma. Discrimination of the honeys was subsequently implemented using multivariate analysis, including hierarchical clustering analysis (HCA) and principal component analysis (PCA). Honeys of the same botanical origin were grouped together in the PCA score plot and HCA dendrogram. SPME-GC/MS and colorimetric sensor array were able to discriminate the honeys effectively with the advantages of being rapid, simple and low-cost. Moreover, partial least squares regression (PLSR) was applied to indicate the relationship between sensory descriptors and aroma compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of ketamine and norketamine in urine by automatic solid-phase extraction (SPE) and positive ion chemical ionization-gas chromatography-mass spectrometry (PCI-GC-MS).

PubMed

Kim, Eun-mi; Lee, Ju-seon; Choi, Sang-kil; Lim, Mi-ae; Chung, Hee-sun

2008-01-30

Ketamine (KT) is widely abused for hallucination and also misused as a "date-rape" drug in recent years. An analytical method using positive ion chemical ionization-gas chromatography-mass spectrometry (PCI-GC-MS) with an automatic solid-phase extraction (SPE) apparatus was studied for the determination of KT and its major metabolite, norketamine (NK), in urine. Six ketamine suspected urine samples were provided by the police. For the research of KT metabolism, KT was administered to SD rats by i.p. at a single dose of 5, 10 and 20mg/kg, respectively, and urine samples were collected 24, 48 and 72 h after administration. For the detection of KT and NK, urine samples were extracted on an automatic SPE apparatus (RapidTrace, Zymark) with mixed mode type cartridge, Drug-Clean (200 mg, Alltech). The identification of KT and NK was by PCI-GC-MS. m/z238 (M+1), 220 for KT, m/z 224 (M+1), 207 for NK and m/z307 (M+1) for Cocaine-D(3) as internal standard were extracted from the full-scan mass spectrum and the underlined ions were used for quantitation. Extracted calibration curves were linear from 50 to 1000 ng/mL for KT and NK with correlation coefficients exceeding 0.99. The limit of detection (LOD) was 25 ng/mL for KT and NK. The limit of quantitation (LOQ) was 50 ng/mL for KT and NK. The recoveries of KT and NK at three different concentrations (86, 430 and 860 ng/mL) were 53.1 to 79.7% and 45.7 to 83.0%, respectively. The intra- and inter-day run precisions (CV) for KT and NK were less than 15.0%, and the accuracies (bias) for KT and NK were also less than 15% at the three different concentration levels (86, 430 and 860 ng/mL). The analytical method was also applied to real six KT suspected urine specimens and KT administered rat urines, and the concentrations of KT and NK were determined. Dehydronorketamine (DHNK) was also confirmed in these urine samples, however the concentration of DHNK was not calculated. SPE is simple, and needs less organic solvent than liquid-liquid extraction (LLE), and PCI-GC-MS can offer both qualitative and quantitative information for urinalysis of KT in forensic analysis.

Combining peak- and chromatogram-based retention time alignment algorithms for multiple chromatography-mass spectrometry datasets.

PubMed

Hoffmann, Nils; Keck, Matthias; Neuweger, Heiko; Wilhelm, Mathias; Högy, Petra; Niehaus, Karsten; Stoye, Jens

2012-08-27

Modern analytical methods in biology and chemistry use separation techniques coupled to sensitive detectors, such as gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). These hyphenated methods provide high-dimensional data. Comparing such data manually to find corresponding signals is a laborious task, as each experiment usually consists of thousands of individual scans, each containing hundreds or even thousands of distinct signals. In order to allow for successful identification of metabolites or proteins within such data, especially in the context of metabolomics and proteomics, an accurate alignment and matching of corresponding features between two or more experiments is required. Such a matching algorithm should capture fluctuations in the chromatographic system which lead to non-linear distortions on the time axis, as well as systematic changes in recorded intensities. Many different algorithms for the retention time alignment of GC-MS and LC-MS data have been proposed and published, but all of them focus either on aligning previously extracted peak features or on aligning and comparing the complete raw data containing all available features. In this paper we introduce two algorithms for retention time alignment of multiple GC-MS datasets: multiple alignment by bidirectional best hits peak assignment and cluster extension (BIPACE) and center-star multiple alignment by pairwise partitioned dynamic time warping (CeMAPP-DTW). We show how the similarity-based peak group matching method BIPACE may be used for multiple alignment calculation individually and how it can be used as a preprocessing step for the pairwise alignments performed by CeMAPP-DTW. We evaluate the algorithms individually and in combination on a previously published small GC-MS dataset studying the Leishmania parasite and on a larger GC-MS dataset studying grains of wheat (Triticum aestivum). We have shown that BIPACE achieves very high precision and recall and a very low number of false positive peak assignments on both evaluation datasets. CeMAPP-DTW finds a high number of true positives when executed on its own, but achieves even better results when BIPACE is used to constrain its search space. The source code of both algorithms is included in the OpenSource software framework Maltcms, which is available from http://maltcms.sf.net. The evaluation scripts of the present study are available from the same source.

Combining peak- and chromatogram-based retention time alignment algorithms for multiple chromatography-mass spectrometry datasets

PubMed Central

2012-01-01

Background Modern analytical methods in biology and chemistry use separation techniques coupled to sensitive detectors, such as gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). These hyphenated methods provide high-dimensional data. Comparing such data manually to find corresponding signals is a laborious task, as each experiment usually consists of thousands of individual scans, each containing hundreds or even thousands of distinct signals. In order to allow for successful identification of metabolites or proteins within such data, especially in the context of metabolomics and proteomics, an accurate alignment and matching of corresponding features between two or more experiments is required. Such a matching algorithm should capture fluctuations in the chromatographic system which lead to non-linear distortions on the time axis, as well as systematic changes in recorded intensities. Many different algorithms for the retention time alignment of GC-MS and LC-MS data have been proposed and published, but all of them focus either on aligning previously extracted peak features or on aligning and comparing the complete raw data containing all available features. Results In this paper we introduce two algorithms for retention time alignment of multiple GC-MS datasets: multiple alignment by bidirectional best hits peak assignment and cluster extension (BIPACE) and center-star multiple alignment by pairwise partitioned dynamic time warping (CeMAPP-DTW). We show how the similarity-based peak group matching method BIPACE may be used for multiple alignment calculation individually and how it can be used as a preprocessing step for the pairwise alignments performed by CeMAPP-DTW. We evaluate the algorithms individually and in combination on a previously published small GC-MS dataset studying the Leishmania parasite and on a larger GC-MS dataset studying grains of wheat (Triticum aestivum). Conclusions We have shown that BIPACE achieves very high precision and recall and a very low number of false positive peak assignments on both evaluation datasets. CeMAPP-DTW finds a high number of true positives when executed on its own, but achieves even better results when BIPACE is used to constrain its search space. The source code of both algorithms is included in the OpenSource software framework Maltcms, which is available from http://maltcms.sf.net. The evaluation scripts of the present study are available from the same source. PMID:22920415

Multicomponent Calibration and Quantitation Methods.

DTIC Science & Technology

1984-11-01

liquid chromatographic peaks (45). Applying rank annihilation to LC /UV data requires that the elution profiles of each individual component in the...measurements, e.g. LC /UV, CC/MS, or GC/FTIR analyses. The response of a single component can be described as M = a x y’ (45) 0 where M contains the...in the second dimension. For example, a GC/MS peak consisting - 3 of 50 mass spectra each composed of 20 distinct m/e ratios would result in a matrix

The gas-chromatographic and gas-chromatographic-mass-spectrometric identification of halogen-containing organic compounds

NASA Astrophysics Data System (ADS)

Gidaspov, B. V.; Zenkevich, I. G.; Rodin, A. A.

1989-09-01

The problem of identifying halogen-containing organic compounds in their gas-chromatographic and gas-chromatographic-mass-spectrometric (GC-MS) determination in different materials has been examined. Particular attention has been paid not to the complete characterisation of methods for carrying out this analysis but to the most important problem of increasing the selectivity at the stages of sampling, separation, and interpretation of the gas-chromatographic and GC-MS information. The bibliography contains 292 references.

Dereplication of pentacyclic triterpenoids in plants by GC-EI/MS.

PubMed

Gu, Jian-Qiao; Wang, Yuehong; Franzblau, Scott G; Montenegro, Gloria; Timmermann, Barbara N

2006-01-01

Three common plant-derived pentacyclic triterpenoids, oleanolic acid (1), betulinic acid (2) and ursolic acid (3), have been found to exhibit moderate anti-tubercular activity in a microplate alamar blue assay. In order to facilitate the discovery of novel anti-tubercular leads with diverse chemical structures, a new and rapid GC-EI/MS method was developed simultaneously and unambiguously to dereplicate 1-3 as their methyl esters with limits of detection of 25.6, 26.9 and 26.8 ng, respectively.

Quantitation of cocaine and cocaethylene in small volumes of rat whole blood using gas chromatography-mass spectrometry.

PubMed

Burdick, J D; Boni, R L; Fochtman, F W

1997-05-01

A simple solid phase extraction (SPE) technique combined with gas chromatography-mass spectrometry (GC/MS) operated in selected ion monitoring (SIM) mode is described for quantitation of cocaine and cocaethylene in small samples (250 microliters) of rat whole blood. Use of (N-[2H3C])-cocaine and (N-[2H3C])-cocaethylene internal standards resulted in high sensitivity and selectivity for this analytical method. Analysis was performed using a Hewlett-Packard 5890 GC equipped with a 7673A Automatic Liquid Sampler linked to a Hewlett-Packard 5972 Mass Selective Detector. Separation of analytes was accomplished on a cross-linked methyl silicone gum capillary column (Ultra 1: 12m x 0.2mm (i.d.) x 0.33 microns). Linearity was established over a wide range of concentrations (5.0-2000.0 ng ml-1) with good precision. Limits of detection (LOD) were 1.0 and 2.0 ng ml-1 for cocaine and cocaethylene, respectively. This analytical method was designed for use in pharmacokinetic experiments studying the formation of cocaethylene following ethanol pretreatment in rats administered cocaine.

Determination of phenobarbital in hair matrix by liquid phase microextraction (LPME) and gas chromatography-mass spectrometry (GC-MS).

PubMed

Roveri, Flávia Lopes; Paranhos, Beatriz Aparecida Passos Bismara; Yonamine, Mauricio

2016-08-01

A method for identification and quantification of phenobarbital in hair samples by liquid phase microextraction (LPME) and gas chromatography-mass spectrometry (GC-MS) has been presented. Drug-free hair specimens were collected and separated in 50mg aliquots. Each aliquot was washed with 2.0mL of dichloromethane for 15min at 37°C. Standards and deuterated internal standards for calibration and quality control samples were added to the washed hair aliquot and the sample was submitted to complete digestion with sodium hydroxide (NaOH) 1.0mol/L for 15min at 70°C. The dissolved sample was submitted to LPME. After extraction, the residue was derivatized with tetramethylammonium hydroxide (TMAH) and analyzed by GC-MS. The limit of detection (LOD) was 0.1ng/mg and the limit of quantification (LOQ) was 0.25ng/mg. The calibration curve was linear over a concentration range of 0.25ng/mg to 10ng/mg (r(2)>0.99). The intra- and inter-assay precisions, given by RSD, were less than 6% for phenobarbital. Fortified samples of secobarbital and pentobarbital were also submitted to the validated method. The method was successfully applied to hair samples collected from three volunteers who reported regular use of phenobarbital (clinical treatment). The concentrations found were 9.5, 15.1 and 16.3ng/mg of phenobarbital. To contemplate the concentrations found, dilution integrity tests were also validated. The LPME and GC-MS method showed to be suitable for the detection of phenobarbital in hair samples and can be promptly used for different purposes whenever required. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Interconversion of ephedrine and pseudoephedrine during chemical derivatization.

PubMed

Wong, Colton H F; Ho, Emmie N M; Kwok, W H; Leung, David K K; Leung, Gary N W; Tang, Francis P W; Wong, April S Y; Wong, Jenny K Y; Yu, Nola H; Wan, Terence S M

2012-12-01

Gas chromatography-mass spectrometry (GC-MS) analysis after heptafluorobutyric anhydride (HFBA) derivatization was one of the published methods used for the quantification of ephedrine (EP) and pseudoephedrine (PE) in urine. This method allows the clear separation of the derivatized diastereoisomers on a methyl-silicone-based column. Recently the authors came across a human urine sample with apparently high levels (µg/ml) of EP and PE upon initial screening. However, duplicate analyses of this sample using the HFBA-GC-MS method revealed an unusual discrepancy in the estimated levels of EP and PE, with the area response ratios of EP/PE at around 29% on one occasion and around 57% on another. The same sample was re-analyzed for EP and PE using other techniques, including GC-MS after trimethylsilylation and ultra-high-performance liquid chromatography-tandem mass spectrometry. Surprisingly, the concentration of EP in the sample was determined to be at least two orders of magnitude less than what was observed with the HFBA-GC-MS method. A thorough investigation was then conducted, and the results showed that both substances could interconvert during HFBA derivatization. Similar diastereoisomeric conversion was also observed using other fluorinated acylating agents (e.g. pentafluoropropionic anhydride and trifluoroacetic anhydride). The extent of interconversion was correlated with the degree of fluorination of the acylating agents, with HFBA giving the highest conversion. This conversion has never been reported before. A mechanism for the interconversion was proposed. These findings indicated that fluorinated acylating agents should not be used for the unequivocal identification or quantification of EP and PE as the results obtained can be erroneous. Copyright © 2012 John Wiley & Sons, Ltd.

Headspace Single-Drop Microextraction Gas Chromatography Mass Spectrometry for the Analysis of Volatile Compounds from Herba Asari

PubMed Central

Wang, Guan-Jie; Tian, Li; Fan, Yu-Ming; Qi, Mei-Ling

2013-01-01

A rapid headspace single-drop microextraction gas chromatography mass spectrometry (SDME-GC-MS) for the analysis of the volatile compounds in Herba Asari was developed in this study. The extraction solvent, extraction temperature and time, sample amount, and particle size were optimized. A mixed solvent of n-tridecane and butyl acetate (1 : 1) was finally used for the extraction with sample amount of 0.750 g and 100-mesh particle size at 70°C for 15 min. Under the determined conditions, the pound samples of Herba Asari were directly applied for the analysis. The result showed that SDME-GC–MS method was a simple, effective, and inexpensive way to measure the volatile compounds in Herba Asari and could be used for the analysis of volatile compounds in Chinese medicine. PMID:23607049

Validation of an Analytical Method for the Determination of Pesticide Residues in Vine Leaves by GC-MS/MS.

PubMed

Maestroni, Britt; Abu Alnaser, Amer; Ghanem, Iyad; Islam, Marivil; Cesio, Veronica; Heinzen, Horacio; Kelly, Simon; Cannavan, Andrew

2018-06-27

A modified and miniaturized SweEt/QuEChERS method for pesticide residue analysis applied to vine leaves is presented. The deep-frozen plant material was cryogenically processed. A 2 g analytical portion was hydrated for 30 min and extracted with acidified ethyl acetate after buffering with NaHCO 3 and adding Na 2 SO 4 . A dispersive solid-phase (d-SPE) cleanup step with primary-secondary amine (PSA) was performed. The pesticide residues were determined using GC-MS/MS. The whole procedure was validated for 54-59 pesticides at 0.01, 0.02, 0.1, and 0.2 mg/kg in fresh vine leaves ( Vitis vinifera). The key method performance parameters investigated were specificity, linearity, trueness, within laboratory repeatability and reproducibility, limit of detection, limit of quantitation, and matrix effects. Recoveries for the 59 pesticides tested ranged from 60 to 110%, and the RSDs were lower than 20% for the majority of the pesticides studied.

Differentiation of wines according to grape variety and geographical origin based on volatiles profiling using SPME-MS and SPME-GC/MS methods.

PubMed

Ziółkowska, Angelika; Wąsowicz, Erwin; Jeleń, Henryk H

2016-12-15

Among methods to detect wine adulteration, profiling volatiles is one with a great potential regarding robustness, analysis time and abundance of information for subsequent data treatment. Volatile fraction fingerprinting by solid-phase microextraction with direct analysis by mass spectrometry without compounds separation (SPME-MS) was used for differentiation of white as well as red wines. The aim was to differentiate between varieties used for wine production and to also differentiate wines by country of origin. The results obtained were compared to SPME-GC/MS analysis in which compounds were resolved by gas chromatography. For both approaches the same type of statistical procedure was used to compare samples: principal component analysis (PCA) followed by linear discriminant analysis (LDA). White wines (38) and red wines (41) representing different grape varieties and various regions of origin were analysed. SPME-MS proved to be advantageous in use due to better discrimination and higher sample throughput. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multi-residue pesticide analysis (gas chromatography-tandem mass spectrometry detection)-Improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals-Benefit and limit of a standardized apple purée calibration (screening).

PubMed

Rasche, Claudia; Fournes, Britta; Dirks, Uwe; Speer, Karl

2015-07-17

Some steps of the QuEChERS method for the analysis of pesticides with GC-MS/MS in cereals and dried fruits were improved or simplified. For the latter, a mixing vessel with stator-rotor-system proved to be advantageous. The extraction procedure of dried fruits is much easier and safer than the Ultra Turrax and results in excellent validation data at a concentration level of 0.01mg/kg (116 of 118 analytes with recoveries in the range of 70-120%, 117 of 118 analytes with RSD <20%). After qualifying problematic lipophilic pesticides in fat-rich cereals (fat content >7%), predominantly organochlorines showed recoveries of <70% in quantification when the standard QuEChERS method with water was used. A second extraction was carried out analogous to the QuEChERS method, however, without the addition of water. With this simple modification, the problematic lipophilic pesticides, which had been strongly affected by the fat content of the commodities, could be determined with recoveries above 70% even at a concentration level of 0.01mg/kg. Moreover, a GC-MS/MS screening method for 120 pesticides at a concentration level of 0.01mg/kg was established by employing analyte protectants (ethylglycerol, gulonolactone, and sorbitol). The use of only one standardized calibration, made of an apple purée extract in combination with analyte protectants, allowed for a qualitative and quantitative analysis of 120 pesticides in different matrix extracts (tomato, red pepper, sour cherries, dried apples, black currant powder, raisins, wheat flour, rolled oats, wheat germ). The analyte protectants leveled the differences in the matrix-induced protection effect of the analyzed extracts over a wide range. The majority of the pesticides were analyzed with good analytical results (recoveries in the range of 70-120% and RSD <20%). Copyright © 2015 Elsevier B.V. All rights reserved.

