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Sample records for chemical ionisation mass

  1. Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

    NASA Astrophysics Data System (ADS)

    Bannan, Thomas; Booth, A. Murray; Alfarra, Rami; Bacak, Asan; Pericval, Carl

    2016-04-01

    Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

  2. Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

    NASA Astrophysics Data System (ADS)

    Bannan, T.; Booth, M.; Benyezzar, M.; Bacak, A.; Alfarra, M. R. R.; Topping, D. O.; Percival, C.

    2015-12-01

    Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

  3. Chemical profile of mango (Mangifera indica L.) using electrospray ionisation mass spectrometry (ESI-MS).

    PubMed

    Oliveira, Bruno G; Costa, Helber B; Ventura, José A; Kondratyuk, Tamara P; Barroso, Maria E S; Correia, Radigya M; Pimentel, Elisângela F; Pinto, Fernanda E; Endringer, Denise C; Romão, Wanderson

    2016-08-01

    Mangifera indica L., mango fruit, is consumed as a dietary supplement with purported health benefits; it is widely used in the food industry. Herein, the chemical profile of the Ubá mango at four distinct maturation stages was evaluated during the process of growth and maturity using negative-ion mode electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI(-)FT-ICR MS) and physicochemical characterisation analysis (total titratable acidity (TA), total soluble solids (TSS), TSS/TA ratio, and total polyphenolic content). Primary (organic acids and sugars) and secondary metabolites (polyphenolic compounds) were mostly identified in the third maturation stage, thus indicating the best stage for harvesting and consuming the fruit. In addition, the potential cancer chemoprevention of the secondary metabolites (phenolic extracts obtained from mango samples) was evaluated using the induction of quinone reductase activity, concluding that fruit polyphenols have the potential for cancer chemoprevention. PMID:26988473

  4. Chemical profile of mango (Mangifera indica L.) using electrospray ionisation mass spectrometry (ESI-MS).

    PubMed

    Oliveira, Bruno G; Costa, Helber B; Ventura, José A; Kondratyuk, Tamara P; Barroso, Maria E S; Correia, Radigya M; Pimentel, Elisângela F; Pinto, Fernanda E; Endringer, Denise C; Romão, Wanderson

    2016-08-01

    Mangifera indica L., mango fruit, is consumed as a dietary supplement with purported health benefits; it is widely used in the food industry. Herein, the chemical profile of the Ubá mango at four distinct maturation stages was evaluated during the process of growth and maturity using negative-ion mode electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI(-)FT-ICR MS) and physicochemical characterisation analysis (total titratable acidity (TA), total soluble solids (TSS), TSS/TA ratio, and total polyphenolic content). Primary (organic acids and sugars) and secondary metabolites (polyphenolic compounds) were mostly identified in the third maturation stage, thus indicating the best stage for harvesting and consuming the fruit. In addition, the potential cancer chemoprevention of the secondary metabolites (phenolic extracts obtained from mango samples) was evaluated using the induction of quinone reductase activity, concluding that fruit polyphenols have the potential for cancer chemoprevention.

  5. Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

    NASA Astrophysics Data System (ADS)

    Le Breton, M.; Bacak, A.; Muller, J. B. A.; O'Shea, S. J.; Xiao, P.; Ashfold, M. N. R.; Cooke, M. C.; Batt, R.; Shallcross, D. E.; Oram, D. E.; Forster, G.; Bauguitte, S. J.-B.; Percival, C. J.

    2013-09-01

    A chemical ionisation mass spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I- reagent ions on board the FAAM BAe-146 research aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere. A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH3CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume-defining techniques employing CO and CH3CN measurements. The 6-sigma technique produced the highest R2 values for correlations with CO. A normalised excess mixing ratio (NEMR) of 3.68 ± 0.149 pptv ppbv-1 was calculated, which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work, the emission total for HCN from BB was 0.92 Tg (N) yr-1.

  6. Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

    NASA Astrophysics Data System (ADS)

    Le Breton, M.; Bacak, A.; Muller, J. B. A.; O'Shea, S. J.; Xiao, P.; Ashfold, M. N. R.; Cooke, M. C.; Batt, R.; Shallcross, D. E.; Oram, D. E.; Forster, G.; Bauguitte, S. J.-B.; Percival, C. J.

    2013-02-01

    A Chemical Ionisation Mass Spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I- reagent ions on board the FAAM BAe-146 research aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere. A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH3CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume defining techniques employing CO and CH3CN measurements. The 6 sigma technique produced the highest R2 values for correlations with CO. A Normalised Excess Mixing Ratio (NEMR) of 3.76 ± 0.022 pptv ppbv-1 was calculated which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work the emission total for HCN from BB was 0.92 Tg (N) yr-1.

  7. Analysis of oilfield produced waters and production chemicals by electrospray ionisation multi-stage mass spectrometry (ESI-MSn).

    PubMed

    McCormack, P; Jones, P; Hetheridge, M J; Rowland, S J

    2001-10-01

    Large quantities of diverse polar organic chemicals are routinely discharged from oil production platforms in so-called produced waters. The environmental fate of many of these is unknown since few methods exist for their characterisation. Preliminary investigations into the use of multistage electrospray ionisation ion trap mass spectrometry (ESI-MSn) show its potential for the identification and quantification of compounds in specialty oilfield chemicals (corrosion inhibitors, scale inhibitors, biocides and demulsifiers) and produced waters. Multiple stage mass spectrometry (MSn) with both positive and negative ion detection allows high specificity detection and characterisation of a wide range of polar and charged molecules. For example, linear alkylbenzenesulfonates (LAS), alkyldimethylbenzylammonium compounds, 2-alkyl-1-ethylamine-2-imidazolines, 2-alkyl-1-[N-ethylalkylamide]-2-imidazolines and a di-[alkyldimethylammonium-ethyl]ether were all identified and characterised in commercial formulations and/or North Sea oilfield produced waters. The technique should allow the marine environmental effects and fates of some of these polar compounds to be studied.

  8. Analysis of wax ester molecular species by high performance liquid chromatography/atmospheric pressure chemical ionisation mass spectrometry.

    PubMed

    Vrkoslav, Vladimír; Urbanová, Klára; Cvacka, Josef

    2010-06-18

    High chromatographic resolution of wax esters (WEs) was achieved by non-aqueous reversed-phase liquid chromatography on a Nova-Pak C18 column by optimising the acetonitrile/ethyl acetate mobile phase gradient. The retention behaviour of WEs was studied in this chromatographic system. The WEs eluted according to their equivalent carbon number (ECN) values; within the group of WEs with the identical ECN, the most unsaturated species tended to elute first. The isobaric WEs with different positions of the ester moiety were separated from each other whenever the lengths of the chains were sufficiently different. The methyl-branched esters eluted at shorter retention times than the straight-chained analogues, and the resolution among methyl-branched WEs depended on the position of the branching. The analytes were detected by atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) using data-dependent scanning. WEs provided simple full-scan spectra with abundant protonated molecules and low-intensity fragments. Collision-induced dissociation (CID) promoted identification of the WE molecular species. The responses of WEs were found to be dependent on the number of double bonds and on the alkyl-chain length; the limits of the detection ranged from 20micromol/L to 200nmol/L. The HPLC/APCI-MS was applied for the analysis of the WEs isolated from honeycomb beeswax, jojoba oil and human hair. Good agreement between reported results and the literature data was achieved, with several novel polyunsaturated WEs also being found.

  9. Multi-residue analysis of pesticides in traditional Chinese medicines using gas chromatography-negative chemical ionisation tandem mass spectrometry.

    PubMed

    Nie, Jing; Miao, Shui; Lehotay, Steven J; Li, Wen-Ting; Zhou, Heng; Mao, Xiu-Hong; Lu, Ji-Wei; Lan, Lan; Ji, Shen

    2015-01-01

    In this study, a residue analysis method for the simultaneous determination of 107 pesticides in traditional Chinese medicines (TCMs), Angelica sinensis, A. dahurica, Leonurus heterophyllus Sweet, Pogostemon cablin and Lonicera japonica Thunb., was developed using gas chromatography coupled with tandem mass spectrometry in negative chemical ionisation mode (GC-NCI-MS/MS). NCI has advantages of high sensitivity and selectivity to chemicals with electron-withdrawing groups, and yields low background interference. For sample preparation, QuEChERS (quick, easy, cheap, effective, rugged and safe) was applied. Due to the unique characteristics of TCMs, the clean-up step was optimised by adjusting amounts of primary secondary amine, C18, graphitised carbon black and silica sorbents. Validation was mainly performed by determining analyte recoveries at four different spiking concentrations of 10, 50, 100 and 200 ng g(-1), with seven replicates at each concentration. Method trueness, precision, linearity of calibration curves, lowest calibrated levels (LCLs) and matrix effects were determined to demonstrate method and instrument performance. Among the 107 pesticides tested, approximately 80% gave recoveries from 80% to 110% and < 10% relative standard deviation (RSD). The LCLs for nearly all pesticides were 5 ng g(-1), and as low as 0.1 ng g(-1) for dichlofenthion, endosulfan sulphate, flumetralin, isofenphos-methyl, methyl-pentachlorophenyl sulphide and trifluralin. The results indicate that GC-NCI-MS/MS is an excellent technique for quantitative and qualitative analysis of targeted GC-amenable pesticides at ultra-trace levels, especially in complex matrices such as TCMs. PMID:26125677

  10. Online antioxidant activity and ultra-performance LC-electrospray ionisation-quadrupole time-of-fight mass spectrometry for chemical fingerprinting of Indian polyherbal formulations.

    PubMed

    Bhandari, Pamita; Kumar, Neeraj; Khan, Shahid M; Bhutani, Kamlesh K

    2016-01-01

    A HPLC-DAD-DPPH method was developed for evaluating the 1, 1-diphenyl-2-picryl hydrazyl free radical scavenging activity of ethylacetate extracts of different polyherbal formulations (draksarista, draksava, lohasava and arvindasava) by using RP-18e column. The ethylacetate extract from polyherbal, 'draksarista' exhibited maximum free radical scavenging activity (99.9 ± 0.38%) followed by draksava (99.8 ± 0.34%), lohasava (98.5 ± 0.30%) and arvindasava (42.3 ± 0.34%) at 100 μg mL(-1). Simultaneously, ultra-performance liquid chromatography coupled with electrospray ionisation-quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS) was used to study chemical composition of the ethylacetate extracts of formulations. The characteristic electrospray mass ionisation reveals the dominance of polyphenols and their glycosides in the four polyherbal formulations.

  11. Simultaneous determination of volatile and non-volatile nitrosamines in processed meat products by liquid chromatography tandem mass spectrometry using atmospheric pressure chemical ionisation and electrospray ionisation.

    PubMed

    Herrmann, S S; Duedahl-Olesen, L; Granby, K

    2014-02-21

    A sensitive, selective and generic method has been developed for the simultaneous determination of the contents (μgkg(-1) range) of both volatile nitrosamines (VNA) and non-volatile nitrosamines (NVNA) in processed meat products. The extraction procedure only requires basic laboratory equipment and a small volume of organic solvent. Separation and quantification were performed by the developed LC-(APCI/ESI)MS/MS method. The method was validated using spiked samples of three different processed meat products. Satisfactory recoveries (50-130%) and precisions (2-23%) were obtained for eight VNA and six NVNAs with LODs generally between 0.2 and 1μgkg(-1), though for a few analyte/matrix combinations higher LODs were obtained (3 to 18μgkg(-1)). The validation results show that results obtained for one meat product is not always valid for other meat products. We were not able to obtain satisfactory results for N-nitrosohydroxyproline (NHPRO), N-nitrosodibenzylamine (NDBzA) and N-nitrosodiphenylamine (NDPhA). Application of the APCI interface improved the sensitivity of the method, because of less matrix interference, and gave the method a wider scope, as some NAs were ionisable only by APCI. However, it was only possible to ionize N-nitroso-thiazolidine-4-carboxylic acid (NTCA) and N-nitroso-2-methyl-thiazolidine-4-carboxylic acid (NMTCA) by ESI. The validated method was applied for the analysis of processed meat products and contents of N-nitrosodimethylamine (NDMA), N-nitrosopyrrolidine (NPYR), N-nitrosomethylaniline (NMA), N-nitrosoproline (NPRO), NTCA, and NMTCA were found in one or several nitrite cured meat products, whereas none were detected in non-nitrite cured bacon.

  12. The application of gas chromatography/atmospheric pressure chemical ionisation time-of-flight mass spectrometry to impurity identification in Pharmaceutical Development.

    PubMed

    Bristow, Tony; Harrison, Mark; Sims, Martin

    2010-06-15

    Accurate mass measurement (used to determine elemental formulae) is an essential tool for impurity identification in pharmaceutical development for process understanding. Accurate mass liquid chromatography/mass spectrometry (LC/MS) is used widely for these types of analyses; however, there are still many occasions when gas chromatography (GC)/MS is the appropriate technique. Therefore, the provision of robust technology to provide accurate mass GC/MS (and GC/MS/MS) for this type of activity is essential. In this report we describe the optimisation and application of a newly available atmospheric pressure chemical ionisation (APCI) interface to couple GC to time-of-flight (TOF) MS.To fully test the potential of the new interface the APCI source conditions were optimised, using a number of standard compounds, with a variety of structures, as used in synthesis at AstraZeneca. These compounds were subsequently analysed by GC/APCI-TOF MS. This study was carried out to evaluate the range of compounds that are amenable to analysis using this technique. The range of compounds that can be detected and characterised using the technique was found to be extremely broad and include apolar hydrocarbons such as toluene. Both protonated molecules ([M + H](+)) and radical cations (M(+.)) were observed in the mass spectra produced by APCI, along with additional ion signals such as [M + H + O](+).The technique has been successfully applied to the identification of impurities in reaction mixtures from organic synthesis in process development. A typical mass accuracy of 1-2 mm/zunits (m/z 80-500) was achieved allowing the reaction impurities to be identified based on their elemental formulae. These results clearly demonstrate the potential of the technique as a tool for problem solving and process understanding in pharmaceutical development. The reaction mixtures were also analysed by GC/electron ionisation (EI)-MS and GC/chemical ionisation (CI)-MS to understand the capability of GC

  13. Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

    PubMed

    Bichon, E; Guiffard, I; Vénisseau, A; Lesquin, E; Vaccher, V; Brosseaud, A; Marchand, P; Le Bizec, B

    2016-08-12

    A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1μmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time.

  14. Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

    PubMed

    Bichon, E; Guiffard, I; Vénisseau, A; Lesquin, E; Vaccher, V; Brosseaud, A; Marchand, P; Le Bizec, B

    2016-08-12

    A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1μmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time. PMID:27425757

  15. Sensitive monitoring of monoterpene metabolites in human urine using two-step derivatisation and positive chemical ionisation-tandem mass spectrometry.

    PubMed

    Schmidt, Lukas; Belov, Vladimir N; Göen, Thomas

    2013-09-01

    A gas chromatographic-positive chemical ionisation-tandem mass spectrometric (GC-PCI-MS/MS) method for the simultaneous determination of 10 oxidative metabolites of the monoterpenoid hydrocarbons α-pinene, (R)-limonene, and Δ(3)-carene ((+)-3-carene) in human urine was developed and tested for the monoterpene biomonitoring of the general population (n=36). The method involves enzymatic cleavage of the glucuronides followed by solid-supported liquid-liquid extraction and derivatisation using a two-step reaction with N,O-bis(trimethylsilyl)-trifluoroacetamide and N-(trimethylsilyl)imidazole. The method proved to be both sensitive and reliable with detection limits ranging from 0.1 to 0.3 μg L(-1). In contrast to the frequent and distinct quantities of (1S,2S,4R)-limonene-1,2-diol, the (1R,2R,4R)-stereoisomer could not be detected. The expected metabolite of (+)-3-carene, 3-caren-10-ol was not detected in any of the samples. All other metabolites were detected in almost all urine samples. The procedure enables for the first time the analysis of trace levels of a broad spectrum of mono- and bicyclic monoterpenoid metabolites (alcohols, diols, and carboxylic acids) in human urine. This analytical procedure is a powerful tool for population studies as well as for the discovery of human metabolism and toxicokinetics of monoterpenes. PMID:23953203

  16. Real-time Measurement of Secondary Organic Aerosols From The Photo-oxidation of Toluene Using Atmospheric Pressure Chemical Ionisation Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Collin, F.; Arias, M. C.; Merritt, J. V.; Hastie, D. R.

    A system has been developed to study the chemical composition of secondary or- ganic aerosol (SOA) from the photo-oxidation of hydrocarbons using real-time atmo- spheric pressure chemical ionisation triple quadrupole mass spectrometry (APCI/MS- MS) analysis. To complement existing work with a smog chamber, a two-litre dynamic reaction cell has been built. This has a residence time of around two minutes (instead of several hours for smog chamber experiments), thus permitting on-line analysis. Sample gases are introduced into the air stream and irradiated by a 1000 W xenon arc lamp. Af- ter dilution, some of the mixture from the reaction cell is introduced in the MS ion source via a heated probe, with the particle number density being determined by a condensation nucleus counter on the remainder. The focus so far has been on SOA from the photo-oxidation of toluene by HO radicals in presence of NO, with the HO radicals being generated by the photolysis of Isopy- lNitrite (IPN). Prior to performing analyses on the SOA, target compounds (detected in the particulate phase in other studies) were selected and three ions designated to make a fingerprint for each compound. Finally, by using either a denuder, a granu- lar bed diffusion battery or a filter, both gas and particulate phases have been studied independently and compared. Preliminary results show that a number of target compounds, such as methylglyoxylic acid, benzaldehyde or cresol, have been detected in both gas and particulate phases. Most of these compounds appear to be present mainly in the gas phase. An exhaustive identification of organic compounds is a part of the on-going work.

  17. Fast gas chromatographic residue analysis in animal feed using split injection and atmospheric pressure chemical ionisation tandem mass spectrometry.

    PubMed

    Tienstra, M; Portolés, T; Hernández, F; Mol, J G J

    2015-11-27

    Significant speed improvement for instrumental runtime would make GC–MS much more attractive for determination of pesticides and contaminants and as complementary technique to LC–MS. This was the trigger to develop a fast method (time between injections less than 10 min) for the determination of pesticides and PCBs that are not (or less) amenable to LC–MS. A key factor in achieving shorter analysis time was the use of split injection (1:10) which allowed the use of a much higher initial GC oven temperature. A shorter column (15 m), higher temperature ramp, and higher carrier gas flow rate (6 mL/min) further contributed to analysis-time reduction. Chromatographic resolution was slightly compromised but still well fit-for-purpose. Due to the high sensitivity of the technique used (GC–APCI-triple quadrupole MS/MS), quantification and identification were still possible down to the 10 μg/kg level, which was demonstrated by successful validation of the method for complex feed matrices according to EU guidelines. Other advantages of the method included a better compatibility of acetonitrile extracts (e.g. QuEChERS) with GC, and a reduced transfer of co-extractants into the GC column and mass spectrometer. PMID:26601712

  18. Fast gas chromatographic residue analysis in animal feed using split injection and atmospheric pressure chemical ionisation tandem mass spectrometry.

    PubMed

    Tienstra, M; Portolés, T; Hernández, F; Mol, J G J

    2015-11-27

    Significant speed improvement for instrumental runtime would make GC–MS much more attractive for determination of pesticides and contaminants and as complementary technique to LC–MS. This was the trigger to develop a fast method (time between injections less than 10 min) for the determination of pesticides and PCBs that are not (or less) amenable to LC–MS. A key factor in achieving shorter analysis time was the use of split injection (1:10) which allowed the use of a much higher initial GC oven temperature. A shorter column (15 m), higher temperature ramp, and higher carrier gas flow rate (6 mL/min) further contributed to analysis-time reduction. Chromatographic resolution was slightly compromised but still well fit-for-purpose. Due to the high sensitivity of the technique used (GC–APCI-triple quadrupole MS/MS), quantification and identification were still possible down to the 10 μg/kg level, which was demonstrated by successful validation of the method for complex feed matrices according to EU guidelines. Other advantages of the method included a better compatibility of acetonitrile extracts (e.g. QuEChERS) with GC, and a reduced transfer of co-extractants into the GC column and mass spectrometer.