Rapid method for the simultaneous detection of boar taint compounds by means of solid phase microextraction coupled to gas chromatography/mass spectrometry.

PubMed

Verplanken, Kaat; Wauters, Jella; Van Durme, Jim; Claus, Dirk; Vercammen, Joeri; De Saeger, Sarah; Vanhaecke, Lynn

2016-09-02

Because of animal welfare issues, the voluntary ban on surgical castration of male piglets, starting January 2018 was announced in a European Treaty. One viable alternative is the fattening of entire male pigs. However, this can cause negative consumer reactions due to the occurrence of boar taint and possibly lead to severe economic losses in pig husbandry. In this study, headspace solid phase microextraction (HS-SPME) coupled to GC-MS was used in the development and optimization of a candidate method for fast and accurate detection of the boar taint compounds. Remarkably fast extraction (45s) of the boar taint compounds from adipose tissue was achieved by singeing the fat with a soldering iron while released volatiles were extracted in-situ using HS-SPME. The obtained method showed good performance characteristics after validation according to CD 2002/657/EC and ISO/IEC 17025 guidelines. Moreover, cross-validation with an in-house UHPLC-HR-Orbitrap-MS method showed good agreement between an in-laboratory method and the new candidate method for the fast extraction and detection of skatole and androstenone, which emphasizes the accuracy of this new SPME-GC-MS method. Threshold detection of the boar taint compounds on a portable GC-MS could not be achieved. However, despite the lack of sensitivity obtained on the latter instrument, a very fast method with run-to-run time of 3.5min for the detection of the boar taint compounds was developed. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants in fish using fast, low-pressure gas chromatography-tandem mass spectrometry.

PubMed

Sapozhnikova, Yelena; Lehotay, Steven J

2013-01-03

A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated using fast low pressure gas chromatography triple quadrupole tandem mass spectrometry (LP-GC/MS-MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) clean-up with zirconium-based sorbent prior to LP-GC/MS-MS analysis. The developed method was evaluated at 4 spiking levels and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974B and 1947. Sample preparation for a batch of 10 homogenized samples took about 1h/analyst, and LP-GC/MS-MS analysis provided fast separation of multiple analytes within 9min achieving high throughput. With the use of isotopically labeled internal standards, recoveries of all but one analyte were between 70 and 120% with relative standard deviations less than 20% (n=5). The measured values for both SRMs agreed with certified/reference values (72-119% accuracy) for the majority of analytes. The detection limits were 0.1-0.5ng g(-1) for PCBs, 0.5-10ng g(-1) for PBDEs, 0.5-5ng g(-1) for select pesticides and PAHs and 1-10ng g(-1) for flame retardants. The developed method was successfully applied for analysis of catfish samples from the market. Published by Elsevier B.V.

Quantitative analysis of the endogenous GHB level in the hair of the Chinese population using GC/MS/MS.

PubMed

Shi, Yan; Cui, Xiaopei; Shen, Min; Xiang, Ping

2016-04-01

Endogenous production complicates interpretation when gamma-hydroxybutyrate (GHB) is measured in hair for forensic purposes. A method capable of quantifying the endogenous concentration of GHB in human head hair was developed and validated using GC/MS/MS. Hair was digested under alkaline conditions (1 mol/L NaOH, 90 °C 10 min), and GHB-d6 was used as an internal standard. Before derivatization with BSTFA and ethyl acetate, a liquid-liquid extraction with ethyl acetate under acidic conditions was performed. GHB-TMS derivatives were detected using GC/MS/MS in the multiple-reaction monitoring mode. This method exhibited good linearity (y = 0.018x + 0.038, R(2) = 0.9998), and the limit of detection was 0.02 ng/mg. The extraction recoveries were more than 60%, and the inter-day and intra-day relative standard deviations (RSD) were less than 15%. This method has been applied for the analysis of the endogenous GHB in hair samples from 66 drug-free Chinese donors. The mean measured concentration for 0-3 cm hair was 1.93 ± 1.40 ng/mg (n = 66), and extreme values were in the range of 0.28-4.91 ng/mg. The mean male endogenous GHB level was 2.95 ng/mg (0.92-4.91 ng/mg, n = 35), while the mean female level was 0.77 ng/mg (0.28-1.95 ng/mg, n = 31). This method was applied to a forensic case for the determination of GHB in hair samples but it is hard to make a reasonable "cut off" in hair. The solution is to use each subject as his own control. Copyright © 2016 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

Compensation for matrix effects in the gas chromatography-mass spectrometry analysis of 186 pesticides in tea matrices using analyte protectants.

PubMed

Li, Yan; Chen, Xi; Fan, Chunlin; Pang, Guofang

2012-11-30

A gas chromatography-mass spectrometry (GC-MS) analytical method was developed for simultaneously determining 186 pesticides in tea matrices using analyte protectants to counteract the matrix-induced effect. The matrix effects were evaluated for green, oolong and black tea, representing unfermented, partially fermented and completely fermented teas respectively and depending on the type of tea, 72%, 94% and 94% of the pesticides presented strong response enhancement effect. Several analyte protectants as well as certain combinations of these protectants were evaluated to check their compensation effects. A mixture of triglycerol and d-ribonic acid-γ-lactone (both at 2mg/mL in the injected samples) was found to be the most effective in improving the chromatographic behavior of the 186 pesticides. More than 96% of the 186 pesticides achieved recoveries within the range of 70-120% when using the selected mixture of analyte protectants. The simple addition of analyte protectants offers a more convenient solution to overcome matrix effects, results in less active sites compared to matrix-matched standardization and can be an effective approach to compensate for matrix effects in the GC-MS analysis of pesticide residues. Copyright © 2012 Elsevier B.V. All rights reserved.

Authenticity of raspberry flavor in food products using SPME-chiral-GC-MS.

PubMed

Hansen, Anne-Mette S; Frandsen, Henrik L; Fromberg, Arvid

2016-05-01

A fast and simple method for authenticating raspberry flavors from food products was developed. The two enantiomers of the compound (E)-α-ionone from raspberry flavor were separated on a chiral gas chromatographic column. Based on the ratio of these two enantiomers, the naturalness of a raspberry flavor can be evaluated due to the fact that a natural flavor will consist almost exclusively of the R enantiomer, while a chemical synthesis of the same compound will result in a racemic mixture. Twenty-seven food products containing raspberry flavors where investigated using SPME-chiral-GC-MS. We found raspberry jam, dried raspberries, and sodas declared to contain natural aroma all contained almost only R-(E)-α-ionone supporting the content of natural raspberry aroma. Six out of eight sweets tested did not indicate a content of natural aroma on the labeling which was in agreement with the almost equal distribution of the R and S isomer. Two products were labeled to contain natural raspberry flavors but were found to contain almost equal amounts of both enantiomers indicating a presence of synthetic raspberry flavors only. Additionally, two products that were labeled to contain both raspberry juice and flavor showed equal amounts of both enantiomers, indicating the presence of synthetic flavor.

Fast, high temperature and thermolabile GC--MS in supersonic molecular beams

NASA Astrophysics Data System (ADS)

Dagan, Shai; Amirav, Aviv

1994-05-01

This work describes and evaluates the coupling of a fast gas chromatograph (GC) based on a short column and high carrier gas flow rate to a supersonic molecular beam mass spectrometer (MS). A 50 cm long megabore column serves for fast GC separation and connects the injector to the supersonic nozzle source. Sampling is achieved with a conventional syringe based splitless sample injection. The injector contains no septum and is open to the atmosphere. The linear velocity of the carrier gas is controlled by a by-pass (make-up) gas flow introduced after the column and prior to the supersonic nozzle. The supersonic expansion serves as a jet separator and the skimmed supersonic molecular beam (SMB) is highly enriched with the heavier organic molecules. The supersonic molecular beam constituents are ionized either by electron impact (EI) or hyperthermal surface ionization (HSI) and mass analyzed. A 1 s fast GC--MS of four aromatic molecules in methanol is demonstrated and some fundamental aspects of fast GC--MS with time limit constraints are outlined. The flow control (programming) of the speed of analysis is shown and the analysis of thermolabile and relatively non-volatile molecules is demonstrated and discussed. The tail-free, fast GC--MS of several mixtures is shown and peak tailing of caffeine is compared with that of conventional GC--MS. The improvement of the peak shapes with the SMB--MS is analyzed with the respect to the elimination of thermal vacuum chamber background. The extrapolated minimum detected amount was about 400 ag of anthracence-d10, with an elution time which was shorter than 2s. Repetitive injections could be performed within less than 10 s. The fast GC--MS in SMB seems to be ideal for fast target compound analysis even in real world, complex mixtures. The few seconds GC--MS separation and quantification of lead (as tetraethyllead) in gasoline, caffeine in coffee, and codeine in a drug is demonstrated. Controlled HSI selectivity is demonstrated in the range of 101 to 104 anthracene/decane which helped to simplify the selective analysis of aromatic molecules in gasoline. The contribution of SMB to the operation of the fast GC--MS is summarized and the compatibility with conventional GC having a megabore column is shown. Splitless injections of 100 [mu]L sample solutions for trace level concentration detection is also presented (with a conventional GC).

Sterol Profile for Natural Juices Authentification by GC-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Culea, M.

A GC-MS analytical method is described for some natural juices analysis. The fingerprint of sterols was used to characterize the natural juice. A rapid liquid-liquid extraction method was used. The sterols were separated on a Rtx-5MS capillary column, 15mx0.25mm, 0.25{mu}m film thickness, in a temperature program from 50 deg. C for 1 min, then ramped at 15 deg. C/min to 300 deg. C and held for 15 min. Identification of sterols and their patterns were used for juice characterization. The sterol profile is a useful approach for confirming the presence of juices of orange, grapefruit, pineapple and passion fruit inmore » compounded beverages and for detecting of adulteration of fruit juices.« less

Experimental design-based isotope-dilution SPME-GC/MS method development for the analysis of smoke flavouring products.

PubMed

Giri, Anupam; Zelinkova, Zuzana; Wenzl, Thomas

2017-12-01

For the implementation of Regulation (EC) No 2065/2003 related to smoke flavourings used or intended for use in or on foods a method based on solid-phase micro extraction (SPME) GC/MS was developed for the characterisation of liquid smoke products. A statistically based experimental design (DoE) was used for method optimisation. The best general conditions to quantitatively analyse the liquid smoke compounds were obtained with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre, 60°C extraction temperature, 30 min extraction time, 250°C desorption temperature, 180 s desorption time, 15 s agitation time, and 250 rpm agitation speed. Under the optimised conditions, 119 wood pyrolysis products including furan/pyran derivatives, phenols, guaiacol, syringol, benzenediol, and their derivatives, cyclic ketones, and several other heterocyclic compounds were identified. The proposed method was repeatable (RSD% <5) and the calibration functions were linear for all compounds under study. Nine isotopically labelled internal standards were used for improving quantification of analytes by compensating matrix effects that might affect headspace equilibrium and extractability of compounds. The optimised isotope dilution SPME-GC/MS based analytical method proved to be fit for purpose, allowing the rapid identification and quantification of volatile compounds in liquid smoke flavourings.

Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

PubMed

Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

2015-12-01

Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400 ng m(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air.

Investigation of Imposter Perfumes Using GC-MS

ERIC Educational Resources Information Center

Mowery, Kelly A.; Blanchard, Daniel E.; Smith, Stephanie; Betts, Thomas A.

2004-01-01

An experiment to initiate students into several features of gas chromatograph-mass spectrometers (GC-MS) through the study of branded and counterfeit perfumes is described. The experiment enables the students to appreciate the power of GC-MS in distinguishing between original and imitation perfumes, and in analyzing data with its application…

Comparison of various extraction methods for policosanol from rice bran wax and establishment of chromatographic fingerprint of policosanol.

PubMed

Wang, Mei-Fei; Lian, Hong-Zhen; Mao, Li; Zhou, Jing-Ping; Gong, Hui-Juan; Qian, Bao-Yong; Fang, Yan; Li, Jie

2007-07-11

A capillary gas chromatographic (GC) method has been developed for the separation and determination of policosanol components extracted from rice bran wax. A Varian CP-sil 8 CB column was employed, and an oven temperature was programmed. Gas chromatography-mass spectrometry (GC-MS) was used to identify the composition of policosanol. Quantitative analysis was carried out by means of hydrogen flame ionization detector (FID) with dinonyl phthalate (DNP) as internal standard. The results indicated that the extract obtained by dry saponification has the highest contents of octacosanol and triacontanol among extracts by all used extraction methods including dry saponification, saponification in alcohol, saponification in water (neutralized and non-neutralized), and transesterification. Meanwhile, the GC-MS fingerprint of policosanol extracted by dry saponification has been established. Euclidean distance similarity calculation showed remarkable consistency of compositions and contents among 12 batches of policosanol from a rice bran wax variety. This protocol provided a rapid and feasible method for quality control of policosanol products.

A multi-residue method for pesticides analysis in green coffee beans using gas chromatography-negative chemical ionization mass spectrometry in selective ion monitoring mode.

PubMed

Pizzutti, Ionara R; de Kok, Andre; Dickow Cardoso, Carmem; Reichert, Bárbara; de Kroon, Marijke; Wind, Wouter; Weber Righi, Laís; Caiel da Silva, Rosselei

2012-08-17

In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 μg kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ≤ 20% at the lowest spike concentration of 10 μg kg(-1), the target method LOQ. For the spike concentrations of 20 and 50 μg kg(-1), the recoveries and RSDs were even better. The validated LOQ(m) was 10, 20 and 50 μg kg(-1) for respectively 33, 3 and 6 of the analytes studied. For five compounds, the European Union method performance requirements for the validation of a quantitative method (average recoveries between 70-120% and repeatability RSD ≤ 20%) were not achieved and 4 problematic pesticides (captan, captafol, folpet and dicofol) could not be detected as their parent compound, but only via their degradation products. Although the matrix effect (matrix-enhanced detector response) was high for all pesticides studied, the matrix interference was minimal, due to the high selectivity obtained with the GC-NCI-MS detection. Matrix-matched calibration for applying the method in routine analysis is recommended for reliable quantitative results. Copyright © 2012 Elsevier B.V. All rights reserved.

GC/GCMS analysis of the petroleum ether and dichloromethane extracts of Moringa oleifera roots

PubMed Central

Faizi, Shaheen; Sumbul, Saima; Versiani, Muhammed Ali; Saleem, Rubeena; Sana, Aisha; Siddiqui, Hira

2014-01-01

Objective To explore the phytochemical constituents from petroleum ether and dichloromethane extracts of Moringa oleifera (M. oleifera) roots using GC/GC-MS. Methods A total of 5.11 kg fresh and undried crushed root of M. oleifera were cut into small pieces and extracted with petroleum ether and dichloromethane (20 L each) at room temperature for 2 d. The concentrated extracts were subjected to their GC-MS analysis. Results The GC-MS analysis of the petroleum ether and dichloromethane extracts of M. oleifera roots, which showed promising biological activities, has resulted in the identification 102 compounds. These constituents belong to 15 classes of compounds including hydrocarbons, fatty acids, esters, alcohols, isothiocyanate, thiocyanate, pyrazine, aromatics, alkamides, cyanides, steroids, halocompounds, urea and N-hydroxyimine derivatives, unsaturated alkenamides, alkyne and indole. GC/GC-MS studies on petroleum ether extract of the roots revealed that it contained 39 compounds, belonging to nine classes. Cyclooctasulfur S8 has been isolated as a pure compound from the extract. The major compounds identified from petroleum ether extract were trans-13-docosene (37.9%), nonacosane (32.6%), cycloartenol (28.6%) nonadecanoic acid (13.9%) and cyclooctasulfur S8 (13.9%). Dichloromethane extract of the roots was composed of 63 compounds of which nasimizinol (58.8%) along with oleic acid (46.5%), N-benzyl-N-(7-cyanato heptanamide (38.3%), N-benzyl-N-(1-chlorononyl) amide (30.3%), bis [3-benzyl prop-2-ene]-1-one (19.5%) and N, N-dibenzyl-2-ene pent 1, 5-diamide (11.6%) were the main constituents. Conclusions This study helps to predict the formula and structure of active molecules which can be used as drugs. This result also enhances the traditional usage of M. oleifera which possesses a number of bioactive compounds. PMID:25183335

Identification of Major Histocompatibility Complex-Regulated Body Odorants by Statistical Analysis of a Comparative Gas Chromatography/Mass Spectrometry Experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willse, Alan R.; Belcher, Ann; Preti, George

2005-04-15

Gas chromatography (GC), combined with mass spectrometry (MS) detection, is a powerful analytical technique that can be used to separate, quantify, and identify volatile compounds in complex mixtures. This paper examines the application of GC-MS in a comparative experiment to identify volatiles that differ in concentration between two groups. A complex mixture might comprise several hundred or even thousands of volatile compounds. Because their number and location in a chromatogram generally are unknown, and because components overlap in populous chromatograms, the statistical problems offer significant challenges beyond traditional two-group screening procedures. We describe a statistical procedure to compare two-dimensional GC-MSmore » profiles between groups, which entails (1) signal processing: baseline correction and peak detection in single ion chromatograms; (2) aligning chromatograms in time; (3) normalizing differences in overall signal intensities; and (4) detecting chromatographic regions that differ between groups. Compared to existing approaches, the proposed method is robust to errors made at earlier stages of analysis, such as missed peaks or slightly misaligned chromatograms. To illustrate the method, we identify differences in GC-MS chromatograms of ether-extracted urine collected from two nearly identical inbred groups of mice, to investigate the relationship between odor and genetics of the major histocompatibility complex.« less

Volatile and key odourant compounds of Turkish Berberis crataegina fruit using GC-MS-Olfactometry.

PubMed

Sonmezdag, Ahmet Salih; Kelebek, Hasim; Selli, Serkan

2018-04-01

This research was conducted to identify the aroma and aroma-active compounds of Berberis crataegina for the first time. Volatile profile of B. crataegina was obtained using the purge and trap extraction method with dichloromethane. Gas chromatography was coupled to mass spectrometry (GC-MS) allowed the quantitative and qualitative detection of 22 compounds in the sample. Aldehydes were the main chemical group in the sample and followed by aromatic alcohols and lactone. Aroma extract dilution analysis was implemented for the specification of key odourants of B. crataegina. In total, eight key odourants were detected in the extract of the sample, using GC-MS-Olfactometry and aldehydes were the leading chemical group. The key odourants, found to be contributing to the overall aroma in B. crataegina, were nonanal (FD = 1024; green, flowery), hexanal (FD = 512; green) and linalool (FD = 256; flowery, rose) because of high FD factors.

Cyclooxygenase and lipoxygenase-like activity in Drosophila melanogaster.

PubMed

Pagés, M; Roselló, J; Casas, J; Gelpí, E; Gualde, N; Rigaud, M

1986-11-01

To determine the possible activity of cyclooxygenase and lipoxygenase like enzymes in Drosophila melanogaster, we have investigated whether fly homogenates can biosynthesize prostaglandins and HETEs. Incubation of fly extracts with AA yields a mixture of 15- 12- 9- and 8-HETE as detected by selected ion monitoring GC-MS. Also the combination of HPLC-RIA using a PGE antibody shows the presence of endogenous PGE2 immunoreactivity in the extracts (405 pg/g in males and 165 pg/g in females). We have also detected the presence of lipoxygenase like immunoreactivity in the reproductive male system by using immunocytochemical techniques in whole body sections of the fly as well as reactivity in the digestive system of both males and females. Finally, we have not been able to detect endogenous AA in the fly by GC-MS methods. However, estimates by GC-MS of the total body fatty acids indicate substantial amounts of potential AA precursors.

[Determination of fatty acids in natural cream and artificial cream by comprehensive two-dimensional gas chromatography-mass spectrometry].

PubMed

Zhou, Ruize; Zhou, Ya; Mao, Ting; Jiang, Jie

2018-01-08

A method for the determination of 37 fatty acids in natural cream and artificial cream was developed by comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS). The samples were extracted with toluene and acetyl chloride-methanol (1:9,v/v) solution was added to the extract for fat esterification. Finally, the fatty acids were analyzed by GC×GC-MS. The GC conditions were as follows:a DB-5 column (30 m×0.25 mm×0.25 μm) was set as the 1st dimensional column and a BPX-50 column (2.5 m×0.1 mm×0.25 μm) was the 2nd dimensional column. The primary oven temperature was programmed from 50℃ (held for 2 min) to 180℃ at a rate of 20℃/min, followed by an increase to 250℃ at 2.5℃/min, then raised up to 300℃ (held for 5 min) at 3℃/min. The ion source temperature was 200℃ with auxiliary temperature of 300℃ in scan mode. All fatty acids were separated effectively and determined accurately while the modulation period was 5s and the scan range of MS was m/z 40-385. This procedure was applied to analyze the fatty acids in commercial natural cream and artificial cream from Chinese markets, among which we found the characteristic components in different kinds of samples. Compared with gas chromatography-flame ionization detector (GC-FID), GC×GC-MS method was more sensitive and more components of fatty acids were detected. Conclusively, this work suggests a new technical approach in analyzing fatty acids in natural cream and artificial cream, which is meaningful to ensure the quality identification and safety of natural cream.

Establishing and performing targeted multi-residue analysis for lipid mediators and fatty acids in small clinical plasma samples.

USDA-ARS?s Scientific Manuscript database

LC-MS/MS and GC-MS based targeted metabolomics is typically conducted by analyzing and quantifying a cascade of metabolites with methods specifically developed for the metabolite class. Here we describe an approach for the development of multi-residue analytical profiles, calibration standards, and ...

Detection of metabolites of lysergic acid diethylamide (LSD) in human urine specimens: 2-oxo-3-hydroxy-LSD, a prevalent metabolite of LSD.

PubMed

Poch, G K; Klette, K L; Hallare, D A; Manglicmot, M G; Czarny, R J; McWhorter, L K; Anderson, C J

1999-03-05

Seventy-four urine specimens previously found to contain lysergic acid diethylamide (LSD) by gas chromatography-mass spectrometry (GC-MS) were analyzed by a new procedure for the LSD metabolite 2-oxo-3-hydroxy-LSD (O-H-LSD) using a Finnigan LC-MS-MS system. This procedure proved to be less complex, shorter to perform and provides cleaner chromatographic characteristics than the method currently utilized by the Navy Drug Screening Laboratories for the extraction of LSD from urine by GC-MS. All of the specimens used in the study screened positive for LSD by radioimmunoassay (Roche Abuscreen). Analysis by GC-MS revealed detectable amounts of LSD in all of the specimens. In addition, isolysergic diethylamide (iso-LSD), a byproduct of LSD synthesis, was quantitated in 64 of the specimens. Utilizing the new LC-MS-MS method, low levels of N-desmethyl-LSD (nor-LSD), another identified LSD metabolite, were detected in some of the specimens. However, all 74 specimens contained O-H-LSD at significantly higher concentrations than LSD, iso-LSD, or nor-LSD alone. The O-H-LSD concentration ranged from 732 to 112 831 pg/ml (mean, 16340 pg/ml) by quantification with an internal standard. The ratio of O-H-LSD to LSD ranged from 1.1 to 778.1 (mean, 42.9). The presence of O-H-LSD at substantially higher concentrations than LSD suggests that the analysis for O-H-LSD as the target analyte by employing LC-MS-MS will provide a much longer window of detection for the use of LSD than the analysis of the parent compound, LSD.

Analytical Challenge in Postmortem Toxicology Applied to a Human Body Found into a Lake after Three Years Immersion.

PubMed

Morini, Luca; Vignali, Claudia; Tricomi, Paolo; Groppi, Angelo

2015-09-01

The body of a 30-year-old woman was found in Como lake at a depth of about 120 meters in her own car after 3 years of immersion. The aim of this study was to evaluate psychoactive drugs as well as alcohol biomarkers in biological matrices. The following analyses were initially performed: GC-MS systematic toxicological analysis on biological fluids and tissues; GC-MS analysis of drugs of abuse on pubic hair; direct ethanol metabolite determination in pubic hair by LC-MS/MS. After 7 years, the samples, that had been stored at -20°C, were re-analyzed and submitted to an LC-MS/MS targeted screening method, using multiple reaction monitoring mode. These analyses detected citalopram (150-3000 ng/mL), desmethylcitalopram (50-2300 ng/mL), clotiapine (20-65 ng/mL), and ethyl glucuronide (97 pg/mg). The methods showed an acceptable reproducibility, and the concentrations of citalopram and desmethylcitalopram calculated through the two analytical techniques did not significantly differ in biological fluids. © 2015 American Academy of Forensic Sciences.

Pistachio oil (Pistacia vera L. cv. Uzun): Characterization of key odorants in a representative aromatic extract by GC-MS-olfactometry and phenolic profile by LC-ESI-MS/MS.

PubMed

Sonmezdag, Ahmet Salih; Kelebek, Hasim; Selli, Serkan

2018-02-01

Volatile, aroma-active, and phenolic compounds of pistachio oil obtained from cv. Uzun were investigated in the current study. To obtain a representative aromatic extract, three of the most widely used extraction methods were compared using a representative test; the solvent-assisted flavour extraction (SAFE) aromatic extract from pistachio oil was found to be the most representative. A total of 50 aroma compounds were determined in pistachio oil and it was found that terpenes, aldehydes, and alcohols were the most abundant volatile compounds. Applying GC-MS-olfactometry and aroma extract dilution analysis (AEDA) resulted in a total of 14 aroma-active areas being detected in the extract of pistachio oil. In the phenolic fraction obtained by the LC-ESI-MS/MS method, a total of 12 phenolic compounds was found in the pistachio oil, of which seven compounds were reported for the first time. Eriodictyol-7-O-glucoside and protocatechuic acid were the most dominant phenolic compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Supercritical fluid chromatography applied to the highly selective isolation of urinary steroid hormones prior to GC/MS analysis.

PubMed

Doué, Mickael; West, Caroline; Bichon, Emmanuelle; Le Bizec, Bruno; Lesellier, Eric

2018-06-01

To assess the presence of prohibited anabolic substances used to promote growth in livestock, calf urine is the most relevant matrix. However, the sample preparation methods (required to remove unwanted matrix components and fractionate isobaric species that may be unresolved by gas chromatography- mass spectrometry GC/MS) are long and complex. In this context, semi-preparative supercritical fluid chromatography (SFC) was considered to possibly simplify the sample preparation in reducing the number of procedures. Fifteen stationary phases were screened with SFC combined with UV and evaporative light-scattering detection (ELSD), among which two columns (Cosmosil π-NAP and Princeton DIOL) were retained for their ability to isolate steroid hormones from other matrix components and, for the second column, for the additional possibility to fractionate steroid hormones into different families (estrogens, mono-hydroxylated and di-hydroxylated androgens). The fractions were further analysed with GC/MS showing the benefit of class fractionation. The final method allows for significant time, solvent and money savings compared to the previously widely used method (solid-phase extraction combined with semi-preparative high-performance liquid chromatography). Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of polyethylene microplastics in environmental samples, using a thermal decomposition method.

PubMed

Dümichen, Erik; Barthel, Anne-Kathrin; Braun, Ulrike; Bannick, Claus G; Brand, Kathrin; Jekel, Martin; Senz, Rainer

2015-11-15

Small polymer particles with a diameter of less than 5 mm called microplastics find their way into the environment from polymer debris and industrial production. Therefore a method is needed to identify and quantify microplastics in various environmental samples to generate reliable concentration values. Such concentration values, i.e. quantitative results, are necessary for an assessment of microplastic in environmental media. This was achieved by thermal extraction in thermogravimetric analysis (TGA), connected to a solid-phase adsorber. These adsorbers were subsequently analysed by thermal desorption gas chromatography mass spectrometry (TDS-GC-MS). In comparison to other chromatographic methods, like pyrolyse gas chromatography mass spectrometry (Py-GC-MS), the relatively high sample masses in TGA (about 200 times higher than used in Py-GC-MS) analysed here enable the measurement of complex matrices that are not homogenous on a small scale. Through the characteristic decomposition products known for every kind of polymer it is possible to identify and even to quantify polymer particles in various matrices. Polyethylene (PE), one of the most important representatives for microplastics, was chosen as an example for identification and quantification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Analysis of ammonium nitrate headspace by on-fiber solid phase microextraction derivatization with gas chromatography mass spectrometry.

PubMed

Lubrano, Adam L; Andrews, Benjamin; Hammond, Mark; Collins, Greg E; Rose-Pehrsson, Susan

2016-01-15

A novel analytical method has been developed for the quantitation of trace levels of ammonia in the headspace of ammonium nitrate (AN) using derivatized solid phase microextraction (SPME) fibers with gas chromatography mass spectrometry (GC-MS). Ammonia is difficult to detect via direct injection into a GC-MS because of its low molecular weight and extreme polarity. To circumvent this issue, ammonia was derivatized directly onto a SPME fiber by the reaction of butyl chloroformate coated fibers with the ammonia to form butyl carbamate. A derivatized externally sampled internal standard (dESIS) method based upon the reactivity of diethylamine with unreacted butyl chloroformate on the SPME fiber to form butyl diethylcarbamate was established for the reproducible quantification of ammonia concentration. Both of these compounds are easily detectable and separable via GC-MS. The optimized method was then used to quantitate the vapor concentration of ammonia in the headspace of two commonly used improvised explosive device (IED) materials, ammonium nitrate fuel oil (ANFO) and ammonium nitrate aluminum powder (Ammonal), as well as identify the presence of additional fuel components within the headspace. Published by Elsevier B.V.

Case Report: GcMAF Treatment in a Patient with Multiple Sclerosis.

PubMed

Inui, Toshio; Katsuura, Goro; Kubo, Kentaro; Kuchiike, Daisuke; Chenery, Leslye; Uto, Yoshihiro; Nishikata, Takahito; Mette, Martin

2016-07-01

Gc protein-derived macrophage-activating factor (GcMAF) has various functions as an immune modulator, such as macrophage activation, anti-angiogenic activity and anti-tumor activity. Clinical trials of second-generation GcMAF demonstrated remarkable clinical effects in several types of cancers. Thus, GcMAF-based immunotherapy has a wide application for use in the treatment of many diseases via macrophage activation that can be used as a supportive therapy. Multiple sclerosis (MS) is considered to be an autoimmune disorder that affects the myelinated axons in the central nervous system (CNS). This study was undertaken to examine the effects of second-generation GcMAF in a patient with MS. This case study demonstrated that treatments of GcMAF in a patient with MS have potent therapeutic actions with early beneficial responses, especially improvement of motor dysfunction. GcMAF shows therapeutic potency in the treatment of MS. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Evaluation of volatiles from two subtropical strawberry cultivars using GC-olfactometry, GC-MS odor activity values, and sensory analysis

USDA-ARS?s Scientific Manuscript database

Flavor profiles of two Florida strawberry cultivars were determined using GC-olfactometry,GC-MS, odor activity values (OAVs) and sensory analysis. Thirty-six aroma active compounds were detected using GC-O. Thirty-four were identified. The major odor-active compounds in decreasing intensity were: me...

Facile synthesis of magnetic carbon nitride nanosheets and its application in magnetic solid phase extraction for polycyclic aromatic hydrocarbons in edible oil samples.

PubMed

Zheng, Hao-Bo; Ding, Jun; Zheng, Shu-Jian; Zhu, Gang-Tian; Yuan, Bi-Feng; Feng, Yu-Qi

2016-01-01

In this study, we proposed a method to fabricate magnetic carbon nitride (CN) nanosheets by simple physical blending. Low-cost CN nanosheets prepared by urea possessed a highly π-conjugated structure; therefore the obtained composites were employed as magnetic solid-phase extraction (MSPE) sorbent for extraction of polycyclic aromatic hydrocarbons (PAHs) in edible oil samples. Moreover, sample pre-treatment time could be carried out within 10 min. Thus, a simple and cheap method for the analysis of PAHs in edible oil samples was established by coupling magnetic CN nanosheets-based MSPE with gas chromatography-mass spectrometry (GC/MS) analysis. Limits of quantitation (LOQs) for eight PAHs ranged from 0.4 to 0.9 ng/g. The intra- and inter-day relative standard deviations (RSDs) were less than 15.0%. The recoveries of PAHs for spiked soybean oil samples ranged from 91.0% to 124.1%, with RSDs of less than 10.2%. Taken together, the proposed method offers a simple and cost-effective option for the convenient analysis of PAHs in oil samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Automated GC-MS analysis of free amino acids in biological fluids.

PubMed

Kaspar, Hannelore; Dettmer, Katja; Gronwald, Wolfram; Oefner, Peter J

2008-07-15

A gas chromatography-mass spectrometry (GC-MS) method was developed for the quantitative analysis of free amino acids as their propyl chloroformate derivatives in biological fluids. Derivatization with propyl chloroformate is carried out directly in the biological samples without prior protein precipitation or solid-phase extraction of the amino acids, thereby allowing automation of the entire procedure, including addition of reagents, extraction and injection into the GC-MS. The total analysis time was 30 min and 30 amino acids could be reliably quantified using 19 stable isotope-labeled amino acids as internal standards. Limits of detection (LOD) and lower limits of quantification (LLOQ) were in the range of 0.03-12 microM and 0.3-30 microM, respectively. The method was validated using a certified amino acid standard and reference plasma, and its applicability to different biological fluids was shown. Intra-day precision for the analysis of human urine, blood plasma, and cell culture medium was 2.0-8.8%, 0.9-8.3%, and 2.0-14.3%, respectively, while the inter-day precision for human urine was 1.5-14.1%.

MEETING IN CHARLOTTE: SOLID-PHASE EXTRACTION OF 35 DBPS WITH ANALYSIS BY GC/ECD AND GC/MS

EPA Science Inventory

An analytical method for 35 disinfection by-products (DBPs) was developed for a U.S. Environmental Protection Agency health effects study. A toxicological evaluation was conducted on drinking water that was scaled-up (using reverse osmosis) by concentrating the total organic car...

Comparison of two extraction methods for the analysis of petroleum hydrocarbon residues in mallard duck eggs by GC and GC-MS

USGS Publications Warehouse

Belisle, A.A.; Gay, M.L.; Coon, N.C.

1981-01-01

Hydrocarbon residues in pooled eggs from a mallard duck on a diet of 25,000 ppm South Louisiana crude oil were compared after cleanup with and without saponification. The saponification procedure yielded superior reproducibility and extraction efficiency

SOLID-PHASE EXTRACTION OF 35 DBPS WITH ANALYSIS BY GC/ECD AND GC/MS

EPA Science Inventory

An analytical method for 35 disinfection by-products (DBPs) was developed for a U.S. Environmental Protection Agency (EPA) health effects study. A toxicological evaluation was conducted on drinking water that was "scaled-up" using reverse osmosis (RO) by concentrating the total ...

SOLID-PHASE EXTRACTION OF 35 DBPS WITH ANALYSIS BY GC/ECD AND GC/MS

EPA Science Inventory

An analytical method for 35 disinfection by-products (DBPs) was developed for a U.S. Environmental Protection Agency (EPA) health effects study. A toxicological evaluation was conducted on drinking water that was ‘scaled-up’ using reverse osmosis (RO) by concentrating the total o...

SOLID-PHASE EXTRACTION OF 35 DBPS WITH ANALYSIS BY GC/ECD AND GC/MS 2007

EPA Science Inventory

An analytical method for 35 disinfection by-products (DBPs) was developed for a U.S. Environmental Protection Agency (EPA) health effects study. A toxicological evaluation was conducted on drinking water that was ‘scaled-up’ using reverse osmosis (RO) by concentrating the total o...

Comparison of two extraction methods for the analysis of petroleum hydrocarbon residues in mallard duck eggs by GC and GC-MS. [NONE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belisle, A.A.; Gay, M.L.; Coon, N.C.