  19. Photo-ionisation mass spectrometry as detection method for gas chromatography. Optical selectivity and multidimensional comprehensive separations.

    PubMed

    Zimmermann, Ralf; Welthagen, Werner; Gröger, Thomas

    2008-03-14

    Mass spectrometry (MS) with soft ionisation techniques (i.e. ionisation without fragmentation of the analyte molecules) for gaseous samples exhibits interesting analytical properties for direct analysis applications (i.e. direct inlet mass spectrometric on-line monitoring) as well as mass spectrometric detection method for gas chromatography (GC-MS). Commonly either chemical ionisation (CI) or field ionisation (FI) is applied as soft ionisation technology for GC-MS. An interesting alternative to the CI and FI technologies methods are photo-ionisation (PI) methods. PI overcomes some of the limitations of CI and FI and furthermore add some unique analytical properties. The resonance enhanced multi-photon ionisation (REMPI) method uses intense UV-laser pulses (wavelength range approximately 350-193 nm) for highly selective, sensitive and soft ionisation of predominately aromatic compounds. The single photon ionisation (SPI) method utilises VUV light (from lamps or laser sources, wavelengths range approximately 150-110 nm) can be used for a universal soft ionisation of organic molecules. In this article the historical development as well as the current status and concepts of gas chromatography hyphenated to photo-ionisation mass spectrometry are reviewed. PMID:17915237

  20. Determination of N-nitrosamines in processed meats by liquid extraction combined with gas chromatography-methanol chemical ionisation/mass spectrometry.

    PubMed

    Scheeren, Marina Bergoli; Sabik, Hassan; Gariépy, Claude; Terra, Nelcindo Nascimento; Arul, Joseph

    2015-01-01

    A simple, accessible and reproducible method was developed and validated as an alternative for the determination of nine volatile N-nitrosamines (NAs) in meat products, using a low volume of organic solvent and without requiring specific apparatus, offering the possibility of practical implementation in routine laboratories. The NAs were extracted with dichloromethane followed by a clean-up with phosphate buffer solution (pH 7.0). The extracts were analysed by gas chromatography-chemical ionisation/mass spectrometry (GC-CI/MS) in positive-ion mode using methanol as reagent. Limits of detection and quantification, recovery and reproducibility were determined for all NAs (N-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosopyrrolidine, N-nitrosodipropylamine, N-nitrosomorpholine, N-nitrosopiperidine, N-nitrosodibutylamine and N-nitrosodiphenylamine). Satisfactory sensitivity and selectivity were obtained even without concentrating the extract by solvent evaporation, avoiding the loss of the nine NAs studied. Limits of detection ranged from 0.15 to 0.37 µg kg(-1), whereas limits of quantification ranged from 0.50 to 1.24 µg kg(-1). Recoveries calculated in cooked ham that had been spiked at 10 and 100 µg kg(-1) were found to be between 70% and 114% with an average relative standard deviation of 13.2%. The method was successfully used to analyse five samples of processed meat products on the day of purchase and 7 days later (after storage at 4°C). The most abundant NAs found in the analysed products were N-nitrosodipropylamine and N-nitrosopiperidine, which ranged from 1.75 to 34.75 µg kg(-1) and from 1.50 to 4.26 µg kg(-1), respectively. In general, an increase in the level of NAs was observed after the storage period. The proposed method may therefore be a useful tool for food safety control once it allows assessing the profile and the dietary intake of NAs in food over time.

  1. Analysis of intact bacteria using rapid evaporative ionisation mass spectrometry.

    PubMed

    Strittmatter, Nicole; Jones, Emrys A; Veselkov, Kirill A; Rebec, Monica; Bundy, Jacob G; Takats, Zoltan

    2013-07-14

    An identification system for microorganisms based on recently developed rapid evaporative ionisation mass spectrometry (REIMS) is presented. Nine bacterial species cultured on various growth media were correctly identified to family-, genus-, and species-level based on their different mass spectral fingerprints using a cross-validated maximum margin criterion model.

  2. Electrospray ionisation mass spectrometry: principles and clinical applications.

    PubMed

    Ho, C S; Lam, C W K; Chan, M H M; Cheung, R C K; Law, L K; Lit, L C W; Ng, K F; Suen, M W M; Tai, H L

    2003-01-01

    This mini-review provides a general understanding of electrospray ionisation mass spectrometry (ESI-MS) which has become an increasingly important technique in the clinical laboratory for structural study or quantitative measurement of metabolites in a complex biological sample. The first part of the review explains the electrospray ionisation process, design of mass spectrometers with separation capability, characteristics of the mass spectrum, and practical considerations in quantitative analysis. The second part then focuses on some clinical applications. The capability of ESI-tandem-MS in measuring bio-molecules sharing similar molecular structures makes it particularly useful in screening for inborn errors of amino acid, fatty acid, purine, pyrimidine metabolism and diagnosis of galactosaemia and peroxisomal disorders. Electrospray ionisation is also efficient in generating cluster ions for structural elucidation of macromolecules. This has fostered a new and improved approach (vs electrophoresis) for identification and quantification of haemoglobin variants. With the understanding of glycohaemoglobin structure, an IFCC reference method for glycohaemoglobin assay has been established using ESI-MS. It represents a significant advancement for the standardisation of HbA1c in diabetic monitoring. With its other applications such as in therapeutic drug monitoring, ESI-MS will continue to exert an important influence in the future development and organisation of the clinical laboratory service.

  3. Impact ionisation mass spectrometry of polypyrrole-coated pyrrhotite microparticles

    NASA Astrophysics Data System (ADS)

    Hillier, Jon K.; Sternovsky, Zoltan; Armes, Steven P.; Fielding, Lee A.; Postberg, Frank; Bugiel, Sebastian; Drake, Keith; Srama, Ralf; Kearsley, Anton T.; Trieloff, Mario

    2014-07-01

    Cation and anion impact ionization mass spectra of polypyrrole-coated pyrrhotite cosmic dust analogue particles are analysed over a range of cosmically relevant impact speeds. Spectra with mass resolutions of 150-300 were generated by hypervelocity impacts of charged particles, accelerated to up to 37 km s-1 in a Van de Graaff electrostatic accelerator, onto a silver target plate in the Large Area Mass Analyzer (LAMA) spectrometer. Ions clearly indicative of the polypyrrole overlayer are identified at masses of 93, 105, 117, 128 and 141 u. Organic species, predominantly derived from the thin (20 nm) polypyrrole layer on the surface of the particles, dominate the anion spectra even at high (>20 km s-1) impact velocities and contribute significantly to the cation spectra at velocities lower than this. Atomic species from the pyrrhotite core (Fe and S) are visible in all spectra at impact velocities above 6 km s-1 for 56Fe+, 9 km s-1 for 32S+ and 16 km s-1 for 32S- ions. Species from the pyrrhotite core are also frequently visible in cation spectra at impact speeds at which surface ionisation is believed to dominate (<10 km s-1), although the large number of organic peaks complicates the identification of characteristic molecular species. A thin oxidised surface layer on the pyrrhotite particles is indicated by weak spectral features assigned to iron oxides and iron oxy-hydroxides, although the definitive identification of sulfates and hydrated sulfates from the oxidation process was not possible. Silver was confirmed as an excellent choice for the target plate of an impact ionization mass spectrometer, as it provided a unique isotope signature for many target-projectile cluster peaks at masses above 107-109 u. The affinity of Ag towards a dominant organic fragment ion (CN-) derived from fragmentation of the polypyrrole component led to molecular cluster formation. This resulted in an enhanced sensitivity to a particular particle component, which may be of great use

  4. Determination of ethylenethiourea (ETU) and propylenethiourea (PTU) in foods by high performance liquid chromatography-atmospheric pressure chemical ionisation-medium-resolution mass spectrometry.

    PubMed

    Startin, James R; Hird, Simon J; Sykes, Mark D

    2005-03-01

    A robust and sensitive method for the determination of ethylenethiourea (ETU) and iso-propylenethiourea (i-PTU) in foods is reported. ETU and i-PTU were extracted by blending with dichloromethane (DCM) in the presence of sodium sulphate, sodium carbonate, thiourea and ascorbic acid. 2H4-ETU and n-PTU were used as internal standards. After filtration the DCM was removed by rotary evaporation and the extract re-dissolved in water before analysis by reversed-phase liquid chromatography with detection by atmospheric pressure chemical ionization-mass spectrometry using a double focusing mass spectrometer at a resolution of 5000. Mean recoveries of ETU and i-PTU from fruit-based, cereal-based and meat-based infant foods, potato chips and tinned potatos at 0.01 mg kg(-1) and from pizza and yoghurt at 0.02-0.1 mg kg(-1) were 95% and 97% respectively. Precision, including both repeatability and internal reproducibility, was in the range of 3.1-13.1%.

  5. Forensic applications of desorption electrospray ionisation mass spectrometry (DESI-MS).

    PubMed

    Morelato, Marie; Beavis, Alison; Kirkbride, Paul; Roux, Claude

    2013-03-10

    Desorption electrospray ionisation mass spectrometry (DESI-MS) is an emerging analytical technique that enables in situ mass spectrometric analysis of specimens under ambient conditions. It has been successfully applied to a large range of forensically relevant materials. This review assesses and highlights forensic applications of DESI-MS including the analysis and detection of illicit drugs, explosives, chemical warfare agents, inks and documents, fingermarks, gunshot residues and drugs of abuse in urine and plasma specimens. The minimal specimen preparation required for analysis and the sensitivity of detection achieved offer great advantages, especially in the field of forensic science.

  6. Rapid isolation of biomarkers for compound specific radiocarbon dating using high-performance liquid chromatography and flow injection analysis-atmospheric pressure chemical ionisation mass spectrometry.

    PubMed

    Smittenberg, Rienk H; Hopmans, Ellen C; Schouten, Stefan; Sinninghe Damsté, Jaap S

    2002-11-29

    Repeated semi-preparative normal-phase HPLC was performed to isolate selected biomarkers from sediment extracts for radiocarbon analysis. Flow injection analysis-mass spectrometry was used for rapid analysis of collected fractions to evaluate the separation procedure, taking only 1 min per fraction. In this way 100-1000 microg of glycerol dialkyl glycerol tetraethers, sterol fractions and chlorophyll-derived phytol were isolated from typically 100 g of marine sediment, i.e., in sufficient quantities for radiocarbon analysis, without significant carbon isotopic fractionation or contamination.