Hydrocarbon residues in pooled eggs from a mallard duck on a diet of 25,000 ppm South Louisiana crude oil were compared after cleanup with and without saponification. The saponification procedure yielded superior reproducibility and extraction efficiency..

Analysis of Volatile Organic Compounds in a Controlled Environment: Ethylene Gas Measurement Studies on Radish

NASA Technical Reports Server (NTRS)

Kong, Suk Bin

2001-01-01

Volatile organic compound(VOC), ethylene gas, was characterized and quantified by GC/FID. 20-50 ppb levels were detected during the growth stages of radish. SPME could be a good analytical tool for the purpose. Low temperature trapping method using dry ice/diethyl ether and liquid nitrogen bath was recommended for the sampling process for GC/PID and GC/MS analysis.

The performance of atmospheric pressure gas chromatography-tandem mass spectrometry compared to gas chromatography-high resolution mass spectrometry for the analysis of polychlorinated dioxins and polychlorinated biphenyls in food and feed samples.

PubMed

Ten Dam, Guillaume; Pussente, Igor Cabreira; Scholl, Georges; Eppe, Gauthier; Schaechtele, Alexander; van Leeuwen, Stefan

2016-12-16

Recently, gas chromatography tandem mass spectrometry (GC-MS/MS) has been added in European Union (EU) legislation as an alternative to magnetic sector high resolution mass spectrometry (HRMS) for the analysis of dioxins and dioxin like polychlorinated biphenyls (dl-PCB) in food and feed. In this study the performance of APGC-MS/MS compared to GC-HRMS is investigated and compared with EU legislation. The study includes the legislative parameters, relative intermediate precision standard deviation (S Rw ,rel), trueness, sensitivity, linear range and ion ratio tolerance. In addition, over 200 real samples of large variety and spanning several orders of magnitude in concentration were analyzed by both techniques and the selectivity was evaluated by comparing chromatograms. The S Rw ,rel and trueness were evaluated using (in-house) reference samples and fulfill to EU legislation, though the S Rw ,rel was better with GC-HRMS. The sensitivity was considerably better than of GC-HRMS while the linear range was similar. Ion ratios were mostly within the tolerable range of ±15%. A (temporary unresolved) systematic deviation in ion ratio was observed for several congeners, yet this did not lead to exceeding of the maximum ion ratio limits. The APGC-MS/MS results for the non-dioxin-like-PCBs (ndl-PCBs) were negatively biased, particularly for PCB138 and 153 in contaminated samples. The selectivity of APGC-MS/MS was lower for several matrices. Particularly for contaminated samples, interfering peaks were observed in the APGC chromatograms of the native compounds (dioxins) and labeled internal standards (PCBs). These can lead to biased results and ultimately to false positive samples. It was concluded that the determination of dioxins and PCBs using APGC-MS/MS meets the requirements set by the European Commission. However, due to generally better selectivity and S Rw ,rel, GC-HRMS is the preferred method for monitoring purposes. Copyright © 2016 Elsevier B.V. All rights reserved.

On-line Analysis of Catalytic Reaction Products Using a High-Pressure Tandem Micro-reactor GC/MS.

PubMed

Watanabe, Atsushi; Kim, Young-Min; Hosaka, Akihiko; Watanabe, Chuichi; Teramae, Norio; Ohtani, Hajime; Kim, Seungdo; Park, Young-Kwon; Wang, Kaige; Freeman, Robert R

2017-01-01

When a GC/MS system is coupled with a pressurized reactor, the separation efficiency and the retention time are directly affected by the reactor pressure. To keep the GC column flow rate constant irrespective of the reaction pressure, a restrictor capillary tube and an open split interface are attached between the GC injection port and the head of a GC separation column. The capability of the attached modules is demonstrated for the on-line GC/MS analysis of catalytic reaction products of a bio-oil model sample (guaiacol), produced under a pressure of 1 to 3 MPa.

Total OH reactivity measurements using a new fast Gas Chromatographic Photo-Ionization Detector (GC-PID)

NASA Astrophysics Data System (ADS)

Nölscher, A. C.; Sinha, V.; Bockisch, S.; Klüpfel, T.; Williams, J.

2012-12-01

The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date, direct measurements of total OH reactivity have been either performed using a Laser-Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photoionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60-70 s), sensitivity (LOD 3-6 s-1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were similar to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.

Metabolomics Characterization of Two Apocynaceae Plants, Catharanthus roseus and Vinca minor, Using GC-MS and LC-MS Methods in Combination.

PubMed

Chen, Qi; Lu, Xueyan; Guo, Xiaorui; Guo, Qingxi; Li, Dewen

2017-06-17

Catharanthus roseus ( C. roseus ) and Vinca minor ( V. minor ) are two common important medical plants belonging to the family Apocynaceae. In this study, we used non-targeted GC-MS and targeted LC-MS metabolomics to dissect the metabolic profile of two plants with comparable phenotypic and metabolic differences. A total of 58 significantly different metabolites were present in different quantities according to PCA and PLS-DA score plots of the GC-MS analysis. The 58 identified compounds comprised 16 sugars, eight amino acids, nine alcohols and 18 organic acids. We subjected these metabolites into KEGG pathway enrichment analysis and highlighted 27 metabolic pathways, concentrated on the TCA cycle, glycometabolism, oligosaccharides, and polyol and lipid transporter (RFOS). Among the primary metabolites, trehalose, raffinose, digalacturonic acid and gallic acid were revealed to be the most significant marker compounds between the two plants, presumably contributing to species-specific phenotypic and metabolic discrepancy. The profiling of nine typical alkaloids in both plants using LC-MS method highlighted higher levels of crucial terpenoid indole alkaloid (TIA) intermediates of loganin, serpentine, and tabersonine in V. minor than in C. roseus . The possible underlying process of the metabolic flux from primary metabolism pathways to TIA synthesis was discussed and proposed. Generally speaking, this work provides a full-scale comparison of primary and secondary metabolites between two medical plants and a metabolic explanation of their TIA accumulation and phenotype differences.

Power of Orbitrap-based LC-high resolution-MS/MS for comprehensive drug testing in urine with or without conjugate cleavage or using dried urine spots after on-spot cleavage in comparison to established LC-MSn or GC-MS procedures.

PubMed

Michely, Julian A; Meyer, Markus R; Maurer, Hans H

2018-01-01

Reliable, sensitive, and comprehensive urine screening procedures by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS) with low or high resolution (HR) are of high importance for drug testing, adherence monitoring, or detection of toxic compounds. Besides conventional urine sampling, dried urine spots are of increasing interest. In the present study, the power of LC-HR-MS/MS was investigated for comprehensive drug testing in urine with or without conjugate cleavage or using dried urine spots after on-spot cleavage in comparison to established LC-MS n or GC-MS procedures. Authentic human urine samples (n = 103) were split in 4 parts. One aliquot was prepared by precipitation (UP), one by UP with conjugate cleavage (UglucP), one spot on filter paper cards and prepared by on-spot cleavage followed by liquid extraction (DUSglucE), and one worked-up by acid hydrolysis, liquid-liquid extraction, and acetylation for GC-MS analysis. The 3 series of LC-HR-MS/MS results were compared among themselves, to corresponding published LC-MS n data, and to screening results obtained by conventional GC-MS. The reference libraries used for the 3 techniques contained over 4500 spectra of parent compounds and their metabolites. The number of all detected hits (770 drug intakes) was set to 100%. The LC-HR-MS/MS approach detected 80% of the hits after UP, 89% after UglucP, and 77% after DUSglucE, which meant over one-third more hits in comparison to the corresponding published LC-MS n results with ≤49% detected hits. The GC-MS approach identified 56% of all detected hits. In conclusion, LC-HR-MS/MS provided the best screening results after conjugate cleavage and precipitation. Copyright © 2017 John Wiley & Sons, Ltd.

Analysis of Alkaloids from Physalis peruviana by Capillary GC, Capillary GC-MS, and GC-FTIR.

PubMed

Kubwabo, C; Rollmann, B; Tilquin, B

1993-04-01

The alkaloid composition of the aerial parts and roots of PHYSALIS PERUVIANA was analysed by capillary GC (GC (2)), GC (2)-MS and GC (2)-FTIR. Eight alkaloids were identified, three of those alkaloids are 3beta-acetoxytropane and two N-methylpyrrolidinylhygrine isomers, which were not previously found in the genus PHYSALIS. A reproduction of the identification of alkaloids detected in the plant by the use of retention indices has been proposed.

Determining the degradation efficiency and mechanisms of ethyl violet using HPLC-PDA-ESI-MS and GC-MS

PubMed Central

2012-01-01

Background The discharge of wastewater that contains high concentrations of reactive dyes is a well-known problem associated with dyestuff activities. In recent years, semiconductor photocatalysis has become more and more attractive and important since it has a great potential to contribute to such environmental problems. One of the most important aspects of environmental photocatalysis is in the selection of semiconductor materials like ZnO and TiO2, which are close to being two of the ideal photocatalysts in several respects. For example, they are relatively inexpensive, and they provide photo-generated holes with high oxidizing power due to their wide band gap energy. In this work, nanostructural ZnO film on the Zn foil of the Alkaline-Manganese Dioxide-Zinc Cell was fabricated to degrade EV dye. The major innovation of this paper is to obtain the degradation mechanism of ethyl violet dyes resulting from the HPLC-PDA-ESI-MS analyses. Results The fabrication of ZnO nanostructures on zinc foils with a simple solution-based corrosion strategy and the synthesis, characterization, application, and implication of Zn would be reported in this study. Other objectives of this research are to identify the reaction intermediates and to understand the detailed degradation mechanism of EV dye, as model compound of triphenylmethane dye, with active Zn metal, by HPLC-ESI-MS and GC-MS. Conclusions ZnO nanostructure/Zn-foils had an excellent potential for future applications on the photocatalytic degradation of the organic dye in the environmental remediation. The intermediates of the degradation process were separated and characterized by the HPLC-PDA-ESI-MS and GC-MS, and twenty-six intermediates were characterized in this study. Based on the variation of the amount of intermediates, possible degradation pathways for the decolorization of dyes are also proposed and discussed. PMID:22748361

Review of Urinalysis Drug Testing Program. Report by a Panel of Army and Civilian Experts in Toxicology and Drug Testing Legal Issues for the Surgeon General of the U.S. Army

DTIC Science & Technology

1983-12-12

the National Institute on Drug Abuse (NIDA). Dr. Simon is a consultant on forensic toxicology and currently is the Director of Industrial...THC ratio algorithm, and no laboratory has the personnel trained to provide forensic testimony on the THC or other drug GC/MS data. d. The GC/MS...adequate expertise to support GC/MS internally and forensically document (for courts-martial) GC/MS. The USAF Homestead AFB case is a glaring example of

A GC-MS method for the detection of toluene and ethylbenzene in volatile substance abuse.

PubMed

El-Haj, B M; Al-Amri, A M; Hassan, M H; Bin-Khadem, R K; Al-Hadi, A A

2000-09-01

The interference of some substances with the gas chromatography-flame ionization detection and gas chromatography-Fourier transform infrared detection of toluene and ethylbenzene in volatile substance abuse poses problems. A gas chromatography-mass spectrometry (GC-MS) method that will overcome such interference has been developed for the detection of toluene and/or ethylbenzene in the headspace of preparations and products containing these substances and in the headspace of blood samples in the cases of volatile substance abuse. The method is based on converting toluene to benzoic acid via the formation of benzotrichloride. The latter compound was obtained upon the reaction of toluene with chlorine gas under direct sunlight conditions. In the presence of water, benzotrichloride was converted to benzoic acid. Ethylbenzene was converted to benzoic acid and two phenylethanols via the formation of side chain chloro-substituted phenylethanes followed by reaction with water. The chloro-substituted phenylethanes were obtained by the reaction of ethylbenzene with chlorine under direct sunlight conditions. The benzoic acid resulting from toluene and/or ethylbenzene and the two phenylethanols resulting from ethylbenzene were detected by GC-MS as their trimethylsilyl (TMS) derivatives. For the method to be viable for the detection of volatile substance abuse, the chlorination reactions were effected in the gaseous state.

75 FR 47036 - Small Business Size Standards: Waiver of the Nonmanufacturer Rule

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-04

... Spectrometry (CS-MS) Systems, High Performance Liquid Chromatography (HPLC) Systems, Gas Chromatography Mass...-portable CS-MS, HPLC, GC-MS, and, ICP-MS Laboratory Equipment under PSC 6640 (Laboratory Equipment and...-portable equipment, SBA is limiting the waiver to not-portable CS-MS Systems, HPLC Systems, GC-MS Systems...

Task 2 Report: Algorithm Development and Performance Analysis

DTIC Science & Technology

1993-07-01

separated peaks ............................................. 39 7-16 Example ILGC data for schedule 3 phosphites showing an analysis method which integrates...more closely follows the baseline ................. 40 7-18 Example R.GC data for schedule 3 phosphites showing an analysis method resulting in unwanted...much of the ambiguity that can arise in GC/MS with trace environmental samples, for example. Correlated chromatography, on the other hand, separates the

Quantitative analysis of fragrance in selectable one dimensional or two dimensional gas chromatography-mass spectrometry with simultaneous detection of multiple detectors in single injection.

PubMed

Tan, Hui Peng; Wan, Tow Shi; Min, Christina Liew Shu; Osborne, Murray; Ng, Khim Hui

2014-03-14

A selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography-mass spectrometry (GC-MS) system coupled with flame ionization detector (FID) and olfactory detection port (ODP) was employed in this study to analyze perfume oil and fragrance in shower gel. A split/splitless (SSL) injector and a programmable temperature vaporization (PTV) injector are connected via a 2-way splitter of capillary flow technology (CFT) in this selectable (1)D/(2)D GC-MS/FID/ODP system to facilitate liquid sample injections and thermal desorption (TD) for stir bar sorptive extraction (SBSE) technique, respectively. The dual-linked injectors set-up enable the use of two different injector ports (one at a time) in single sequence run without having to relocate the (1)D capillary column from one inlet to another. Target analytes were separated in (1)D GC-MS/FID/ODP and followed by further separation of co-elution mixture from (1)D in (2)D GC-MS/FID/ODP in single injection without any instrumental reconfiguration. A (1)D/(2)D quantitative analysis method was developed and validated for its repeatability - tR; calculated linear retention indices (LRI); response ratio in both MS and FID signal, limit of detection (LOD), limit of quantitation (LOQ), as well as linearity over a concentration range. The method was successfully applied in quantitative analysis of perfume solution at different concentration level (RSD≤0.01%, n=5) and shower gel spiked with perfume at different dosages (RSD≤0.04%, n=5) with good recovery (96-103% for SSL injection; 94-107% for stir bar sorptive extraction-thermal desorption (SBSE-TD). Copyright © 2014 Elsevier B.V. All rights reserved.

Application of mass spectrometry in the characterization of chemicals in coal-derived liquids.

PubMed

Liu, Fang-Jing; Fan, Maohong; Wei, Xian-Yong; Zong, Zhi-Min

2017-07-01

Coal-derived liquids (CDLs) are primarily generated from pyrolysis, carbonization, gasification, direct liquefaction, low-temperature extraction, thermal dissolution, and mild oxidation. CDLs are important feedstocks for producing value-added chemicals and clean liquid fuels as well as high performance carbon materials. Accordingly, the compositional characterization of chemicals in CDLs at the molecular level with advanced analytical techniques is significant for the efficient utilization of CDLs. Although reviews on advancements have been rarely reported, great progress has been achieved in this area by using gas chromatography/mass spectrometry (GC/MS), two-dimensional GC-time of flight mass spectrometry (GC × GC-TOFMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This review focuses on characterizing hydrocarbon, oxygen-containing, nitrogen-containing, sulfur-containing, and halogen-containing chemicals in various CDLs with these three mass spectrometry techniques. Small molecular (< 500 u), volatile and semi-volatile, and less polar chemicals in CDLs have been identified with GC/MS and GC × GC-TOFMS. By equipped with two-dimensional GC, GC × GC-TOFMS can achieve a clearly chromatographic separation of complex chemicals in CDLs without prior fractionation, and thus can overcome the disadvantages of co-elution and serious peak overlap in GC/MS analysis, providing much more compositional information. With ultrahigh resolving power and mass accuracy, FT-ICR MS reveals a huge number of compositionally distinct compounds assigned to various chemical classes in CDLs. It shows excellent performance in resolving and characterizing higher-molecular, less volatile, and polar chemicals that cannot be detected by GC/MS and GC × GC-TOFMS. The application of GC × GC-TOFMS and FT-ICR MS to chemical characterization of CDLs is not as prevalent as that of petroleum and largely remains to be developed in many respects. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:543-579, 2017. © 2016 Wiley Periodicals, Inc.

Molecularly imprinted polymer coupled with dispersive liquid-liquid microextraction and injector port silylation: a novel approach for the determination of 3-phenoxybenzoic acid in complex biological samples using gas chromatography-tandem mass spectrometry.

PubMed

Mudiam, Mohana Krishna Reddy; Chauhan, Abhishek; Jain, Rajeev; Dhuriya, Yogesh Kumar; Saxena, Prem Narain; Khanna, Vinay Kumar

2014-01-15

A novel analytical approach based on molecularly imprinted solid phase extraction (MISPE) coupled with dispersive liquid-liquid microextraction (DLLME), and injector port silylation (IPS) has been developed for the selective preconcentration, derivatization and analysis of 3-phenoxybenzoic acid (3-PBA) using gas chromatography-tandem mass spectrometry (GC-MS/MS) in complex biological samples such as rat blood and liver. Factors affecting the synthesis of MIP were evaluated and the best monomer and cross-linker were selected based on binding affinity studies. Various parameters of MISPE, DLLME and IPS were optimized for the selective preconcentration and derivatization of 3-PBA. The developed method offers a good linearity over the calibration range of 0.02-2.5ngmg(-1) and 7.5-2000ngmL(-1) for liver and blood respectively. Under optimized conditions, the recovery of 3-PBA in liver and blood samples were found to be in the range of 83-91%. The detection limit was found to be 0.0045ngmg(-1) and 1.82ngmL(-1) in liver and blood respectively. SRM transition of 271→227 and 271→197 has been selected as quantifier and qualifier transition for 3-PBA derivative. Intra and inter-day precision for five replicates in a day and for five, successive days was found to be less than 8%. The method developed was successfully applied to real samples, i.e. rat blood and tissue for quantitative evaluation of 3-PBA. The analytical approach developed is rapid, economic, simple, eco-friendly and possess immense utility for the analysis of analytes with polar functional groups in complex biological samples by GC-MS/MS. Copyright © 2013 Elsevier B.V. All rights reserved.

Hollow-fiber-supported liquid phase microextraction with in situ derivatization and gas chromatography-mass spectrometry for determination of chlorophenols in human urine samples.

PubMed

Ito, Rie; Kawaguchi, Migaku; Honda, Hidehiro; Koganei, Youji; Okanouchi, Noriya; Sakui, Norihiro; Saito, Koichi; Nakazawa, Hiroyuki

2008-09-01

A simple and highly sensitive method that involves hollow-fiber-supported liquid phase microextraction (HF-LPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS) was developed for the determination of chlorophenols (CPs) such as 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TrCP), 2,3,4,6-tetrachlorophenol (TeCP) and pentachlorophenol (PCP) in human urine samples. Human urine samples were enzymatically de-conjugated with beta-glucuronidase and sulfatase. After de-conjugation, HF-LPME with in situ derivatization was performed. After extraction, 2 microl of extract was carefully withdrawn into a syringe and injected into the GC-MS system. The limits of detection (S/N=3) and quantification (S/N>10) of CPs in the human urine samples are 0.1-0.2 ng ml(-1) and 0.5-1 ng ml(-1), respectively. The calibration curve for CPs is linear with a correlation coefficient of >0.99 in the range of 0.5-500 ng ml(-1) for DCP and TrCP, and of 1-500 ng ml(-1) for TeCP and PCP, respectively. The average recoveries of CPs (n=6) in human urine samples are 81.0-104.0% (R.S.D.: 1.9-6.6%) with correction using added surrogate standards. When the proposed method was applied to human urine samples, CPs were detected at sub-ng ml(-1) level.

Multiplex gas chromatography: an alternative concept for gas chromatographic analysis of planetary atmospheres

NASA Technical Reports Server (NTRS)

Valentin, J. R.

1989-01-01

Gas chromatography (GC) is a powerful technique for analyzing gaseous mixtures. Applied to the earth's atmosphere, GC can be used to determine the permanent gases--such as carbon dioxide, nitrogen, and oxygen--and to analyze organic pollutants in air. The U.S. National Aeronautics and Space Administration (NASA) has used GC in spacecraft missions to Mars (the Viking Biology Gas Exchange Experiment [GEX] and the Viking Gas Chromatograph-Mass Spectrometer [GC-MS]) and to Venus (the Pioneer Venus Gas Chromatograph [PVGC] on board the Pioneer Venus sounder probe) for determining the atmospheric constituents of these two planets. Even though conventional GC was very useful in the Viking and Pioneer missions, spacecraft constraints and limitations intrinsic to the technique prevented the collection of more samples. With the Venus probe, for instance, each measurement took a relatively long time to complete (10 min), and successive samples could not be introduced until the previous samples had left the column. Therefore, while the probe descended through the Venusian atmosphere, only three samples were acquired at widely separated altitudes. With the Viking mission, the sampling rate was not a serious problem because samples were acquired over a period of one year. However, the detection limit was a major disadvantage. The GC-MS could not detect simple hydrocarbons and simple alcohols below 0.1 ppm, and the GEX could not detect them below 1 ppm. For more complex molecules, the detection limits were at the parts-per-billion level for both instruments. Finally, in both the Viking and Pioneer missions, the relatively slow rate of data acquisition limited the number of analyses, and consequently, the amount of information returned. Similar constraints are expected in future NASA missions. For instance, gas chromatographic instrumentation is being developed to collect and analyze organic gases and aerosols in the atmosphere of Titan (one of Saturn's satellites). The Titan-Cassini entry probe, which is being jointly planned by NASA and the European Space Agency (ESA), might be launched as early as 1994. As in the Pioneer mission, limited time--perhaps only 3-4 h--will be available for the completion of all analyses while the probe descends through the atmosphere. A conventional GC or GC-MS system would be able to analyze no more than two aerosol and two gas samples during the probe's descent. Conventional GC also is limited by the sensitivity of the detector and by the sample volume. For the Titan mission, the sensitivity problems will be worse because the atmospheric pressure at the time of instrument deployment is expected to be < 3 torr. Consequently, the sample volume might not be large enough to satisfy the detector sensitivity requirements. Because of such limitations, alternative GC analysis techniques have been investigated for future NASA missions. Multiplex gas chromatography has been investigated as a possible candidate for chemical analysis within a spacecraft or other restricted environment, and chemical modulators have been developed and used when needed with this technique to reduce the size and weight of the instrumentation. Also, several new multiplex techniques have been developed for use in specific applications.

Long-term detection of methyltestosterone (ab-) use by a yeast transactivation system.

PubMed

Wolf, Sylvi; Diel, Patrick; Parr, Maria Kristina; Rataj, Felicitas; Schänzer, Willhelm; Vollmer, Günter; Zierau, Oliver

2011-04-01

The routinely used analytical method for detecting the abuse of anabolic steroids only allows the detection of molecules with known analytical properties. In our supplementary approach to structure-independent detection, substances are identified by their biological activity. In the present study, urines excreted after oral methyltestosterone (MT) administration were analyzed by a yeast androgen screen (YAS). The aim was to trace the excretion of MT or its metabolites in human urine samples and to compare the results with those from the established analytical method. MT and its two major metabolites were tested as pure compounds in the YAS. In a second step, the ability of the YAS to detect MT and its metabolites in urine samples was analyzed. For this purpose, a human volunteer ingested of a single dose of 5 mg methyltestosterone. Urine samples were collected after different time intervals (0-307 h) and were analyzed in the YAS and in parallel by GC/MS. Whereas the YAS was able to trace MT in urine samples at least for 14 days, the detection limits of the GC/MS method allowed follow-up until day six. In conclusion, our results demonstrate that the yeast reporter gene system could detect the activity of anabolic steroids like methyltestosterone with high sensitivity even in urine. Furthermore, the YAS was able to detect MT abuse for a longer period of time than classical GC/MS. Obviously, the system responds to long-lasting metabolites yet unidentified. Therefore, the YAS can be a powerful (pre-) screening tool with the potential that to be used to identify persistent or late screening metabolites of anabolic steroids, which could be used for an enhancement of the sensitivity of GC/MS detection techniques.

GC-MS analysis of headspace and liquid extracts for metabolomic differentiation of citrus Huanglongbing and zinc deficiency in leaves of 'Valencia' sweet orange from commercial groves.

PubMed

Cevallos-Cevallos, Juan Manuel; García-Torres, Rosalía; Etxeberria, Edgardo; Reyes-De-Corcuera, José Ignacio

2011-01-01

Citrus Huanglongbing (HLB) is considered the most destructive citrus disease worldwide. Symptoms-based detection of HLB is difficult due to similarities with zinc deficiency. To find metabolic differences between leaves from HLB-infected, zinc-deficient, and healthy 'Valencia' orange trees by using GC-MS based metabolomics. Analysis based on GC-MS methods for untargeted metabolite analysis of citrus leaves was developed and optimized. Sample extracts from healthy, zinc deficient, or HLB-infected sweet orange leaves were submitted to headspace solid phase micro-extraction (SPME) and derivatization treatments prior to GC-MS analysis. Principal components analysis achieved correct classification of all the derivatized liquid extracts. Analysis of variance revealed 6 possible biomarkers for HLB, of which 5 were identified as proline, β-elemene, (-)trans- caryophyllene, and α-humulene. Significant (P < 0.05) differences in oxo-butanedioic acid, arabitol, and neo-inositol were exclusively detected in samples from plants with zinc deficiency. Levels of isocaryophyllen, α-selinene, β-selinene, and fructose were significantly (P < 0.05) different in healthy leaves only. Results suggest the potential of using identified HLB biomarkers for rapid differentiation of HLB from zinc deficiency. Copyright © 2010 John Wiley & Sons, Ltd.

A Simple and Fast Method for the Production and Characterization of Methylic and Ethylic Biodiesels from Tucum Oil via an Alkaline Route

PubMed Central

de Oliveira, Marcelo Firmino; Vieira, Andressa Tironi; Batista, Antônio Carlos Ferreira; Rodrigues, Hugo de Souza; Stradiotto, Nelson Ramos

2011-01-01

A simple, fast, and complete route for the production of methylic and ethylic biodiesel from tucum oil is described. Aliquots of the oil obtained directly from pressed tucum (pulp and almonds) were treated with potassium methoxide or ethoxide at 40°C for 40 min. The biodiesel form was removed from the reactor and washed with 0.1 M HCl aqueous solution. A simple distillation at 100°C was carried out in order to remove water and alcohol species from the biodiesel. The oxidative stability index was obtained for the tucum oil as well as the methylic and ethylic biodiesel at 6.13, 2.90, and 2.80 h, for storage times higher than 8 days. Quality control of the original oil and of the methylic and ethylic biodiesels, such as the amount of glycerin produced during the transesterification process, was accomplished by the TLC, GC-MS, and FT-IR techniques. The results obtained in this study indicate a potential biofuel production by simple treatment of tucum, an important Amazonian fruit. PMID:21629751

Review of the use of phytosterols as a detection tool for adulteration of olive oil with hazelnut oil.

PubMed

Azadmard-Damirchi, Sodeif

2010-01-01

Adulteration of virgin olive oil with less expensive oils such as hazelnut oil is a serious problem for quality control of olive oil. Detection of the presence of hazelnut oil in olive oil at low percentages (<20%) is limited with current official standard methods. In this review, various classes of phytosterols in these two oils are assessed as possible markers to detect adulterated olive oil. The composition of 4-desmethyl- and 4-monomethylsterols is similar in both oils, but the 4,4'-dimethylsterols differ. Lupeol and an unknown (lupane skeleton) compound from 4,4'-dimethylsterols are exclusively present in hazelnut oil and can be used as markers via GC-MS monitoring to detect adulteration at levels as low as 2%. The phytosterol classes need to be separated and enriched by a preparative method prior to analysis by GC or GC/MS; these SPE and TLC methods are also described in this review.

Environmental and forensic applications of field-portable GC-MS: an overview.

PubMed

Eckenrode, B A

2001-06-01

GC-MS can provide analytical information that is most reliable for many types of organic analyses. As field-portable GC-MS analytical systems evolve, the application scenarios have diversified as well. With the development of rugged fieldable systems, these instruments were demonstrated to be usable in the harsh environment of the jungle and in chemical demilitarization or military reconnaissance situations. Continuous unattended operations of a GC-MS for 12- or 24-hour monitoring applications in the field have been shown to be possible. A real-time algorithm strategy is proposed, which can be developed to aid in the advancement of field-portable mass spectrometry applied to chemical warfare agent analysis in military vehicles and can be used to raise the standard for field data quality. Each of these capabilities is discussed with the intent on reviewing analysis situations that can be expanded because of developments in field GC-MS instrumentation.

Composition and Variability of the Essential Oil of the Flowers of Lavandula stoechas from Various Geographical Sources.

PubMed

La Bella, Salvatore; Tuttolomondo, Teresa; Dugo, Giacomo; Ruberto, Giuseppe; Leto, Claudio; Napoli, Edoardo M; Potorti, Angela Giorgia; Fede, Maria Rita; Virga, Giuseppe; Leone, Raffaele; D'Anna, Eleonora; Licata, Mario

2015-11-01

Samples of flowers of wild Lavandula stoechas L. spp. stoechas populations were collected in three areas of Sicily (Italy) and were characterized in agronomic and chemical terms. Essential oil (EO) was extracted by hydrodistillation and analyzed by GC-FID and GC-MS. GC-FID and GC-MS analyses permitted identification of 89 compounds from the EO. The samples were separated into 3 groups using PCA (Principal Component Analysis) statistical method, with reference to the chemical composition of the EO. All three Sicilian populations of lavender were identified as the fenchone chemotype with percentage content ranged between 52.8-71.1%. The population of Partinico showed the highest dry weight of flowers per plant (221.3 g), but the lowest EO yield (0.37%). The essential oils of the three wild Sicilian populations of L. stoechas L. spp. stoechas showed a greater chemical differentiation than those obtained from other Mediterranean areas.

Product Deformulation to Inform High-throughput Exposure ...

EPA Pesticide Factsheets

The health risks posed by the thousands of chemicals in our environment depends on both chemical hazard and exposure. However, relatively few chemicals have estimates of exposure intake, limiting the understanding of risks. We have previously developed a heuristics-based exposure estimation method that depends on simple factors such as the presence or absence of chemicals in consumer products to estimate exposure for thousands of chemicals. Although this method was predictive when compared with human biomonitoring data, limited data are available on the chemical constituents within most articles of commerce. We aim to broaden the number of products with constituent chemical information and refine exposure models by quantifying constituent concentration. A selection of five samples each from 20 diverse consumer product categories (e.g., lotion, clothing, carpet) were analyzed using solvent extraction followed by gas chromatograph (GC) x GC Time of Flight Mass Spectrometry (GCxGC-TOF/MS), which is suited for forensic investigation of complex matrices. In an examination of five plastic children’s toys, a total of 306 unique compounds were identified across all toys, including 102 Tox21 chemicals such as diethyl phthalate and bisphenol AF. As many as 114 and as few as 56 chemicals were identified in each toy. Across the five toys, a range of 0 to 40 unique peaks remain unidentified. Interestingly, bisphenol A (BPA) was identified in a children’s toy marked

Highly selective solid-phase extraction and large volume injection for the robust gas chromatography-mass spectrometric analysis of TCA and TBA in wines.

PubMed

Insa, S; Anticó, E; Ferreira, V

2005-09-30

A reliable solid-phase extraction (SPE) method for the simultaneous determination of 2,4,6-trichloroanisole (TCA) and 2,4,6-tribromoanisole (TBA) in wines has been developed. In the proposed procedure 50 mL of wine are extracted in a 1 mL cartridge filled with 50 mg of LiChrolut EN resins. Most wine volatiles are washed up with 12.5 mL of a water:methanol solution (70%, v/v) containing 1% of NaHCO3. Analytes are further eluted with 0.6 mL of dichloromethane. A 40 microL aliquot of this extract is directly injected into a PTV injector operated in the solvent split mode, and analysed by gas chromatography (GC)-ion trap mass spectrometry using the selected ion storage mode. The solid-phase extraction, including sample volume and rinsing and elution solvents, and the large volume GC injection have been carefully evaluated and optimized. The resulting method is precise (RSD (%) < 6% at 100 ng L(-1)), sensitive (LOD were 0.2 and 0.4 ng/L for TCA and TBA, respectively), robust (the absolute recoveries of both analytes are higher than 80% and consistent wine to wine) and friendly to the GC-MS system (the extract is clean, simple and free from non-volatiles).

[Simultaneous determination of cocaine and its metabolite ecgonine methyl ester in human blood using microwave extraction-gas chromatography].

PubMed

Wang, Xiaobo; Ye, Nengsheng; Wang, Jifen; Gu, Xuexin

2010-07-01

A method was developed for the simultaneous determination of cocaine (COC) and its metabolite ecgonine methyl ester (EME) in human blood using gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID). The blood sample was prepared by microwave extraction (MWE). The optimal parameters of MWE were as follows: 6 mL of chloroform-isopropanol (9: 1, v/v) mixture as extraction solvent, the pH value of the sample was adjusted at 10.0 with 0.05 mol/L Na2CO3-NaHCO3 buffer, the extraction was performed at 40 degrees C for 6 min. The COC and EME in the extract were qualified using GC-MS and quantitated using GC-FID. The average recoveries of COC and EME were from 79.91% to 99.85%, the relative standard deviations were less than 3.10%, and the limits of detection (LOD) were 60 and 40 mg/L, respectively. In the method COC and EME were detected without derivatization. The method is rapid, accurate and sensitive, and can be used for the simultaneous determination of COC and EME in blood samples.

Automated solid-phase extraction-liquid chromatography-tandem mass spectrometry analysis of 6-acetylmorphine in human urine specimens: application for a high-throughput urine analysis laboratory.

PubMed

Robandt, P V; Bui, H M; Scancella, J M; Klette, K L

2010-10-01

An automated solid-phase extraction-liquid chromatography- tandem mass spectrometry (SPE-LC-MS-MS) method using the Spark Holland Symbiosis Pharma SPE-LC coupled to a Waters Quattro Micro MS-MS was developed for the analysis of 6-acetylmorphine (6-AM) in human urine specimens. The method was linear (R² = 0.9983) to 100 ng/mL, with no carryover at 200 ng/mL. Limits of quantification and detection were found to be 2 ng/mL. Interrun precision calculated as percent coefficient of variation (%CV) and evaluated by analyzing five specimens at 10 ng/mL over nine batches (n = 45) was 3.6%. Intrarun precision evaluated from 0 to 100 ng/mL ranged from 1.0 to 4.4%CV. Other opioids (codeine, morphine, oxycodone, oxymorphone, hydromorphone, hydrocodone, and norcodeine) did not interfere in the detection, quantification, or chromatography of 6-AM or the deuterated internal standard. The quantified values for 41 authentic human urine specimens previously found to contain 6-AM by a validated gas chromatography (GC)-MS method were compared to those obtained by the SPE-LC-MS-MS method. The SPE-LC-MS-MS procedure eliminates the human factors of specimen handling, extraction, and derivatization, thereby reducing labor costs and rework resulting from human error or technique issues. The time required for extraction and analysis was reduced by approximately 50% when compared to a validated 6-AM procedure using manual SPE and GC-MS analysis.

Metabolomics and Trace Element Analysis of Camel Tear by GC-MS and ICP-MS.