  7. High ionisation absorption in low mass X-ray binaries

    NASA Astrophysics Data System (ADS)

    Ponti, G.; Bianchi, S.; Muñoz-Darias, T.; De, K.; Fender, R.; Merloni, A.

    2016-05-01

    The advent of the new generation of X-ray telescopes yielded a significant step forward in our understanding of ionised absorption generated in the accretion discs of X-ray binaries. It has become evident that these relatively weak and narrow absorption features, sporadically present in the X-ray spectra of some systems, are actually the signature of equatorial outflows, which might carry away more matter than that being accreted. Therefore, they play a major role in the accretion phenomenon. These outflows (or ionised atmospheres) are ubiquitous during the softer states but absent during the power-law dominated, hard states, suggesting a strong link with the state of the inner accretion disc, presence of the radio-jet and the properties of the central source. Here, we discuss the current understanding of this field.

  8. Identification of carbohydrates by matrix-free material-enhanced laser desorption/ionisation mass spectrometry.

    PubMed

    Hashir, Muhammad Ahsan; Stecher, Guenther; Bakry, Rania; Kasemsook, Saowapak; Blassnig, Bernhard; Feuerstein, Isabel; Abel, Gudrun; Popp, Michael; Bobleter, Ortwin; Bonn, Guenther K

    2007-01-01

    Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is a sensitive mass spectrometric technique which utilises acidic materials as matrices for laser energy absorption, desorption and ionisation of analytes. These matrix materials produce background signals particularly in the low-mass range and make the detection and identification of small molecules difficult and nearly impossible. To overcome this problem this paper introduces matrix-free material-enhanced laser desorption/ionisation mass spectrometry (mf-MELDI-MS) for the screening and analysis of small molecules such as carbohydrates. For this purpose, 4,4'-azo-dianiline was immobilised on silica gel enabling the absorption of laser energy sufficient for successful desorption and ionisation of low molecular weight compounds. The particle and pore sizes, the solvent system for suspension and the sample preparation procedures have been optimised. The newly synthesised MELDI material delivered excellent spectra with regard to signal-to-noise ratio and detection sensitivity. Finally, wheat straw degradation products and Salix alba L. plant extracts were analysed proving the high performance and excellent behaviour of the introduced material.

  9. Single-stage accelerator mass spectrometer radiocarbon-interference identification and positive-ionisation characterisation

    NASA Astrophysics Data System (ADS)

    Wilcken, K. M.; Freeman, S. P. H. T.; Xu, S.; Dougans, A.

    2013-01-01

    A single-stage accelerator mass spectrometer (SSAMS) is a good alternative to conventional spectrometers based on tandem electrostatic acceleration for radiocarbon measurement and permits experimentation with both negative and positive carbon ions. However, such 14C AMS of either polarity ions is limited by an interference. In the case of anion acceleration we have newly determined this to be summed 13C and 16O by improvising an additional Wien filter on our SSAMS deck. Also, 14C AMS might be improved by removing its dependency on negative-ionisation in a sputter ion source. This requires negative-ionisation of sample atoms elsewhere to suppress the 14N interference, which we accomplish by transmitting initially positive ions through a thin membrane. The ionisation dependence on ion-energy is found to be consistent with previous experimentation with vapours and thicker foils.

  10. A Carbon Nano Tube electron impact ionisation source for low-power, compact spacecraft mass spectrometers

    NASA Astrophysics Data System (ADS)

    Sheridan, S.; Bardwell, M. W.; Morse, A. D.; Morgan, G. H.

    2012-04-01

    A novel ionisation source which uses commercially available Carbon Nano Tube devices is demonstrated as a replacement for a filament based ionisation source in an ion trap mass spectrometer. The carbon nanotube ion source electron emission was characterised and exhibited typical emission of 30 ± 1.7 μA with an applied voltage differential of 300 V between the carbon nanotube tips and the extraction grid. The ion source was tested for longevity and operated under a condition of continuous emission for a period of 44 h; there was an observed reduction in emission current of 26.5% during operation. Spectra were generated by installing the ion source into a Finnigan Mat ITD700 ion trap mass spectrometer; the spectra recorded showed all of the characteristic m/z peaks from m/z 69 to m/z 219. Perfluorotributylamine spectra were collected and averaged contiguously for a period of 48 h with no significant signal loss or peak mass allocation shift. The low power requirements and low mass of this novel ionisation source are considered be of great value to future space missions where mass spectrometric technology will be employed.

  11. Letter: characterisation and identification of spermine and spermidine derivatives in Microdesmis keayana and Microdesmis puberula roots by electrospray ionisation tandem mass spectrometry and high-performance liquid chromatography/electrospray ionisation tandem mass spectrometry.

    PubMed

    Roumy, Vincent; Hennebelle, Thierry; Zamblé, Alexis; Zamblé Yao, Jacques; Sahpaz, Sevser; Bailleul, François

    2008-01-01

    Three new N(1),N(5),N(14)-tris(4- hydroxycinnamoyl)spermines were identified in hydromethanolic root extracts of Microdesmis keayana J. Léonard and Microdesmis puberula Hook f. The electrospray ionisation tandem mass spectrometry (ESI-MS/MS) technique with specific nuclear magnetic resonance analysis of hydrolysed products made it possible to identify N(1),N(5),N(14)-tris(p-coumaroyl)spermine, N(1)-feruloyl,N(5),N(14)-di(p-coumaroyl)spermine and N(1),N(5),N(14)-tris(feruloyl)spermine, named keayanines B, C and D, respectively. ESI-MS/MS analysis most effectively provided structural data although high-performance liquid chromatography/electrospray ionisation tandem mass spectrometry was also used to characterise four other compounds from Microdesmis puberula-keayanidines A, B, C and keayanine A-which had already been identified in M. keayana. This chemical data is the first to be published for M. puberula which is a commonly used plant in Central African traditional medicine. PMID:18493101

  12. Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives: a review.

    PubMed

    Paine, Martin R L; Barker, Philip J; Blanksby, Stephen J

    2014-01-15

    The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis.

  13. HCO+ and N2H+ as ionisation tracers in the low-mass protostar IRAS16293-2422

    NASA Astrophysics Data System (ADS)

    Quénard, D.; Bottinelli, S.; Caux, E.

    2016-05-01

    Ionisation in the molecular environment of star-forming regions gives important clues on the chemical processes that take place in the environment of a young protostar. Ionisation can be traced with molecules like HCO+ and N2H+ and it regulates the formation of larger molecules such as complex organic molecules (COMs). The ionisation degree can also play an important role in the free-fall timescale of the protostar since it prevents the neutral material to collapse through collisions with ions and electrons bound to the magnetic field of the central protostar.

  14. On the determination of underivatised fatty alcohol ethoxylates by electrospray ionisation-mass spectrometry.

    PubMed

    Bernabé-Zafón, Virginia; Simó-Alfonso, Ernesto F; Ramis-Ramos, Guillermo

    2006-06-23

    The oligomers of fatty alcohol ethoxylates (FAEs) exhibit large sensitivity differences in mass spectrometry with electrospray ionisation (ESI-MS) and atmospheric pressure chemical ionization (APCI). Standards of the oligomers from m=1 to 7 ethylene oxide units (EOs) and linear alkyl chains from n=10 to 18 carbon atoms were infused to examine the relative sensitivities or response factors in several media. The response factors of the [M+H]+ and [M+Na]+ peaks in 9:1 acetonitrile/water and methanol/water media containing acid buffers increased following irregular patterns when n and m increased. In methanol/water the response factors depended on the parity of m, being larger than the average trend for the oligomers with an even value of m with respect to those having an odd value. This was attributed to the presence of an uncompensated C-O-C or C-O-H dipole in the former oligomers. The advantages of using ESI over APCI and of measuring the [M+H]+ peaks in an acid methanol/water medium containing 0.1 M HCl are discussed. The advantages and limitations of using models of the response factors to evaluate oligomer concentrations with a reduced set of selected standards are examined. The determination of underivatised FAEs using acid media was made compatible with previous HPLC separation by implementing either a triconcentric nebulizer fed with an acid liquid sheath, or a capillary T-union inserted between the column outlet and the biconcentric nebulizer, and fed with an acid stream provided by a syringe pump.

  15. A novel arsenical in clam kidney identified by liquid chromatography/electrospray ionisation mass spectrometry.

    PubMed

    Francesconi, K A; Edmonds, J S

    2001-01-01

    Kidneys of clams of the genus Tridacna accumulate metabolic products from symbiotic unicellular algae that grow in the mantles of the clams. These metabolites include organoarsenic compounds that are biosynthesised by algae from arsenate in seawater. The arsenic compounds in aqueous extracts of the kidney of the giant clam T. derasa were investigated by liquid chromatography/electrospray ionisation mass spectrometry. About 50% of the water-soluble arsenic was present as dimethylarsinoylribosides and dimethylarsinate which are common algal metabolites. The major compound in the kidney (50% of water-soluble arsenic) was identified as a 5-dimethylarsinoyl-2,3,4-trihydroxycarboxylic acid, a new natural product.

  16. Age determination of plutonium material in nuclear forensics by thermal ionisation mass spectrometry.

    PubMed

    Wallenius, M; Mayer, K

    2000-02-01

    Age is a key parameter when deducing the history of plutonium material, i.e. the plutonium produced in the nuclear reactors. This is of vital importance, when a smuggled plutonium sample has been seized and the origin has to be determined. A methodology is described which allows accurately to determine the age of plutonium material by thermal ionisation mass spectrometry using independent parent/daughter relations. This has been demonstrated for Reference Materials of known ages as well as for real samples. The already established method using gamma spectrometry is compared to this.

  17. High throughput volatile fatty acid skin metabolite profiling by thermal desorption secondary electrospray ionisation mass spectrometry.