PubMed

Ahamad, Syed Rizwan; Raish, Mohammad; Yaqoob, Syed Hilal; Khan, Altaf; Shakeel, Faiyaz

2017-06-01

Camel tear metabolomics and elemental analysis are useful in getting the information regarding the components responsible for maintaining the protective system that allows living in the desert and dry regions. The aim of this study was to correlate that the camel tears can be used as artificial tears for the evaluation of dryness in the eye. Eye biomarkers of camel tears were analyzed by gas chromatography-mass spectroscopy (GC-MS) and inductively coupled plasma mass spectroscopy (ICP-MS). The major compounds detected in camel tears by GC-MS were alanine, valine, leucine, norvaline, glycine, cadaverine, urea, ribitol, sugars, and higher fatty acids like octadecanoic acid and hexadecanoic acid. GC-MS analysis of camel tears also finds several products of metabolites and its associated metabolic participants. ICP-MS analysis showed the presence of different concentration of elemental composition in the camel tears.

Determination of phenylalanine isotope ratio enrichment by liquid chromatography/time- of-flight mass spectrometry.

PubMed

Wu, Zhanpin; Zhang, Xiao-Jun; Cody, Robert B; Wolfe, Robert R

2004-01-01

The application of time-of-flight mass spectrometry to isotope ratio measurements has been limited by the relatively low dynamic range of the time-to-digital converter detectors available on commercial LC/ToF-MS systems. Here we report the measurement of phenylalanine isotope ratio enrichment by using a new LC/ToF-MS system with wide dynamic range. Underivatized phenylalanine was injected onto a C18 column directly with 0.1% formic acid/acetonitrile as the mobile phase. The optimal instrument parameters for the time-of-flight mass spectrometer were determined by tuning the instrument with a phenylalanine standard. The accuracy of the isotope enrichment measurement was determined by the injection of standard solutions with known isotope ratios ranging from 0.02% to 9.2%. A plot of the results against the theoretical values gave a linear curve with R2 of 0.9999. The coefficient of variation for the isotope ratio measurement was below 2%. The method is simple, rapid, and accurate and presents an attractive alternative to traditional GC/MS applications.

Chromatographic and Spectral Analysis of Two Main Extractable Compounds Present in Aqueous Extracts of Laminated Aluminum Foil Used for Protecting LDPE-Filled Drug Vials

PubMed Central

Akapo, Samuel O.; Syed, Sajid; Mamangun, Anicia; Skinner, Wayne

2009-01-01

Laminated aluminum foils are increasingly being used to protect drug products packaged in semipermeable containers (e.g., low-density polyethylene (LDPE)) from degradation and/or evaporation. The direct contact of such materials with primary packaging containers may potentially lead to adulteration of the drug product by extractable or leachable compounds present in the closure system. In this paper, we described a simple and reliable HPLC method for analysis of an aqueous extract of laminated aluminum foil overwrap used for packaging LDPE vials filled with aqueous pharmaceutical formulations. By means of combined HPLC-UV, GC/MS, LC/MS/MS, and NMR spectroscopy, the two major compounds detected in the aqueous extracts of the representative commercial overwraps were identified as cyclic oligomers with molecular weights of 452 and 472 and are possibly formed from poly-condensation of the adhesive components, namely, isophthalic acid, adipic acid, and diethylene glycol. Lower molecular weight compounds that might be associated with the “building blocks” of these compounds were not detected in the aqueous extracts. PMID:20140083

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of semivolatile organic compounds in bottom sediment by solvent extraction, gel permeation chromatographic fractionation, and capillary-column gas chromatography/mass spectrometry

USGS Publications Warehouse

Furlong, E.T.; Vaught, D.G.; Merten, L.M.; Foreman, W.T.; Gates, Paul M.

1996-01-01

A method for the determination of 79 semivolatile organic compounds (SOCs) and 4 surrogate compounds in soils and bottom sediment is described. The SOCs are extracted from bottom sediment by solvent extraction, followed by partial isolation using high-performance gel permeation chromatography (GPC). The SOCs then are qualitatively identified and quantitative concentrations determined by capillary-column gas chromatography/mass spectrometry (GC/MS). This method also is designed for an optional simultaneous isolation of polychlorinated biphenyls (PCBs) and organochlorine (OC) insecticides, including toxaphene. When OCs and PCBs are determined, an additional alumina- over-silica column chromatography step follows GPC cleanup, and quantitation is by dual capillary- column gas chromatography with electron-capture detection (GC/ECD). Bottom-sediment samples are centrifuged to remove excess water and extracted overnight with dichloromethane. The extract is concentrated, centrifuged, and then filtered through a 0.2-micrometer polytetrafluoro-ethylene syringe filter. Two aliquots of the sample extract then are quantitatively injected onto two polystyrene- divinylbenzene GPC columns connected in series. The SOCs are eluted with dichloromethane, a fraction containing the SOCs is collected, and some coextracted interferences, including elemental sulfur, are separated and discarded. The SOC-containing GPC fraction then is analyzed by GC/MS. When desired, a second aliquot from GPC is further processed for OCs and PCBs by combined alumina-over-silica column chromatography. The two fractions produced in this cleanup then are analyzed by GC/ECD. This report fully describes and is limited to the determination of SOCs by GC/MS.

Aroma characterization of chinese rice wine by gas chromatography-olfactometry, chemical quantitative analysis, and aroma reconstitution.

PubMed

Chen, Shuang; Xu, Yan; Qian, Michael C

2013-11-27

The aroma profile of Chinese rice wine was investigated in this study. The volatile compounds in a traditional Chinese rice wine were extracted using Lichrolut EN and further separated by silica gel normal phase chromatography. Seventy-three aroma-active compounds were identified by gas chromatography-olfactometry (GC-O) and gas chromatography-mass spectrometry (GC-MS). In addition to acids, esters, and alcohols, benzaldehyde, vanillin, geosmin, and γ-nonalactone were identified to be potentially important to Chinse rice wine. The concentration of these aroma-active compounds in the Chinese rice wine was further quantitated by combination of four different methods, including headsapce-gas chromatography, solid phase microextraction-gas chromatography (SPME)-GC-MS, solid-phase extraction-GC-MS, and SPME-GC-pulsed flame photometric detection (PFPD). Quantitative results showed that 34 aroma compounds were at concentrations higher than their corresponding odor thresholds. On the basis of the odor activity values (OAVs), vanillin, dimethyl trisulfide, β-phenylethyl alcohol, guaiacol, geosmin, and benzaldehyde could be responsible for the unique aroma of Chinese rice wine. An aroma reconstitution model prepared by mixing 34 aroma compounds with OAVs > 1 in an odorless Chinese rice wine matrix showed a good similarity to the aroma of the original Chinese rice wine.

Matrix-enhanced degradation of p,p'-DDT during gas chromatographic analysis: A consideration

USGS Publications Warehouse

Foreman, W.T.; Gates, Paul M.

1997-01-01

Analysis of p,p‘-DDT in environmental samples requires monitoring the GC-derived breakdown of this insecticide, which produces p,p‘-DDD and/or p,p‘-DDE, both also primary environmental degradation products. A performance evaluation standard (PES) containing p,p‘-DDT but notp,p‘-DDD or p,p‘-DDE can be injected at regular intervals throughout an analytical sequence to monitor GC degradation. Some U.S. EPA methods limit GC breakdown of DDT in the PES to ≤20%. GC/MS analysis of large-volume natural water samples fortified with deuterium- and 13C-labeled p,p‘-DDT exhibited up to 65% DDT breakdown by the GC inlet. These matrix-enhanced GC degradation amounts substantially exceeded the <20% breakdown levels indicated by bracketing injections of the PES containing unlabeled and labeled DDT. Substantial matrix-enhanced GC degradation was not observed during analysis of a limited number of fractionated bed-sediment extracts containing labeled DDT. Use of isotopically labeled DDT seems to provide an effective tool for monitoring sample-specific DDT breakdown during GC/MS analysis. However, analyte co-elutions render impractical their use in GC/ECD analysis. The oc currence of matrix-enhanced GC degradation might have important implications on data quality and the resultant interpretations of the environmental degradation of DDT and other thermolabile contaminants.

Analysis of plant gums and saccharide materials in paint samples: comparison of GC-MS analytical procedures and databases

PubMed Central

2012-01-01

Background Saccharide materials have been used for centuries as binding media, to paint, write and illuminate manuscripts and to apply metallic leaf decorations. Although the technical literature often reports on the use of plant gums as binders, actually several other saccharide materials can be encountered in paint samples, not only as major binders, but also as additives. In the literature, there are a variety of analytical procedures that utilize GC-MS to characterize saccharide materials in paint samples, however the chromatographic profiles are often extremely different and it is impossible to compare them and reliably identify the paint binder. Results This paper presents a comparison between two different analytical procedures based on GC-MS for the analysis of saccharide materials in works-of-art. The research presented here evaluates the influence of the analytical procedure used, and how it impacts the sugar profiles obtained from the analysis of paint samples that contain saccharide materials. The procedures have been developed, optimised and systematically used to characterise plant gums at the Getty Conservation Institute in Los Angeles, USA (GCI) and the Department of Chemistry and Industrial Chemistry of the University of Pisa, Italy (DCCI). The main steps of the analytical procedures and their optimisation are discussed. Conclusions The results presented highlight that the two methods give comparable sugar profiles, whether the samples analysed are simple raw materials, pigmented and unpigmented paint replicas, or paint samples collected from hundreds of centuries old polychrome art objects. A common database of sugar profiles of reference materials commonly found in paint samples was thus compiled. The database presents data also from those materials that only contain a minor saccharide fraction. This database highlights how many sources of saccharides can be found in a paint sample, representing an important step forward in the problem of identifying polysaccharide binders in paint samples. PMID:23050842

Analysis of plant gums and saccharide materials in paint samples: comparison of GC-MS analytical procedures and databases.

PubMed

Lluveras-Tenorio, Anna; Mazurek, Joy; Restivo, Annalaura; Colombini, Maria Perla; Bonaduce, Ilaria

2012-10-10

Saccharide materials have been used for centuries as binding media, to paint, write and illuminate manuscripts and to apply metallic leaf decorations. Although the technical literature often reports on the use of plant gums as binders, actually several other saccharide materials can be encountered in paint samples, not only as major binders, but also as additives. In the literature, there are a variety of analytical procedures that utilize GC-MS to characterize saccharide materials in paint samples, however the chromatographic profiles are often extremely different and it is impossible to compare them and reliably identify the paint binder. This paper presents a comparison between two different analytical procedures based on GC-MS for the analysis of saccharide materials in works-of-art. The research presented here evaluates the influence of the analytical procedure used, and how it impacts the sugar profiles obtained from the analysis of paint samples that contain saccharide materials. The procedures have been developed, optimised and systematically used to characterise plant gums at the Getty Conservation Institute in Los Angeles, USA (GCI) and the Department of Chemistry and Industrial Chemistry of the University of Pisa, Italy (DCCI). The main steps of the analytical procedures and their optimisation are discussed. The results presented highlight that the two methods give comparable sugar profiles, whether the samples analysed are simple raw materials, pigmented and unpigmented paint replicas, or paint samples collected from hundreds of centuries old polychrome art objects. A common database of sugar profiles of reference materials commonly found in paint samples was thus compiled. The database presents data also from those materials that only contain a minor saccharide fraction. This database highlights how many sources of saccharides can be found in a paint sample, representing an important step forward in the problem of identifying polysaccharide binders in paint samples.

Multi-residue analysis of 26 organochlorine pesticides in Alpinia oxyphylla by GC-ECD after solid phase extraction and acid cleanup.

PubMed

Zhao, Xiangsheng; Zhou, Yakui; Kong, Weijun; Gong, Bao; Chen, Deli; Wei, Jianhe; Yang, Meihua

2016-04-01

A simple and effective multi-residue method was developed and validated for the analysis of 26 organochlorine pesticide residues in Alpinia oxyphylla by a gas chromatography with an electron capture detector (GC-ECD). The target pesticides were extracted by sonication and cleaned up with florisil solid phase extraction and sulphuric acid. Some crucial parameters, including extraction solvent and time, sorbent type, elute solvent and concentration of sulphuric acid were optimized to improve the performance of sample preparation procedure. The optimized method gave high sensitivity with detection limit ranging from 0.1 to 2.0μg/kg. Matrix-matched calibration was employed for the quantification, and a wide linear range (from 1.0 to 1000μg/kg) with r(2) values ranging from 0.9971 to 0.9998 was obtained. For the majority of the tested pesticides, the average recoveries were in acceptable range (between 70% and 110%) with relative standard deviation values below 15.0%. Matrix effect was evaluated for target compounds through the study of ratio of peak area obtained in the solvent and blank matrix. The proposed method was applied to simultaneously analyze 26 pesticides in 55 batches of Alpinia oxyphylla samples. 3 samples were found to be positive with four pesticides (α-BHC, quintozene, trans-chlordane and op'-DDD), which were confirmed by gas chromatography-mass spectrometry (GC-MS) in selective ion monitoring (SIM) mode. Copyright © 2016 Elsevier B.V. All rights reserved.

Phytochemical Profiles and Antimicrobial Activities of Allium cepa Red cv. and A. sativum Subjected to Different Drying Methods: A Comparative MS-Based Metabolomics.

PubMed

Farag, Mohamed A; Ali, Sara E; Hodaya, Rashad H; El-Seedi, Hesham R; Sultani, Haider N; Laub, Annegret; Eissa, Tarek F; Abou-Zaid, Fouad O F; Wessjohann, Ludger A

2017-05-08

Plants of the Allium genus produce sulphur compounds that give them a characteristic (alliaceous) flavour and mediate for their medicinal use. In this study, the chemical composition and antimicrobial properties of Allium cepa red cv. and A. sativum in the context of three different drying processes were assessed using metabolomics. Bulbs were dried using either microwave, air drying, or freeze drying and further subjected to chemical analysis of their composition of volatile and non-volatile metabolites. Volatiles were collected using solid phase micro-extraction (SPME) coupled to gas chromatography-mass spectrometry (GC/MS) with 42 identified volatiles including 30 sulphur compounds, four nitriles, three aromatics, and three esters. Profiling of the polar non-volatile metabolites via ultra-performance liquid chromatography coupled to high resolution MS (UPLC/MS) annotated 51 metabolites including dipeptides, flavonoids, phenolic acids, and fatty acids. Major peaks in GC/MS or UPLC/MS contributing to the discrimination between A. sativum and A. cepa red cv. were assigned to sulphur compounds and flavonoids. Whereas sulphur conjugates amounted to the major forms in A. sativum , flavonoids predominated in the chemical composition of A. cepa red cv. With regard to drying impact on Allium metabolites, notable and clear separations among specimens were revealed using principal component analysis (PCA). The PCA scores plot of the UPLC/MS dataset showed closer metabolite composition of microwave dried specimens to freeze dried ones, and distant from air dried bulbs, observed in both A. cepa and A. sativum . Compared to GC/MS, the UPLC/MS derived PCA model was more consistent and better in assessing the impact of drying on Allium metabolism. A phthalate derivative was found exclusively in a commercial garlic preparation via GC/MS, of yet unknown origin. The freeze dried samples of both Allium species exhibited stronger antimicrobial activities compared to dried specimens with A. sativum being in general more active than A. cepa red cv.

Development of the GC-MS organic aerosol monitor (GC-MS OAM) for in-field detection of particulate organic compounds

NASA Astrophysics Data System (ADS)

Cropper, Paul M.; Overson, Devon K.; Cary, Robert A.; Eatough, Delbert J.; Chow, Judith C.; Hansen, Jaron C.

2017-11-01

Particulate matter (PM) is among the most harmful air pollutants to human health, but due to its complex chemical composition is poorly characterized. A large fraction of PM is composed of organic compounds, but these compounds are not regularly monitored due to limitations in current sampling and analysis techniques. The Organic Aerosol Monitor (GC-MS OAM) combines a collection device with thermal desorption, gas chromatography and mass spectrometry to quantitatively measure the carbonaceous components of PM on an hourly averaged basis. The GC-MS OAM is fully automated and has been successfully deployed in the field. It uses a chemically deactivated filter for collection followed by thermal desorption and GC-MS analysis. Laboratory tests show that detection limits range from 0.2 to 3 ng for 16 atmospherically relevant compounds, with the possibility for hundreds more. The GC-MS OAM was deployed in the field for semi-continuous measurement of the organic markers, levoglucosan, dehydroabietic acid, and polycyclic aromatic hydrocarbons (PAHs) from January to March 2015. Results illustrate the significance of this monitoring technique to characterize the organic components of PM and identify sources of pollution.

Two-dimensional on-line detection of brominated and iodinated volatile organic compounds by ECD and ICP-MS after GC separation.

PubMed

Schwarz, A; Heumann, K G

2002-09-01

Inductively coupled plasma-mass spectrometry (ICP-MS) was coupled to a gas chromatographic (GC) system with electron capture detector (ECD), which enables relatively easy characterization and quantification of brominated and iodinated (halogenated) volatile organic compounds (HVOCs) in aquatic and air samples. The GC-ECD system is connected in series with an ICP-MS by a directly heated transfer line and an outlet port-hole for elimination of the ECD make-up gas during ignition of the plasma. The hyphenated GC-ECD/ICP-MS system provides high selectivity and sensitivity for monitoring individual HVOCs under fast chromatographic conditions. The ECD is most sensitive for the detection of chlorinated and brominated but the ICP-MS for iodinated compounds. The greatest advantage of the use of an ICP-MS is its element-specific detection, which allows clear identification of compounds in most cases. The absolute detection limits for ICP-MS are 0.5 pg for iodinated, 10 pg for brominated, and 50 pg for chlorinated HVOCs with the additional advantage that calibration is almost independent on different compounds of the same halogen. In contrast to that detection limits for ECD vary for the different halogenated compounds and lie in the range of 0.03-11 pg. The two-dimensional GC-ECD/ICP-MS instrumentation is compared with electron impact mass spectrometry (EI-MS) and microwave induced plasma atomic emission detection (MIP-AED). Even if EI-MS has additional power in identifying unknown peaks by its scan mode, the detection limits are much higher compared with GC-ECD/ICP-MS, whereas the selective ion monitoring mode (SIM) reaches similar detection limits. The MIP-AED detection limits are at the same level as EI-MS in the scan mode.

Inexpensive Screening for Smoked Drugs Using An Autosampler/DART/TOFMS

EPA Science Inventory

Introduction. In 2008 alone, 6783 clandestine, methamphetamine labs were tallied by the DEA. Smoked drug residues on surfaces pose serious health risks, especially to toddlers. NIOSH methods 9106, 9109 (GC/MS with derivitization), and 9111 (LC/MS) provide detection limits for w...

Global and selective detection of organohalogens in environmental samples by comprehensive two-dimensional gas chromatography-tandem mass spectrometry and high-resolution time-of-flight mass spectrometry.

PubMed

Hashimoto, Shunji; Takazawa, Yoshikatsu; Fushimi, Akihiro; Tanabe, Kiyoshi; Shibata, Yasuyuki; Ieda, Teruyo; Ochiai, Nobuo; Kanda, Hirooki; Ohura, Takeshi; Tao, Qingping; Reichenbach, Stephen E

2011-06-17

We successfully detected halogenated compounds from several kinds of environmental samples by using a comprehensive two-dimensional gas chromatograph coupled with a tandem mass spectrometer (GC×GC-MS/MS). For the global detection of organohalogens, fly ash sample extracts were directly measured without any cleanup process. The global and selective detection of halogenated compounds was achieved by neutral loss scans of chlorine, bromine and/or fluorine using an MS/MS. It was also possible to search for and identify compounds using two-dimensional mass chromatograms and mass profiles obtained from measurements of the same sample with a GC×GC-high resolution time-of-flight mass spectrometer (HRTofMS) under the same conditions as those used for the GC×GC-MS/MS. In this study, novel software tools were also developed to help find target (halogenated) compounds in the data provided by a GC×GC-HRTofMS. As a result, many dioxin and polychlorinated biphenyl congeners and many other halogenated compounds were found in fly ash extract and sediment samples. By extracting the desired information, which concerned organohalogens in this study, from huge quantities of data with the GC×GC-HRTofMS, we reveal the possibility of realizing the total global detection of compounds with one GC measurement of a sample without any pre-treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

Multifamily determination of pesticide residues in soya-based nutraceutical products by GC/MS-MS.

PubMed

Páleníková, Agneša; Martínez-Domínguez, Gerardo; Arrebola, Francisco Javier; Romero-González, Roberto; Hrouzková, Svetlana; Frenich, Antonia Garrido

2015-04-15

An analytical method based on a modified QuEChERS extraction coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS) was evaluated for the determination of 177 pesticides in soya-based nutraceutical products. The QuEChERS method was optimised and different extraction solvents and clean-up approaches were tested, obtaining the most efficient conditions with a mixture of sorbents (PSA, C18, GBC and Zr-Sep(+)). Recoveries were evaluated at 10, 50 and 100 μg/kg and ranged between 70% and 120%. Precision was expressed as relative standard deviation (RSD), and it was evaluated for more than 160 pesticides as intra and inter-day precision, with values always below 20% and 25%, respectively. Limits of detection (LODs) ranged from 0.1 to 10 μg/kg, whereas limits of quantification (LOQs) from 0.5 to 20 μg/kg. The applicability of the method was proved by analysing soya-based nutraceuticals. Two pesticides were found in these samples, malathion and pyriproxyfen, at 11.1 and 1.5 μg/kg respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Co-liquefaction with acetone and GC analysis of volatile compounds in exhaled breath as lung cancer biomarkers

PubMed Central

Jouyban, Abolghasem; Djozan, Djavanshir; Mohammadandashti, Parastou; Alizadeh-Nabil, Aliakbar; Ghorbanpour, Hooshangh; Khoubnasabjafari, Maryam; Mohammadzadeh, Mohammad

2017-01-01

Introduction: A simple, rapid and low cost method for enrichment of volatile organic compounds (VOCs) from exhaled breath (EB) is presented. Methods: A 1000 mL home-made extraction device was filled with EB. The VOCs were extracted and condensed in 0.5 mL acetone. Recognition of volatiles in the real studied EB samples was performed by a GC-MS. Results: The method displays an extraction efficiency of >86% with the enrichment factor of 1929 for octanal. Limits of detection and quantification, and linear dynamic range were 0.008, 0.026 and 0.026-400 ng/mL respectively. Analysis of real samples showed the existence of more than 100 compounds in EB of healthy volunteers and patients with lung cancer before and after treatment. Exhaled octanal concentration was significantly higher in lung cancer patient than in healthy volunteers and lung cancer patient after treatment. Conclusion: Having used the proposed approach, high extraction recovery (up to 86%) was attained for the lung cancer marker, octanal, as an important biomarker. Our findings on smaples of EB of healthy controls and patients with lung cancer before and after treatment provide complelling evidence upon the effectiveness of the developed method. PMID:28752074

Compressible and Recyclable Monolithic g-C3N4/Melamine Sponge: A Facile Ultrasonic-Coating Approach and Enhanced Visible-Light Photocatalytic Activity.

PubMed

Yang, Ye; Zhang, Qian; Zhang, Ruiyang; Ran, Tao; Wan, Wenchao; Zhou, Ying

2018-01-01

Powdery photocatalysts seriously restrict their practical application due to the difficult recycle and low photocatalytic activity. In this work, a monolithic g-C 3 N 4 /melamine sponge (g-C 3 N 4 /MS) was successfully fabricated by a cost-effective ultrasonic-coating route, which is easy to achieve the uniform dispersion and firm loading of g-C 3 N 4 on MS skeleton. The monolithic g-C 3 N 4 /MS entirely inherits the porous structure of MS and results in a larger specific surface area (SSA) than its powdery counterpart. Benefit from this monolithic structure, g-C 3 N 4 /MS gains more exposed active sites, enhanced visible-light absorption and separation of photogenerated carriers, thus achieving noticeable photocatalytic activity on nitric oxide (NO) removal and CO 2 reduction. Specifically, NO removal ratio is as high as 78.6% which is 4.5 times higher than that of the powdery g-C 3 N 4 , and yield rate of CO and CH 4 attains 7.48 and 3.93 μmol g -1 h -1 . Importantly, the features of low-density, high porosity, good elasticity, and firmness, not only endow g-C 3 N 4 /MS with flexibility in various environmental applications, but also make it easy to recycle and stable for long-time application. Our work provides a feasible approach to fabricate novel monolithic photocatalysts with large-scale production and application.

Compressible and Recyclable Monolithic g-C3N4/Melamine Sponge: A Facile Ultrasonic-Coating Approach and Enhanced Visible-Light Photocatalytic Activity

PubMed Central

Yang, Ye; Zhang, Qian; Zhang, Ruiyang; Ran, Tao; Wan, Wenchao; Zhou, Ying

2018-01-01

Powdery photocatalysts seriously restrict their practical application due to the difficult recycle and low photocatalytic activity. In this work, a monolithic g-C3N4/melamine sponge (g-C3N4/MS) was successfully fabricated by a cost-effective ultrasonic-coating route, which is easy to achieve the uniform dispersion and firm loading of g-C3N4 on MS skeleton. The monolithic g-C3N4/MS entirely inherits the porous structure of MS and results in a larger specific surface area (SSA) than its powdery counterpart. Benefit from this monolithic structure, g-C3N4/MS gains more exposed active sites, enhanced visible-light absorption and separation of photogenerated carriers, thus achieving noticeable photocatalytic activity on nitric oxide (NO) removal and CO2 reduction. Specifically, NO removal ratio is as high as 78.6% which is 4.5 times higher than that of the powdery g-C3N4, and yield rate of CO and CH4 attains 7.48 and 3.93 μmol g−1 h−1. Importantly, the features of low-density, high porosity, good elasticity, and firmness, not only endow g-C3N4/MS with flexibility in various environmental applications, but also make it easy to recycle and stable for long-time application. Our work provides a feasible approach to fabricate novel monolithic photocatalysts with large-scale production and application.

Classification of organic aerosol in the atmosphere over Seoul based on chemical group separation using two dimensional gas chromatography-time of flight mass spectrometry (GC×GC TOFMS) data

NASA Astrophysics Data System (ADS)

Jeon, S.; Lim, H. B.; Choi, N.; Lee, J.; Ahn, Y. K.; Kim, Y. P.

2016-12-01

Organic aerosols contain thousands of organic compounds and contribute to 20-90% of the total fine aerosol mass. For analyzing organic aerosols, a wide range of analytical techniques have been used such as gas chromatography mass spectrometer (GC/MS), liquid chromatography mass spectrometer (LC/MS), aerosol mass spectrometer (AMS), etc. Among them, comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometer (GCxGC/TOF-MS) can provide higher chemical resolution than AMS and analyze more mass fractions of organic aerosols than GC/MS. In this study, we suggest a new data processing method using GCxGC/TOF-MS data for analyzing organic compounds in the ambient aerosols. TSP samples were collected on the roof of the Asan engineering building, Ewha Womans University, Seoul, South Korea (37.56 °N, 126.94 °E, 20 m above ground level). A total of 67 samples were obtained during summer (August 2013) and winter (January and February 2014) with a PUF sampler (Tisch, TE-1000) on quartz fiber filter. Filters were extracted using accelerated solvent extractor with a mixture of dichloromethane and methanol (3:1, v/v). Total extracts were blown down to 0.5 mL using a nitrogen evaporator (Turbo Vap Ⅱ, caliper Life Sciences). Organic compounds in the TSP samples were separated into 6 chemical groups, depending on their retention time in two dimensions for their volatility and polarity. All area of peaks in each group was summed and variance of total area in each group was compared depending on season and diurnal cycle.

The MetabolomeExpress Project: enabling web-based processing, analysis and transparent dissemination of GC/MS metabolomics datasets.

PubMed

Carroll, Adam J; Badger, Murray R; Harvey Millar, A

2010-07-14

Standardization of analytical approaches and reporting methods via community-wide collaboration can work synergistically with web-tool development to result in rapid community-driven expansion of online data repositories suitable for data mining and meta-analysis. In metabolomics, the inter-laboratory reproducibility of gas-chromatography/mass-spectrometry (GC/MS) makes it an obvious target for such development. While a number of web-tools offer access to datasets and/or tools for raw data processing and statistical analysis, none of these systems are currently set up to act as a public repository by easily accepting, processing and presenting publicly submitted GC/MS metabolomics datasets for public re-analysis. Here, we present MetabolomeExpress, a new File Transfer Protocol (FTP) server and web-tool for the online storage, processing, visualisation and statistical re-analysis of publicly submitted GC/MS metabolomics datasets. Users may search a quality-controlled database of metabolite response statistics from publicly submitted datasets by a number of parameters (eg. metabolite, species, organ/biofluid etc.). Users may also perform meta-analysis comparisons of multiple independent experiments or re-analyse public primary datasets via user-friendly tools for t-test, principal components analysis, hierarchical cluster analysis and correlation analysis. They may interact with chromatograms, mass spectra and peak detection results via an integrated raw data viewer. Researchers who register for a free account may upload (via FTP) their own data to the server for online processing via a novel raw data processing pipeline. MetabolomeExpress https://www.metabolome-express.org provides a new opportunity for the general metabolomics community to transparently present online the raw and processed GC/MS data underlying their metabolomics publications. Transparent sharing of these data will allow researchers to assess data quality and draw their own insights from published metabolomics datasets.

Comprehensive two-dimensional gas chromatography with flame ionization and time-of-flight mass spectrometry detection: qualitative and quantitative analysis of West Australian sandalwood oil.

PubMed

Shellie, Robert; Marriott, Philip; Morrison, Paul

2004-09-01

The use of gas chromatography (GC)-mass spectrometry (MS), GC-time-of-flight MS (TOFMS), comprehensive two-dimensional GC (GCxGC)-flame ionization detection (FID), and GCxGC-TOFMS is discussed for the characterization of the eight important representative components, including Z-alpha-santalol, epi-alpha-bisabolol, Z-alpha-trans-bergamotol, epi-beta-santalol, Z-beta-santalol, E,E-farnesol, Z-nuciferol, and Z-lanceol, in the oil of west Australian sandalwood (Santalum spicatum). Single-column GC-MS lacks the resolving power to separate all of the listed components as pure peaks and allow precise analytical measurement of individual component abundances. With enhanced peak resolution capabilities in GCxGC, these components are sufficiently well resolved to be quantitated using flame ionization detection, following initial characterization of components by using GCxGC-TOFMS.

University Research Initiative Program for Combat Readiness, Annual Report for the Period June 1, 1997 - June 30, 1998

DTIC Science & Technology

1998-05-01

polysaccharides ) can be interpreted by matching to these chemical markers. Differentiation of the aldohexose monosaccharides or determination of simple...experiments involving qualitative and quantitative analysis of monomeric carbohydrate content in bacterial polysaccharides by Py-GC/MS has been...residues in the group-specific polysaccharide of group B streptococci8 and differentiation of B. anthracis strains by a pyrolysis product from its

The micro-scale synthesis of (117)Sn-enriched tributyltin chloride and its characterization by GC-ICP-MS and NMR techniques.

PubMed

Peeters, Kelly; Iskra, Jernej; Zuliani, Tea; Ščančar, Janez; Milačič, Radmila

2014-07-01

Organotin compounds (OTCs) are among the most toxic substances ever introduced to the environment by man. They are common pollutants in marine ecosystems, but are also present in the terrestrial environment, accumulated mainly in sewage sludge and landfill leachates. In investigations of the degradation and methylation processes of OTC in environmental samples, the use of enriched isotopic tracers represents a powerful analytical tool. Sn-enriched OTC are also necessary in application of the isotope dilution mass spectrometry technique for their accurate quantification. Since Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) are not commercially available as single species, "in house" synthesis of individual butyltin-enriched species is necessary. In the present work, the preparation of the most toxic butyltin, namely TBT, was performed via a simple synthetic path, starting with bromination of metallic Sn, followed by butylation with butyl lithium. The tetrabutyltin (TeBT) formed was transformed to tributyltin chloride (TBTCl) using concentrated hydrochloric acid (HCl). The purity of the synthesized TBT was verified by speciation analysis using the techniques of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) and nuclear magnetic resonance (NMR). The results showed that TBT had a purity of more than 97%. The remaining 3% corresponded to DBT. TBT was quantified by reverse isotope dilution GC-ICP-MS. The synthesis yield was around 60%. The advantage of this procedure over those previously reported lies in its possibility to be applied on a micro-scale (starting with 10mg of metallic Sn). This feature is of crucial importance, since enriched metallic Sn is extremely expensive. The procedure is simple and repeatable, and was successfully applied for the preparation of (117)Sn-enriched TBTCl from (117)Sn-enriched metal. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Karlsruhe Metabolomics and Nutrition (KarMeN) Study: Protocol and Methods of a Cross-Sectional Study to Characterize the Metabolome of Healthy Men and Women

PubMed Central

Kriebel, Anita; Dörr, Claudia; Bandt, Susanne; Rist, Manuela; Roth, Alexander; Hummel, Eva; Kulling, Sabine; Hoffmann, Ingrid; Watzl, Bernhard

2016-01-01

Background The human metabolome is influenced by various intrinsic and extrinsic factors. A precondition to identify such biomarkers is the comprehensive understanding of the composition and variability of the metabolome of healthy humans. Sample handling aspects have an important impact on the composition of the metabolome; therefore, it is crucial for any metabolomics study to standardize protocols on sample collection, preanalytical sample handling, storage, and analytics to keep the nonbiological variability as low as possible. Objective The main objective of the KarMeN study is to analyze the human metabolome in blood and urine by targeted and untargeted metabolite profiling (gas chromatography-mass spectrometry [GC-MS], GC×GC-MS, liquid chromatography-mass spectrometry [LC-MS/MS], and1H nuclear magnetic resonance [NMR] spectroscopy) and to determine the impact of sex, age, body composition, diet, and physical activity on metabolite profiles of healthy women and men. Here, we report the outline of the study protocol with special regard to all aspects that should be considered in studies applying metabolomics. Methods Healthy men and women, aged 18 years or older, were recruited. In addition to a number of anthropometric (height, weight, body mass index, waist circumference, body composition), clinical (blood pressure, electrocardiogram, blood and urine clinical chemistry) and functional parameters (lung function, arterial stiffness), resting metabolic rate, physical activity, fitness, and dietary intake were assessed, and 24-hour urine, fasting spot urine, and plasma samples were collected. Standard operating procedures were established for all steps of the study design. Using different analytical techniques (LC-MS, GC×GC-MS,1H NMR spectroscopy), metabolite profiles of urine and plasma were determined. Data will be analyzed using univariate and multivariate as well as predictive modeling methods. Results The project was funded in 2011 and enrollment was carried out between March 2012 and July 2013. A total of 301 volunteers were eligible to participate in the study. Metabolite profiling of plasma and urine samples has been completed and data analysis is currently underway. Conclusions We established the KarMeN study applying a broad set of clinical and physiological examinations with a high degree of standardization. Our experimental approach of combining scheduled timing of examinations and sampling with the multiplatform approach (GC×GC-MS, GC-MS, LC-MS/MS, and1H NMR spectroscopy) will enable us to differentiate between current and long-term effects of diet and physical activity on metabolite profiles, while enabling us at the same time to consider confounders such as age and sex in the KarMeN study. Trial Registration German Clinical Trials Register DRKS00004890; https://drks-neu.uniklinik-freiburg.de/drks_web/navigate.do? navigationId=trial.HTML&TRIAL_ID=DRKS00004890 (Archived by WebCite at http://www.webcitation.org/6iyM8dMtx) PMID:27421387

GC-MS analyses of the volatiles of Houttuynia cordata Thunb.

PubMed

Yang, Zhan-Nan; Luo, Shi-Qiong; Ma, Jing; Wu, Dan; Hong, Liang; Yu, Zheng-Wen

2016-09-01

GC-MS is the basis of analysis of plant volatiles. Several protocols employed for the assay have resulted in inconsistent results in the literature. We developed a GC-MS method, which were applied to analyze 25 volatiles (α-pinene, camphene, β-pinene, 2-methyl-2-pentenal, myrcene, (+)-limonene, eucalyptol, trans-2-hexenal, γ-terpinene, cis-3-hexeneyl-acetate, 1-hexanol, α-pinene oxide, cis-3-hexen-1-ol, trans-2-hexen-1-ol, decanal, linalool, acetyl-borneol, β-caryophyllene, 2-undecanone, 4-terpineol, borneol, decanol, eugenol, isophytol and phytol) of Houttuynia cordata Thunb. Linear behaviors for all analytes were observed with a linear regression relationship (r2>0.9991) at the concentrations tested. Recoveries of the 25 analytes were 98.56-103.77% with RSDs <3.0%. Solution extraction (SE), which involved addition of an internal standard, could avoid errors for factors in sample preparation by steam distillation (SD) and solidphase micro extraction (SPME). Less sample material (≍0.05g fresh leaves of H. cordata) could be used to determine the contents of 25 analytes by our proposed method and, after collection, did not affect the normal physiological activity or growth of H. cordata. This method can be used to monitor the metabolic accumulation of H. cordata volatiles.