    PubMed

    Martin, Helen J; Reynolds, James C; Riazanskaia, Svetlana; Thomas, C L Paul

    2014-09-01

    The non-invasive nature of volatile organic compound (VOC) sampling from skin makes this a priority in the development of new screening and diagnostic assays. Evaluation of recent literature highlights the tension between the analytical utility of ambient ionisation approaches for skin profiling and the practicality of undertaking larger campaigns (higher statistical power), or undertaking research in remote locations. This study describes how VOC may be sampled from skin and recovered from a polydimethylsilicone sampling coupon and analysed by thermal desorption (TD) interfaced to secondary electrospray ionisation (SESI) time-of-flight mass spectrometry (MS) for the high throughput screening of volatile fatty acids (VFAs) from human skin. Analysis times were reduced by 79% compared to gas chromatography-mass spectrometry methods (GC-MS) and limits of detection in the range 300 to 900 pg cm(-2) for VFA skin concentrations were obtained. Using body odour as a surrogate model for clinical testing 10 Filipino participants, 5 high and 5 low odour, were sampled in Manilla and the samples returned to the UK and screened by TD-SESI-MS and TD-GC-MS for malodour precursors with greater than >95% agreement between the two analytical techniques. Eight additional VFAs were also identified by both techniques with chains 4 to 15 carbons long being observed. TD-SESI-MS appears to have significant potential for the high throughput targeted screening of volatile biomarkers in human skin.

  18. Beer fingerprinting by Matrix-Assisted Laser Desorption-Ionisation-Time of Flight Mass Spectrometry.

    PubMed

    Šedo, Ondrej; Márová, Ivana; Zdráhal, Zbyněk

    2012-11-15

    A method allowing parallel fingerprinting of proteins and maltooligosaccharides directly from untreated beer samples is presented. These two classes of compounds were detected by Matrix-Assisted Laser Desorption-Ionisation-Time of Flight-Mass Spectrometry (MALDI-TOF-MS) analysis of beer mixed with 2,5-dihydroxybenzoic acid solution. The maltooligosaccharide profiles acquired from the MALDI sample spot center were not found characteristic for beers of different source and technology. On the other hand, according to profiles containing protein signals acquired from crystals formed on the border of the MALDI sample spot, we were able to distinguish beer samples of the same brand produced by different breweries. The discriminatory abilities of the method were further examined on a set of 17 lager beers, where the fingerprints containing protein signals enabled resolution of majority of examined brands. We propose MALDI-TOF-MS profiling as a rapid tool for beer brewing technology process monitoring, quality control, and determination of beer authenticity.

  19. Towards the integration of matrix assisted laser desorption ionisation mass spectrometry imaging into the current fingermark examination workflow.

    PubMed

    Bradshaw, Robert; Bleay, Stephen; Wolstenholme, Rosalind; Clench, Malcolm Ronald; Francese, Simona

    2013-10-10

    A wide range of fingermark enhancement techniques (FET) is currently employed to visualise latent fingermarks at crime scenes. However, if smudged, partial, distorted or absent in the National Fingerprint Database, crime scene marks may be not useful for identification purposes. In these circumstances, a technology enabling chemical imaging of both endogenous and exogenous species contained within the fingermark could provide additional and associative investigative information, to profile the suspect's activities prior to the crime. Matrix Assisted Laser Desorption Ionisation Mass Spectrometry Imaging (MALDI MSI) has proven to be such a technique, enabling investigative information to be gathered, for example, on what substances the donor has come in contact with and what they have ingested. Nonetheless, to be employed, MALDI MSI has to be validated and its compatibility with FET tested for integration into the standard fingermark examination workflow. For the first time, a direct comparison has been made between the efficiency of a range of FET and MALDI MSI under different conditions. This information will build towards validation of the technology. Also, for the first time, MALDI MSI has been successfully employed as a sequential step following fingermark enhancement using many of the currently employed FET. Additionally, known enhancers have been "re-visited" by combining them with a MALDI matrix, providing both improved fingermark development and chemical species detection via MALDI MSI. The result reported here are good indication in favour of the integration of MALDI MSI into the current fingermark examination workflow for gathering additional investigative information.

  20. Quantitative analysis of clenbuterol in meat products using liquid chromatography-electrospray ionisation tandem mass spectrometry.

    PubMed

    Guy, P A; Savoy, M C; Stadler, R H

    1999-12-24

    A method is presented that allows quantitation of clenbuterol in meat and liver products at the ng/kg level by liquid chromatography-electrospray ionisation tandem mass spectrometry (LC-ESIMS-MS) using a stable isotopically labeled internal standard. The practical procedure involves acid extraction followed by two solid-phase clean-up steps with C18 and strong cation-exchange (SCX) resins. The typical recovery of the analyte spiked at 0.4 microg/kg in meat and liver samples was at 63+/-7%. Mass spectral acquisition was done in multiple reaction monitoring (MRM) to provide a high degree of sensitivity, achieving a limit of detection and quantitation at 10 and 15 ng/kg, respectively. Two precursor ions at m/z 277 and 279, corresponding to the characteristic isotopic cluster of the two chlorine atoms of clenbuterol, were monitored by LC-ESIMS-MS to provide unambiguous identity of the analyte. Samples of meat and liver of various origins with either incurred residues or spiked with known amounts of clenbuterol were used to validate the method.

  1. Artificially-aged cachaça samples characterised by direct infusion electrospray ionisation mass spectrometry.

    PubMed

    de Souza, Patterson P; Resende, Ana M M; Augusti, Daniella V; Badotti, Fernanda; Gomes, Fátima de Cássia O; Catharino, Rodrigo R; Eberlin, Marcos N; Augusti, Rodinei

    2014-01-15

    Direct infusion electrospray ionisation mass spectrometry in the negative ion mode [ESI(-)-MS] was employed to evaluate the authenticity of aged cachaças, a traditional and valuable Brazilian alcoholic beverage prepared from the distillation of brewed sugarcane juice and aged in barrels made of common woods. Counterfeit samples were prepared by adding dyes, sawdust or essences to a freshly-distiled, much less valuable sample (white cachaça) to simulate the 1-2years long natural ageing in wooden barrels. A simple visual inspection revealed remarkable differences between the ESI(-)-MS of the authentic samples (aged in oak or amburana casks) and the artificially-aged counterfeit samples. A set of diagnostic ions were detectable in the ESI(-)-MS of the authentic samples aged in oak (m/z 197, 241, 301 and 307) and amburana (m/z 271 and 377/379). This fast and direct methodology seems useful as a routine procedure to monitor this highly profitable and common counterfeit practice. PMID:24054215

  2. Artificially-aged cachaça samples characterised by direct infusion electrospray ionisation mass spectrometry.

    PubMed

    de Souza, Patterson P; Resende, Ana M M; Augusti, Daniella V; Badotti, Fernanda; Gomes, Fátima de Cássia O; Catharino, Rodrigo R; Eberlin, Marcos N; Augusti, Rodinei

    2014-01-15

    Direct infusion electrospray ionisation mass spectrometry in the negative ion mode [ESI(-)-MS] was employed to evaluate the authenticity of aged cachaças, a traditional and valuable Brazilian alcoholic beverage prepared from the distillation of brewed sugarcane juice and aged in barrels made of common woods. Counterfeit samples were prepared by adding dyes, sawdust or essences to a freshly-distiled, much less valuable sample (white cachaça) to simulate the 1-2years long natural ageing in wooden barrels. A simple visual inspection revealed remarkable differences between the ESI(-)-MS of the authentic samples (aged in oak or amburana casks) and the artificially-aged counterfeit samples. A set of diagnostic ions were detectable in the ESI(-)-MS of the authentic samples aged in oak (m/z 197, 241, 301 and 307) and amburana (m/z 271 and 377/379). This fast and direct methodology seems useful as a routine procedure to monitor this highly profitable and common counterfeit practice.

  3. Nanostructured weathering steel for matrix-free laser desorption ionisation mass spectrometry and imaging of metabolites, drugs and complex glycans.

    PubMed

    Etxebarria, Juan; Calvo, Javier; Reichardt, Niels-Christian

    2014-06-01

    Weathering steel has been employed for the first time to prepare sample plates for matrix-free laser desorption ionisation mass spectrometry (LDI-MS) of small molecules up to a mass range of around 1500 Da. The effective UV absorption, heat conductivity and porosity of the nanostructured inner rust layer formed during passivation determine the excellent performance in LDI-MS for a broad range of different analyte classes. The inexpensive material was evaluated in a series of relevant analytical applications ranging from the matrix-free detection of serum metabolites, lactose quantification, lipid analysis in milk to the glycoprofiling of antibodies and imaging mass spectrometry of brain tissue samples. PMID:24737011

  4. Capillary electrophoresis with electrospray ionisation-mass spectrometry for the characterisation of degradation products in aged papers.

    PubMed

    Dupont, Anne-Laurence; Seemann, Agathe; Lavédrine, Bertrand

    2012-01-30

    A methodology for capillary electrophoresis/electrospray ionisation mass spectrometry (CE/ESI-MS) was developed for the simultaneous analysis of degradation products from paper among two families of compounds: low molar mass aliphatic organic acids, and aromatic (phenolic and furanic) compounds. The work comprises the optimisation of the CE separation and the ESI-MS parameters for improved sensitivity with model compounds using two successive designs of experiments. The method was applied to the analysis of lignocellulosic paper at different stages of accelerated hygrothermal ageing. The compounds of interest were identified. Most of them could be quantified and several additional analytes were separated.

  5. Laser ablation and ionisation by laser plasma radiation in the atmospheric-pressure mass spectrometry of organic compounds

    SciTech Connect

    Pento, A V; Nikiforov, S M; Simanovsky, Ya O; Grechnikov, A A; Alimpiev, S S

    2013-01-31

    A new method was developed for the mass spectrometric analysis of organic and bioorganic compounds, which involves laser ablation with the ionisation of its products by laser-plasma radiation and enables analysing gaseous, liquid, and solid substances at atmospheric pressure without sample preparation. The capabilities of this method were demonstrated by the examples of fast pharmaceutical composition screening, real-time atmosphere composition analysis, and construction of the mass spectrometric images of organic compound distributions in biological materials. (interaction of laser radiation with matter)

  6. Current status of matrix-assisted laser desorption ionisation-time of flight mass spectrometry in the clinical microbiology laboratory.

    PubMed

    Kok, Jen; Chen, Sharon C A; Dwyer, Dominic E; Iredell, Jonathan R

    2013-01-01

    The integration of matrix-assisted laser desorption ionisation-time of flight mass spectrometry (MALDI-TOF MS) into many clinical microbiology laboratories has revolutionised routine pathogen identification. MALDI-TOF MS complements and has good potential to replace existing phenotypic identification methods. Results are available in a more clinically relevant timeframe, particularly in bacteraemic septic shock. Novel applications include strain typing and the detection of antimicrobial resistance, but these are not widely used. This review discusses the technical aspects, current applications, and limitations of MALDI-TOF MS.

  7. Determination of alkyl benzyl and dialkyl dimethyl quaternary ammonium biocides in occupational hygiene and environmental media by liquid chromatography with electrospray ionisation mass spectrometry and tandem mass spectrometry.

    PubMed

    Ford, Michael J; Tetler, Lee W; White, John; Rimmer, Duncan

    2002-04-01

    A new method for the simultaneous qualitative and quantitative determination of alkyl benzyl and dialkyl quaternary ammonium compounds (QACs) has been developed. Analysis is by reversed-phase high-performance liquid chromatography coupled with electrospray ionisation mass spectrometry. QACs are extremely amenable to the electrospray ionisation technique (limit of detection of BAC C12 homologue 3 ng ml(-1)). The selectivity of mass spectrometric detection allows simultaneous determination of benzyl and dialkyl dimethyl ammonium compounds. The method was successfully applied to the analysis of real samples (occupational hygiene sampling devices, products and swimming pool water). Structural information was obtained by MS-MS and cone voltage ion dissociation techniques. Ion dissociation enabled the structural elucidation of an unknown quaternary ammonium compound present in a commercial formulation.

  8. Survey of Natural Cadmium Isotope Fractionation by Double Spike Thermal Ionisation Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Schmitt, A.; Galer, S. J.; Abouchami, W.

    2006-12-01

    Wombacher et al. (2003) have shown recently that natural Cd isotope fractionations in terrestrial materials are extremely limited (~100 ppm/amu or less). Thus, excellent external precision is absolutely paramount if Cd isotope fractionations are to be adequately quantified. Here we present a new high-precision double spike (DS) technique for Cd isotopes in which the Cd is measured by thermal ionisation mass spectrometry (TIMS, ThermoElectron Triton), which draws on the pioneering work of Rosman et al. (1980). We observe pronounced anomalous odd-even isotope mass bias during TIMS measurement of Cd with silica gel activator, and avoid such effects by utilizing even isotopes of Cd only. The double spike and its composition were carefully optimized (cf. Galer, 1999), and the "natural" Cd isotope fractionation is expressed as the relative deviations in ^{112}Cd/^{110}Cd (in parts per 104) from our JMC Cd shelf standard. The external reproducibility for 100 ng loads of double-spiked JMC Cd shelf is ± 0.14 ɛ^{112/110}Cd (2SD, N=57) -- i.e. ±7 ppm/amu -- which is a factor of 4 to 10 times better than that reported in published studies using MC-ICP-MS techniques (e.g. Wombacher et al., 2003; Cloquet et al., 2005). The DS-TIMS method offers further benefits in terms of superior sensitivity, while Cd abundances are obtained as a biproduct by isotope dilution. We have analyzed ɛ^{112/110}Cd in over sixty samples from different terrestrial reservoirs and environments in order to delimit the extent of natural isotope fractionation of Cd. Most samples were duplicated or triplicated. To facilitate inter-lab comparison, our measured ɛ^{112/110}Cd for the standards "Münster Cd" and BAM-1012 averaged +21.46 and -7.42, respectively. On the whole, our study confirms the conclusions of Wombacher et al. (2003) that Cd isotope variations in terrestrial materials are limited -- nearly all samples fall within the range -1.0 to +1.0 in ɛ^{112/110}Cd. Nevertheless, we are able for the

  9. Surface analysis using a new plasma assisted desorption/ionisation source for mass spectrometry in ambient air

    NASA Astrophysics Data System (ADS)

    Bowfield, A.; Barrett, D. A.; Alexander, M. R.; Ortori, C. A.; Rutten, F. M.; Salter, T. L.; Gilmore, I. S.; Bradley, J. W.

    2012-06-01

    The authors report on a modified micro-plasma assisted desorption/ionisation (PADI) device which creates plasma through the breakdown of ambient air rather than utilising an independent noble gas flow. This new micro-PADI device is used as an ion source for ambient mass spectrometry to analyse species released from the surfaces of polytetrafluoroethylene, and generic ibuprofen and paracetamol tablets through remote activation of the surface by the plasma. The mass spectra from these surfaces compare favourably to those produced by a PADI device constructed using an earlier design and confirm that the new ion source is an effective device which can be used to achieve ambient mass spectrometry with improved spatial resolution.

  10. Matrix-assisted laser desorption/ionisation mass spectrometry imaging and its development for plant protein imaging

    PubMed Central

    2011-01-01

    Matrix-Assisted Laser Desorption/Ionisation (MALDI) mass spectrometry imaging (MSI) uses the power of high mass resolution time of flight (ToF) mass spectrometry coupled to the raster of lasers shots across the cut surface of tissues to provide new insights into the spatial distribution of biomolecules within biological tissues. The history of this technique in animals and plants is considered and the potential for analysis of proteins by this technique in plants is discussed. Protein biomarker identification from MALDI-MSI is a challenge and a number of different approaches to address this bottleneck are discussed. The technical considerations needed for MALDI-MSI are reviewed and these are presented alongside examples from our own work and a protocol for MALDI-MSI of proteins in plant samples. PMID:21726462

  11. Solvent Separating Secondary Metabolites Directly from Biosynthetic Tissue for Surface-Assisted Laser Desorption Ionisation Mass Spectrometry

    PubMed Central

    Rudd, David; Benkendorff, Kirsten; Voelcker, Nicolas H.

    2015-01-01

    Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry (MS) methods namely nanostructure-assisted laser desorption ionisation (NALDI) and desorption ionisation on porous silicon (DIOS) surfaces have been developed to enable the direct detection of low molecular weight metabolites. Since direct tissue NALDI-MS or DIOS-MS produce complex spectra due to the wide variety of other metabolites and fragments present in the low mass range, we report here the use of “on surface” solvent separation directly from mollusc tissue onto nanostructured surfaces for MS analysis, as a mechanism for simplifying data annotation and detecting possible artefacts from compound delocalization during the preparative steps. Water, ethanol, chloroform and hexane selectively extracted a range of choline esters, brominated indoles and lipids from Dicathais orbita hypobranchial tissue imprints. These compounds could be quantified on the nanostructured surfaces by comparison to standard curves generated from the pure compounds. Surface-assisted MS could have broad utility for detecting a broad range of secondary metabolites in complex marine tissue samples. PMID:25786067

  12. Mass Transfer with Chemical Reaction.

    ERIC Educational Resources Information Center

    DeCoursey, W. J.

    1987-01-01

    Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

  13. Optimisation of the quantitative determination of chlormequat by matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Horak, J; Werther, W; Schmid, E R

    2001-01-01

    The plant growth regulator chlormequat, an involatile quaternary ammonium salt, has been quantified by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). Restrictions for quantitative MALDI-TOFMS analysis, such as irreproducible crystallisation and unsatisfactory laser stability, have been overcome by the application of two synthesised isotopically labelled standards and the optimisation of the measurement protocol. Data acquisition at constant laser power was compared to data acquisition at approximately constant ion abundance of the relevant ions (analyte and internal standards). Data acquisition at constant ion abundance performed better and enabled a high number of consecutive firings to the same sample deposition area. Furthermore an increased sample-to-sample repeatability and a high reproducibility over several weeks without re-calibration have been attained by this method. Linearity over three orders of magnitude (0.05 to 30 ng/microL chlormequat), with a correlation coefficient of 0.9997, was achieved using [13C3]-chlormequat as internal standard. Limit of detection and limit of determination were determined to be in the low pg/microL range for pure standard solutions. Thin-layer chromatography was applied for the removal of high amounts of choline, which is often present in plant tissue extracts and can adversely affect the ionisation and detection of chlormequat by MALDI-TOFMS. The use of two internal standards ([13C3]- and [2H9]-chlormequat) enabled direct quantification and simultaneous control of the recovery. PMID:11223954

  14. Determination of potato glycoalkaloids using high-pressure liquid chromatography-electrospray ionisation/mass spectrometry.

    PubMed

    Matsuda, Fumio; Morino, Keiko; Miyazawa, Haruna; Miyashita, Masahiro; Miyagawa, Hisashi

    2004-01-01

    A method for quantifying two toxic glycoalkaloids, alpha-solanine and alpha-chaconine, in potato (Solanum tuberosum) tuber tissue was developed using HPLC-electrospray ionisation (ESI)/MS. Potato samples were extracted with 5% aqueous acetic acid, and the extracts were subjected directly to HPLC-ESI/MS after filtration. By determining the intensities of the protonated molecules of alpha-solanine (m/z 868) and alpha-chaconine (m/z 852) using selected ion monitoring (positive ion mode), a sensitive assay was attained with detection limits of 38 and 14 ppb for the two glycoalkaloids, respectively. The high sensitivity and selectivity of MS detection effectively reduced the time of analysis thus enabling a high throughput assay of glycoalkaloids in potato tubers.

  15. Real-time analysis of organic compounds in ship engine aerosol emissions using resonance-enhanced multiphoton ionisation and proton transfer mass spectrometry.