Estimation of perimortal percent carboxy-heme in nonstandard postmortem specimens using analysis of carbon monoxide by GC/MS and iron by flame atomic absorption spectrophotometry.

PubMed

Middleberg, R A; Easterling, D E; Zelonis, S F; Rieders, F; Rieders, M F

1993-01-01

In decomposed, formalin-fixed, embalmed, exhumed, and some fire-dried cases in which normal blood is unavailable, the usual methods for determination of carboxyhemoglobin saturation frequently fail. To address these specimens, a method utilizing both gas chromatography/mass spectrometric (GC/MS) determination of carbon monoxide (CO) and flame atomic absorption spectrophotometry (FAAS) determination of iron (Fe), in the same specimen, was developed. The method is reported here, along with its application to seven pertinent forsensic death investigations. The CO analytical methodology involves acid liberation of the gas from the specimen aliquot in a headspace vial. After heating and equilibrating, a sample of the headspace vapor is injected into the GC/MS system with a gastight syringe. Quantitation is achieved by standard addition comparison utilizing the ideal gas law equation. Iron is quantified by FAAS analysis of the same aliquot used for the CO determination, following nitric acid digestion. The concentration is determined by comparison to a standard curve. A formula for determining the minimum percent carboxy-heme saturation was derived by using the ratio of the amount of CO to the amount of Fe in the aliquot analyzed. Tissue types analyzed include spleen, liver, muscle, dried blood, and unspecified decomposed tissue.

Rapid sample preparation and fast GC-MS/MS for the analysis of pesticides and environmental contaminants in fish

USDA-ARS?s Scientific Manuscript database

A rapid high-throughput analytical method for the simultaneous determination of pesticides and environmental contaminants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and flame retardants (FRs) in fish was developed and ...

Automated Peak Detection and Matching Algorithm for Gas Chromatography–Differential Mobility Spectrometry

PubMed Central

Fong, Sim S.; Rearden, Preshious; Kanchagar, Chitra; Sassetti, Christopher; Trevejo, Jose; Brereton, Richard G.

2013-01-01

A gas chromatography–differential mobility spectrometer (GC-DMS) involves a portable and selective mass analyzer that may be applied to chemical detection in the field. Existing approaches examine whole profiles and do not attempt to resolve peaks. A new approach for peak detection in the 2D GC-DMS chromatograms is reported. This method is demonstrated on three case studies: a simulated case study; a case study of headspace gas analysis of Mycobacterium tuberculosis (MTb) cultures consisting of three matching GC-DMS and GC-MS chromatograms; a case study consisting of 41 GC-DMS chromatograms of headspace gas analysis of MTb culture and media. PMID:21204557

The utility of ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) for clinically relevant steroid analysis.

PubMed

Storbeck, Karl-Heinz; Gilligan, Lorna; Jenkinson, Carl; Baranowski, Elizabeth S; Quanson, Jonathan L; Arlt, Wiebke; Taylor, Angela E

2018-05-15

Liquid chromatography tandem mass spectrometry (LC-MS/MS) assays are considered the reference standard for serum steroid hormone analyses, while full urinary steroid profiles are only achievable by gas chromatography (GC-MS). Both LC-MS/MS and GC-MS have well documented strengths and limitations. Recently, commercial ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) systems have been developed. These systems combine the resolution of GC with the high-throughput capabilities of UHPLC. Uptake of this new technology into research and clinical labs has been slow, possibly due to the perceived increase in complexity. Here we therefore present fundamental principles of UHPSFC-MS/MS and the likely applications for this technology in the clinical research setting, while commenting on potential hurdles based on our experience to date. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

[Optimization for supercritical CO2 extraction with response surface methodology and component analysis of Sapindus mukorossi oil].

PubMed

Wu, Yan; Xiao, Xin-yu; Ge, Fa-huan

2012-02-01

To study the extraction conditions of Sapindus mukorossi oil by Supercritical CO2 Extraction and identify its components. Optimized SFE-CO2 Extraction by response surface methodology and used GC-MS to analysie Sapindus mukorossi oil compounds. Established the model of an equation for the extraction rate of Sapindus mukorossi oil by Supercritical CO2 Extraction, and the optimal parameters for the Supercritical CO2 Extraction determined by the equation were: the extraction pressure was 30 MPa, temperature was 40 degrees C; The separation I pressure was 14 MPa, temperature was 45 degrees C; The separation II pressure was 6 MPa, temperature was 40 degrees C; The extraction time was 60 min and the extraction rate of Sapindus mukorossi oil of 17.58%. 22 main compounds of Sapindus mukorossi oil extracted by supercritical CO2 were identified by GC-MS, unsaturated fatty acids were 86.59%. This process is reliable, safe and with simple operation, and can be used for the extraction of Sapindus mukorossi oil.

Studies of long chain lipids in insects by high temperature gas chromatography and high temperature gas chromatography-mass spectrometry.

PubMed

Sutton, Paul A; Wilde, Michael J; Martin, Stephen J; Cvačka, Josef; Vrkoslav, Vladimír; Rowland, Steven J

2013-07-05

The organic compounds occurring naturally on the cuticles (surfaces) of insects are important for insect communication, help to act as protective water barriers and are useful in chemical taxonomy. Typically the cuticular lipids are only studied by gas chromatography-mass spectrometry (GC-MS) of hexane or pentane extracts, so the normal limitations of GC-MS makes it perhaps unsurprising that compounds with more than about 35 carbon atoms have only rarely been reported. Here we show by high temperature (HT) GC and HTGC-MS of extracts of eleven species of insects from nine genera, that longer chain compounds are actually common. Wax esters and triacylglycerides are virtually ubiquitous in such extracts, but long chain (>C35) hydrocarbons also sometimes occur. Whilst the latter have occasionally been reported previously from mass spectrometry studies, the use of the HTGC combination with MS allowed even some isobaric isomers to be separated and thus more complete lipid distributions to be monitored. Since the physical properties of cuticular compounds depend on this composition of the mixtures, such differences may influence the water loss rates of the insects, amongst other effects. In addition, the high molecular weight compound profiles may allow species to be more easily differentiated, one from another. It would be interesting to apply these methods to examination of the cuticular lipids of insects on a more routine basis, ideally in combination with MALDI-TOF-MS and imaging methods. Copyright © 2013 Elsevier B.V. All rights reserved.

Publications - GMC 427 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 427 Publication Details Title: Gas Chromatography coupled to Tandem Mass Spectrometry (GC/MS Tandem Mass Spectrometry (GC/MS/MS) analyses of cuttings for 16 Arctic Slope wells: Alaska Division of

Metabolomics driven analysis of six Nigella species seeds via UPLC-qTOF-MS and GC-MS coupled to chemometrics.

PubMed

Farag, Mohamed A; Gad, Haidy A; Heiss, Andreas G; Wessjohann, Ludger A

2014-05-15

Nigella sativa, commonly known as black cumin seed, is a popular herbal supplement that contains numerous phytochemicals including terpenoids, saponins, flavonoids, alkaloids. Only a few of the ca. 15 species in the genus Nigella have been characterized in terms of phytochemical or pharmacological properties. Here, large scale metabolic profiling including UPLC-PDA-MS and GC-MS with further multivariate analysis was utilized to classify 6 Nigella species. Under optimized conditions, we were able to annotate 52 metabolites including 8 saponins, 10 flavonoids, 6 phenolics, 10 alkaloids, and 18 fatty acids. Major peaks in UPLC-MS spectra contributing to the discrimination among species were assigned as kaempferol glycosidic conjugates, with kaempferol-3-O-[glucopyranosyl-(1→2)-galactopyranosyl-(1→2)-glucopyranoside, identified as potential taxonomic marker for N. sativa. Compared with GC-MS, UPLC-MS was found much more efficient in Nigella sample classification based on genetic and geographical origin. Nevertheless, both GC-MS and UPLC-MS support the remote position of Nigella nigellastrum in relation to the other taxa. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fast analysis of 4-tertoctylphenol, pentachlorophenol and 4-nonylphenol in river sediments by QuEChERS extraction procedure combined with GC-QqQ-MS/MS.

PubMed

Czech, T; Bonilla, N Barco; Gambus, F; González, R Romero; Marín-Sáez, J; Vidal, J L Martínez; Frenich, A Garrido

2016-07-01

A quick, easy, cheap, effective, rugged and safe (QuEChERS)-based extraction method has been optimized for the determination of pentachlorophenol, 4-tertoctylphenol and 4-nonylphenol in river sediments. The extraction method was followed by gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) analysis, which ensures the reliable identification of the target compounds. The proposed method has been validated allowing the successful determination of the selected compounds, with recoveries ranging from 72 to 96%, when three concentration levels were evaluated (10, 50 and 100μgkg(-1)) and inter-day and intra-day precision, expressed as relative standard deviation (RSD), were lower than 20%. The method showed limits of detection (LODs) and limits of quantification (LOQs) ranging from 0.1 to 2.0μgkg(-1) and from 0.5 to 5.0μgkg(-1), respectively. Finally, 25 real samples from Poland have been analyzed, and only 4-tertoctylphenol was detected at concentrations up to 8.9μgkg(-1) of soil dry weight. Copyright © 2016 Elsevier B.V. All rights reserved.

The combination of four analytical methods to explore skeletal muscle metabolomics: Better coverage of metabolic pathways or a marketing argument?

PubMed

Bruno, C; Patin, F; Bocca, C; Nadal-Desbarats, L; Bonnier, F; Reynier, P; Emond, P; Vourc'h, P; Joseph-Delafont, K; Corcia, P; Andres, C R; Blasco, H

2018-01-30

Metabolomics is an emerging science based on diverse high throughput methods that are rapidly evolving to improve metabolic coverage of biological fluids and tissues. Technical progress has led researchers to combine several analytical methods without reporting the impact on metabolic coverage of such a strategy. The objective of our study was to develop and validate several analytical techniques (mass spectrometry coupled to gas or liquid chromatography and nuclear magnetic resonance) for the metabolomic analysis of small muscle samples and evaluate the impact of combining methods for more exhaustive metabolite covering. We evaluated the muscle metabolome from the same pool of mouse muscle samples after 2 metabolite extraction protocols. Four analytical methods were used: targeted flow injection analysis coupled with mass spectrometry (FIA-MS/MS), gas chromatography coupled with mass spectrometry (GC-MS), liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS), and nuclear magnetic resonance (NMR) analysis. We evaluated the global variability of each compound i.e., analytical (from quality controls) and extraction variability (from muscle extracts). We determined the best extraction method and we reported the common and distinct metabolites identified based on the number and identity of the compounds detected with low analytical variability (variation coefficient<30%) for each method. Finally, we assessed the coverage of muscle metabolic pathways obtained. Methanol/chloroform/water and water/methanol were the best extraction solvent for muscle metabolome analysis by NMR and MS, respectively. We identified 38 metabolites by nuclear magnetic resonance, 37 by FIA-MS/MS, 18 by GC-MS, and 80 by LC-HRMS. The combination led us to identify a total of 132 metabolites with low variability partitioned into 58 metabolic pathways, such as amino acid, nitrogen, purine, and pyrimidine metabolism, and the citric acid cycle. This combination also showed that the contribution of GC-MS was low when used in combination with other mass spectrometry methods and nuclear magnetic resonance to explore muscle samples. This study reports the validation of several analytical methods, based on nuclear magnetic resonance and several mass spectrometry methods, to explore the muscle metabolome from a small amount of tissue, comparable to that obtained during a clinical trial. The combination of several techniques may be relevant for the exploration of muscle metabolism, with acceptable analytical variability and overlap between methods However, the difficult and time-consuming data pre-processing, processing, and statistical analysis steps do not justify systematically combining analytical methods. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of organo-zinc based fungicides in timber treatments employing gas chromatographic analysis with mass selective detection and/or inductively coupled plasma atomic emission spectroscopy.

PubMed

Rimmer, D A; Johnson, P D; Bradley, S D

2001-09-14

A method for the determination of zinc octoate (zinc 2-ethylhexanoate) and acypetacs zinc in occupational hygiene samples and wood treatments formulations is described. The zinc carboxylates are liquid-liquid partitioned between toluene and 1 M HCl, with the liberated acids being extracted into the toluene and zinc (chloride) into the acid. The carboxylic acids are then methylated using trimethylsilyldiazomethane-methanol and the resultant methyl esters are selectively and sensitively analysed by gas chromatography with mass selective detection (GC-MS). Alternatively, the zinc content of the acid extract can be analysed by inductively coupled plasma atomic emission spectroscopy (ICP-AES). GC-MS is the preferred method of analysis for zinc octoate, where a single analyte (methyl-2-ethylhexanoate) is produced for analysis. Because acypetacs zinc contains a complex mixture of carboxylates, quantitative GC-MS analysis of the methyl esters produced is impractical and ICP-AES is the preferred method for quantitation. In this case, GC-MS can be used to confirm the identity of the product used. The analysis of occupational hygiene samples (cotton pads, gloves and socks as well as Tenax tubes and GF/A filters) spiked with metal carboxylates is demonstrated. Recoveries around 70-90% and reproducibilities of 5-23% (n=6-8) were typically achieved for the determination of tin octoate (a surrogate for zinc octoate) at spiking levels ranging from 4 to 190 microg per sampling device. Recoveries around 102-106% and reproducibilities of 10-12% (n=5-6) were typically achieved for acypetacs zinc at spiking levels ranging from 100 mg per sampling device. Reaction yields for the octoate methylation reaction were in the region of 85-87%. The method was used to monitor for occupational exposure to zinc octoate and acypetacs zinc during the application of wood treatments to fences.

COMPARATIVE EVALUATION OF GC/MS (GAS CHROMATOGRAPHY/MASS SPECTROMETRY) DATA ANALYSIS PROCESSING

EPA Science Inventory

Mass spectra obtained by fused silica capillary gas chromatography/mass spectrometry/data system (GC/MS/DS) analysis of mixtures of organic chemicals adsorbed on Tenax GC cartridges was subjected to manual and automated interpretative techniques. Synthetic mixtures (85 chemicals ...

IDENTIFICATION OF NEW OZONE DISINFECTION BY PRODUCTS IN DRINKING WATER

EPA Science Inventory

Using a combination of spectral identification techniques-gas chromatography coupled with low- and high-resolution electron-impact mass spectrometry (GC/EI-MS), low- and high-resolution chemical ionization mass spectrometry (GC/CI-MS), and infrared spectroscopy (GC/ IR)-we identi...

Application of gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to detect the abuse of 17β-estradiol in cattle.

PubMed

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

2013-07-31

Although the ability to differentiate between endogenous steroids and synthetic homologues on the basis of their (13)C/(12)C isotopic ratio has been known for over a decade, this technique has been scarcely implemented for food safety purposes. In this study, a method was developed using gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to demonstrate the abuse of 17β-estradiol in cattle, by comparison of the (13)C/(12)C ratios of the main metabolite 17α-estradiol and an endogenous reference compound (ERC), 5-androstene-3β,17α-diol, in bovine urine. The intermediate precisions were determined as 0.46 and 0.26‰ for 5-androstene-3β,17α-diol and 17α-estradiol, respectively. This is, to the authors' knowledge, the first reported use of GC-MS/C/IRMS for the analysis of steroid compounds for food safety issues.

Acrylamide in Caribbean foods - residual levels and their relation to reducing sugar and asparagine content.

PubMed

Bent, Grace-Anne; Maragh, Paul; Dasgupta, Tara

2012-07-15

The acrylamide levels in commercial and homemade Caribbean foods were determined by pre-derivatisation of acrylamide to 2-bromopropenamide and analysed by gas chromatography with mass spectrometric (GC/MS) detection. Over 100 Caribbean food samples were analysed for the presence of acrylamide. These samples include: biscuits, breakfast cereals, banana chips and home-prepared foods: breadfruit; Artocarpus altilis, banana fritters, and dumplings. The limit of detection (LOD) for the GC/MS method was found to be dependent on the type of column used for the GC/MS analysis. The DB-1701 and the DB-VRX columns gave LODs of 20 and 4 μg/kg, respectively. Acrylamide has not been found in raw foods or foods which have been cooked by boiling. Its content in all other foods had concentrations in the range, 65-3,640 μg/kg. The relationship between acrylamide levels and precursor concentration as well as the health implications of our findings are discussed. Copyright © 2012 Elsevier Ltd. All rights reserved.

IR and py/GC/MS examination of amber relics excavated from 6th century royal tomb in Korean Peninsula.

PubMed

Park, Jongseo; Yun, Eunyoung; Kang, Hyungtae; Ahn, Jooyoung; Kim, Gyuho

2016-08-05

Relics of amber were excavated from King Muryeong's tomb constructed in the 6th century on the Korean peninsula. To estimate the provenance, FTIR (Fourier transform infrared spectroscopy) and py/GC/MS (pyrolysis/gas chromatography/mass spectrometry) analysis were utilized. The reference Baltic amber sample was also analyzed with the same method for comparison. The relics were confirmed to be amber from the FTIR analysis where an absorption band near 1150cm(-1), characteristic one in Baltic amber, was also observed. In py/GC/MS analysis, pyrolyzed products like butanedioic acid and dehydroabietic acid, known constituents of amber, were observed. In addition, d-fenchyl alcohol, camphor, borneol and butanedioic acid, typical constituents of Baltic amber, were observed in some samples. From this, it appears that some of relics were made from Baltic amber and that Baltic amber was transported to the Korean peninsula in the time of tomb construction. Copyright © 2016 Elsevier B.V. All rights reserved.