    PubMed

    Radischat, Christian; Sippula, Olli; Stengel, Benjamin; Klingbeil, Sophie; Sklorz, Martin; Rabe, Rom; Streibel, Thorsten; Harndorf, Horst; Zimmermann, Ralf

    2015-08-01

    Organic combustion aerosols from a marine medium-speed diesel engine, capable to run on distillate (diesel fuel) and residual fuels (heavy fuel oil), were investigated under various operating conditions and engine parameters. The online chemical characterisation of the organic components was conducted using a resonance-enhanced multiphoton ionisation time-of-flight mass spectrometer (REMPI TOF MS) and a proton transfer reaction-quadrupole mass spectrometer (PTR-QMS). Oxygenated species, alkenes and aromatic hydrocarbons were characterised. Especially the aromatic hydrocarbons and their alkylated derivatives were very prominent in the exhaust of both fuels. Emission factors of known health-hazardous compounds (e.g. mono- and poly-aromatic hydrocarbons) were calculated and found in higher amounts for heavy fuel oil (HFO) at typical engine loadings. Lower engine loads lead in general to increasing emissions for both fuels for almost every compound, e.g. naphthalene emissions varied for diesel fuel exhaust between 0.7 mg/kWh (75 % engine load, late start of injection (SOI)) and 11.8 mg/kWh (10 % engine load, late SOI) and for HFO exhaust between 3.3 and 60.5 mg/kWh, respectively. Both used mass spectrometric techniques showed that they are particularly suitable methods for online monitoring of combustion compounds and very helpful for the characterisation of health-relevant substances. Graphical abstract Three-dimensional REMPI data of organic species in diesel fuel and heavy fuel oil exhaust.

  16. Fragmentation of mycosporine-like amino acids by hydrogen/deuterium exchange and electrospray ionisation tandem mass spectrometry.

    PubMed

    Cardozo, Karina H M; Carvalho, Valdemir M; Pinto, Ernani; Colepicolo, Pio

    2006-01-01

    The determination and identification of mycosporine-like amino acids (MAAs) from algae remain a major challenge due to the low concentration. Mass spectrometry (MS) can make an invaluable contribution in the search and identification of MAAs because of its high sensitivity, possibility of coupling with liquid chromatography, and the availability of powerful tandem mass spectrometric techniques. However, the unequivocal determination of the presence and location of important functional groups present on the basic skeleton of the MAAs is often elusive due to their inherent instability under MS conditions. In this study, the use of hydrogen/deuterium (H/D) exchange and electrospray ionisation tandem mass spectrometry (ESI-MS/MS) for characterisation of four MAAs (palythine, asterina, palythinol and shinorine) isolated from the macroalgae Gracilaria tenuistipitata Chang et Xia was investigated. The accurate-mass confirmation of the protonated molecules was performed on a Q-TOF instrument. We demonstrate that employing deuterium labelling in ESI-MS/MS analysis provides a convenient tool for the determination of new MAAs. Although the fragmentation patterns of MAAs were discussed earlier, to our knowledge, this is the first time that mechanisms are proposed.

  17. Detection of drugs in lifted cyanoacrylate-developed latent fingermarks using two laser desorption/ionisation mass spectrometric methods.

    PubMed

    Sundar, Latha; Rowell, Frederick

    2014-02-01

    This paper describes a method for lifting cyanoacrylate (CNA)-developed latent fingermarks from a glass surface and the detection of five drugs in lifted marks from fingers that had been in contact with the drugs, using Surface Assisted Laser Desorption Ionisation Time of Flight Mass Spectrometry (SALDI-TOF-MS) or Matrix Assisted Laser Desorption Ionisation TOF-MS (MALDI-TOF-MS). Two drugs of abuse (cocaine and methadone) and three therapeutic drugs (aspirin, paracetamol and caffeine) were used as contact residues. Latent fingermarks spiked with the drugs were subjected to CNA fuming followed by dusting with ARRO SupraNano™ MS black magnetic powder (SALDI-TOF-MS) or 2,5-dihydroxybenzoic acid (DHB) (MALDI-TOF-MS). The dusted mark was then exposed to solvent vapour before lifting with a commercial fingerprint lifting tape following established procedures. The presence of the drugs was then confirmed by direct analysis on the tape without further processing using SALDI- or MALDI-TOF-MS. The black magnetic fingerprint powder provided visual enhancement of the CNA-fingermark while no visual enhancement was observed for marks dusted with DHB powder. Similar [M + H](+) peaks for all the drug analytes were observed for both methods along with some sodium and potassium adducts for SALDI-MS and some major fragment ions but the SALDI signals were generally more intense. Simple exposure to acetone vapour of the CNA-developed marks enabled their effective transfer onto the tape which was crucial for subsequent MS detection of the analytes.

  18. Rapid assignment of malting barley varieties by matrix-assisted laser desorption-ionisation - Time-of-flight mass spectrometry.

    PubMed

    Šedo, Ondrej; Kořán, Michal; Jakešová, Michaela; Mikulíková, Renata; Boháč, Michal; Zdráhal, Zbyněk

    2016-09-01

    A method for discriminating malting barley varieties based on direct matrix-assisted laser desorption-ionisation - time-of-flight mass spectrometry (MALDI-TOF MS) fingerprinting of proteins was developed. Signals corresponding to hordeins were obtained by simple mixing of powdered barley grain with a MALDI matrix solution containing 12.5mgmL(-1) of ferulic acid in an acetonitrile:water:formic acid 50:33:17 v/v/v mixture. Compared to previous attempts at MALDI-TOF mass spectrometric analysis of barley proteins, the extraction and fractionation steps were practically omitted, resulting in a significant reduction in analytical time and costs. The discriminatory power was examined on twenty malting barley varieties and the practicability of the method was tested on sixty barley samples acquired from Pilsner Urquell Brewery. The method is proposed as a rapid tool for variety assignment and purity determination of malting barley that may replace gel electrophoresis currently used for this purpose. PMID:27041307

  19. Characterisation of a proposed internet synthesis of N,N-dimethyltryptamine using liquid chromatography/electrospray ionisation tandem mass spectrometry.

    PubMed

    Martins, Cláudia P B; Freeman, Sally; Alder, John F; Brandt, Simon D

    2009-08-14

    The psychoactive properties of N,N-dimethyltryptamine (DMT) are known to induce altered states of consciousness in humans. These properties attract great interest from clinical, neuroscientific, clandestine and forensic communities. The Breath of Hope Synthesis was reported on an internet website as a convenient two-step methodology for the preparation of DMT. The analytical characterisation of the first stage was the subject of previous publications by the authors and involved the thermal decarboxylation of tryptophan and the formation of tryptamine. The present study reports on the characterisation of the second step of this procedure which was based on the methylation of tryptamine. This employed methyl iodide and benzyltriethylammonium chloride/sodium hydroxide as a phase transfer catalyst. The reaction product was characterised by liquid chromatography/electrospray ionisation tandem mass spectrometry and orthogonal acceleration time-of-flight mass spectrometry. Quantitative evaluation was carried out in positive multiple reaction monitoring mode (MRM), which included synthesis of the identified reaction products. MRM screening of the product did not lead to the detection of DMT. Instead, 11.1% tryptamine starting material, 21.0% N,N,N-trimethyltryptammonium iodide (TMT) and 47.4% 1-N-methyl-TMT were detected. A 0.5% trace of the monomethylated N-methyltryptamine was also detected. This study demonstrated the impact on product purity of doubtful synthetic methodologies discussed on the internet. PMID:19592003

  20. High-performance liquid chromatographic separation of natural and synthetic desulphoglucosinolates and their chemical validation by UV, NMR and chemical ionisation-MS methods.

    PubMed

    Kiddle, G; Bennett, R N; Botting, N P; Davidson, N E; Robertson, A A; Wallsgrove, R M

    2001-01-01

    Methods are described for the optimised extraction, desulphation and HPLC separation of desulphoglucosinolates. These methods provide rapid separation, identification and quantitative measurements of glucosinolates extracted from Brassica napus L and related crops, of unusual glucosinolates found in crucifer weed species, and also of synthetic alkylglucosinolates. The desulphoglucosinolates used in these studies were either chemically synthesised (at least one example from each major structural class), or purified from various plant sources. Validation of the identities of the desulphoglucosinolates was by comparison of retention times with standards, and by UV, 1H- and 13C-NMR and chemical ionisation MS analysis. A list of useful species, and the specific tissues, from which high concentrations of standards can be extracted is included. PMID:11705329

  1. Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

    PubMed

    Warren, Alexander D; Conway, Ulric; Arthur, Christopher J; Gates, Paul J

    2016-07-01

    The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd.

  2. Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

    PubMed

    Warren, Alexander D; Conway, Ulric; Arthur, Christopher J; Gates, Paul J

    2016-07-01

    The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27434807

  3. A new approach for plasma (xeno)metabolomics based on solid-phase extraction and nanoflow liquid chromatography-nanoelectrospray ionisation mass spectrometry.

    PubMed

    David, Arthur; Abdul-Sada, Alaa; Lange, Anke; Tyler, Charles R; Hill, Elizabeth M

    2014-10-24

    Current metabolite profiling methods based on liquid chromatography-mass spectrometry (LC-MS) platforms do not detect many of the components present at trace concentrations in extracts of plasma due to their low ionisation efficiency or to interference from highly abundant compounds. Nanoflow LC-nanospray MS platforms, which are commonly used in proteomics, could overcome these limitations and significantly increase analytical sensitivity and coverage of the plasma (xeno)metabolome (i.e., metabolites and xenobiotics), but require small injection volumes (<0.5μL). In this study, we developed sample preparation methods to remove ion suppressive phospholipids and concentrate remaining components of the plasma (xeno)metabolome in order to analyse sub-microliter volumes of plasma extracts for nanoflow ultra-high-performance liquid chromatography-nanoelectrospray ionisation-time-of-flight mass spectrometry (nUHPLC-nESI-TOFMS). These methods use phospholipid filtration plates in combination with polymeric or mixed mode exchange solid-phase extraction (SPE). The phospholipid filtration plates removed >94% of the predominant phospholipid/lysophospholipid species from plasma, whilst absolute recoveries of 63 selected (xeno)metabolites from spiked plasma were generally between 60 and 104%. After a further SPE step, recoveries of test compounds were between 50 and 81%. Studies revealed that both the sample preparation methodology and nUHPLC-nESI-TOFMS analyses gave acceptable repeatability. A qualitative comparison of SPE methods revealed that sample concentration by either polymer or mixed mode ion-exchange SPE gave comprehensive metabolite coverage of plasma extracts, but the use of cation exchange SPE significantly increased detection of many cationic compounds in the sample extracts. Method detection limits for steroid, eicosanoid and bile metabolites were <1.0ng/mL plasma and for pharmaceutical contaminants were between 0.01 and 30ng/mL plasma. Comparison of the

  4. A new approach for plasma (xeno)metabolomics based on solid-phase extraction and nanoflow liquid chromatography-nanoelectrospray ionisation mass spectrometry.

    PubMed

    David, Arthur; Abdul-Sada, Alaa; Lange, Anke; Tyler, Charles R; Hill, Elizabeth M

    2014-10-24

    Current metabolite profiling methods based on liquid chromatography-mass spectrometry (LC-MS) platforms do not detect many of the components present at trace concentrations in extracts of plasma due to their low ionisation efficiency or to interference from highly abundant compounds. Nanoflow LC-nanospray MS platforms, which are commonly used in proteomics, could overcome these limitations and significantly increase analytical sensitivity and coverage of the plasma (xeno)metabolome (i.e., metabolites and xenobiotics), but require small injection volumes (<0.5μL). In this study, we developed sample preparation methods to remove ion suppressive phospholipids and concentrate remaining components of the plasma (xeno)metabolome in order to analyse sub-microliter volumes of plasma extracts for nanoflow ultra-high-performance liquid chromatography-nanoelectrospray ionisation-time-of-flight mass spectrometry (nUHPLC-nESI-TOFMS). These methods use phospholipid filtration plates in combination with polymeric or mixed mode exchange solid-phase extraction (SPE). The phospholipid filtration plates removed >94% of the predominant phospholipid/lysophospholipid species from plasma, whilst absolute recoveries of 63 selected (xeno)metabolites from spiked plasma were generally between 60 and 104%. After a further SPE step, recoveries of test compounds were between 50 and 81%. Studies revealed that both the sample preparation methodology and nUHPLC-nESI-TOFMS analyses gave acceptable repeatability. A qualitative comparison of SPE methods revealed that sample concentration by either polymer or mixed mode ion-exchange SPE gave comprehensive metabolite coverage of plasma extracts, but the use of cation exchange SPE significantly increased detection of many cationic compounds in the sample extracts. Method detection limits for steroid, eicosanoid and bile metabolites were <1.0ng/mL plasma and for pharmaceutical contaminants were between 0.01 and 30ng/mL plasma. Comparison of the

  5. Analysis of organophosphate flame retardants and plasticisers in water by isotope dilution gas chromatography-electron ionisation tandem mass spectrometry.

    PubMed

    Teo, Tiffany L L; McDonald, James A; Coleman, Heather M; Khan, Stuart J

    2015-10-01

    The widespread use of organophosphate flame retardants (PFRs) in commercial products have led to their increased presence in the environment. In this study, a rapid and reliable analytical method was developed for the analysis of five PFRs in water using gas chromatography tandem mass spectrometry (GC-MS/MS) with electron ionisation (EI) and a run time of 13 min. The PFRs investigated were tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP) and triphenyl phosphate (TPP). Solid phase extraction (SPE) was undertaken to extract and concentrate target analytes from aqueous matrices. All water samples were extracted from a volume of 500 mL. Isotopically labelled compounds were used to account for analytical variability and for accurate quantification by isotope dilution. Method recoveries for all compounds were above 80% in all tested water samples. Method detection limits for all target analytes ranged from 0.3 to 24 ng/L in ultrapure water, tap water, seawater, surface water, secondary effluent and swimming pool water. Validation of this method confirmed satisfactory method stability with less than 1% coefficients of variation, verifying that this approach produced good reproducibility. PMID:26078137

  6. Neutral and acidic products derived from hydroxyl radical-induced oxidation of arabinotriose assessed by electrospray ionisation mass spectrometry.

    PubMed

    Moreira, Ana S P; da Costa, Elisabete V; Evtuguin, Dmitry V; Coimbra, Manuel A; Nunes, Fernando M; Domingues, M Rosário M

    2014-04-01

    The oxidation of α-(1 → 5)-L-arabinotriose (Ara3), an oligosaccharide structurally related to side chains of coffee arabinogalactans, was studied in reaction with hydroxyl radicals generated under conditions of Fenton reaction (Fe(2+)/H2O2). The acidic and neutral oxidation products were separated by ligand exchange/size-exclusion chromatography, subsequently identified by electrospray ionisation mass spectrometry (ESI-MS) and structurally characterised by tandem MS (ESI-MS/MS). In acidic fraction were identified several oxidation products containing an acidic residue at the corresponding reducing end of Ara3, namely arabinonic acid, and erythronic, glyceric and glycolic acids formed by oxidative scission of the furanose ring. In neutral fractions were identified derivatives containing keto, hydroxy and hydroperoxy moieties, as well as derivatives resulting from the ring scission at the reducing end of Ara3. In both acidic and neutral fractions, beyond the trisaccharide derivatives, the corresponding di- and monosaccharide derivatives were identified indicating the occurrence of oxidative depolymerisation. The structural characterisation of these oxidation products by ESI-MS/MS allowed the differentiation of isobaric and isomeric species of acidic and neutral character. The species identified in this study may help in detection of roasting products associated with the free radical-mediated oxidation of coffee arabinogalactans.

  7. A simple protocol for combinatorial cyclic depsipeptide libraries sequencing by matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Gurevich-Messina, Juan M; Giudicessi, Silvana L; Martínez-Ceron, María C; Acosta, Gerardo; Erra-Balsells, Rosa; Cascone, Osvaldo; Albericio, Fernando; Camperi, Silvia A

    2015-01-01

    Short cyclic peptides have a great interest in therapeutic, diagnostic and affinity chromatography applications. The screening of 'one-bead-one-peptide' combinatorial libraries combined with mass spectrometry (MS) is an excellent tool to find peptides with affinity for any target protein. The fragmentation patterns of cyclic peptides are quite more complex than those of their linear counterparts, and the elucidation of the resulting tandem mass spectra is rather more difficult. Here, we propose a simple protocol for combinatorial cyclic libraries synthesis and ring opening before MS analysis. In this strategy, 4-hydroxymethylbenzoic acid, which forms a benzyl ester with the first amino acid, was used as the linker. A glycolamidic ester group was incorporated after the combinatorial positions by adding glycolic acid. The library synthesis protocol consisted in the following: (i) incorporation of Fmoc-Asp[2-phenylisopropyl (OPp)]-OH to Ala-Gly-oxymethylbenzamide-ChemMatrix, (ii) synthesis of the combinatorial library, (iii) assembly of a glycolic acid, (iv) couple of an Ala residue in the N-terminal, (v) removal of OPp, (vi) peptide cyclisation through side chain Asp and N-Ala amino terminus and (vii) removal of side chain protecting groups. In order to simultaneously open the ring and release each peptide, benzyl and glycolamidic esters were cleaved with ammonia. Peptide sequences could be deduced from the tandem mass spectra of each single bead evaluated. The strategy herein proposed is suitable for the preparation of one-bead-one-cyclic depsipeptide libraries that can be easily open for its sequencing by matrix-assisted laser desorption/ionisation MS. It employs techniques and reagents frequently used in a broad range of laboratories without special expertise in organic synthesis.

  8. Mass-sensitive chemical preconcentrator

    DOEpatents

    Manginell, Ronald P.; Adkins, Douglas R.; Lewis, Patrick R.

    2007-01-30

    A microfabricated mass-sensitive chemical preconcentrator actively measures the mass of a sample on an acoustic microbalance during the collection process. The microbalance comprises a chemically sensitive interface for collecting the sample thereon and an acoustic-based physical transducer that provides an electrical output that is proportional to the mass of the collected sample. The acoustic microbalance preferably comprises a pivot plate resonator. A resistive heating element can be disposed on the chemically sensitive interface to rapidly heat and release the collected sample for further analysis. Therefore, the mass-sensitive chemical preconcentrator can optimize the sample collection time prior to release to enable the rapid and accurate analysis of analytes by a microanalytical system.

  9. Analysis of triacetone triperoxide complexes with alkali metal ions by electrospray and extractive electrospray ionisation combined with ion mobility spectrometry and mass spectrometry.

    PubMed

    Hill, Alex R; Edgar, Mark; Chatzigeorgiou, Maria; Reynolds, James C; Kelly, Paul F; Creaser, Colin S

    2015-01-01

    The complexation of triacetone triperoxide (TATP) with a range of alkali metals has been studied by electrospray ionisation-mass spectrometry yield [M+Cat](+) ions for all of the alkali metals. The formation of [2TATP+Li+LiX](+) (X = Br, Cl) sandwich complexes was also observed. Collision cross- sections for the lithium-containing complexes of TATP were measured by travelling wave ion mobility spectrometry mass spectrometry, and compared well with computationally determined structures. Extractive electrospray ionisation (EESI) using a lithium doped electrospray is demonstrated for the detection of TATP vapours desorbed from a metal surface. The limit of detection for EESI was shown to be 20 ng using the [TATP+Li](+) ion. PMID:26307706

  10. Identification of Tsetse (Glossina spp.) Using Matrix-Assisted Laser Desorption/Ionisation Time of Flight Mass Spectrometry

    PubMed Central

    Hoppenheit, Antje; Murugaiyan, Jayaseelan; Bauer, Burkhard; Steuber, Stephan; Clausen, Peter-Henning; Roesler, Uwe

    2013-01-01

    Glossina (G.) spp. (Diptera: Glossinidae), known as tsetse flies, are vectors of African trypanosomes that cause sleeping sickness in humans and nagana in domestic livestock. Knowledge on tsetse distribution and accurate species identification help identify potential vector intervention sites. Morphological species identification of tsetse is challenging and sometimes not accurate. The matrix-assisted laser desorption/ionisation time of flight mass spectrometry (MALDI TOF MS) technique, already standardised for microbial identification, could become a standard method for tsetse fly diagnostics. Therefore, a unique spectra reference database was created for five lab-reared species of riverine-, savannah- and forest- type tsetse flies and incorporated with the commercial Biotyper 3.0 database. The standard formic acid/acetonitrile extraction of male and female whole insects and their body parts (head, thorax, abdomen, wings and legs) was used to obtain the flies' proteins. The computed composite correlation index and cluster analysis revealed the suitability of any tsetse body part for a rapid taxonomical identification. Phyloproteomic analysis revealed that the peak patterns of G. brevipalpis differed greatly from the other tsetse. This outcome was comparable to previous theories that they might be considered as a sister group to other tsetse spp. Freshly extracted samples were found to be matched at the species level. However, sex differentiation proved to be less reliable. Similarly processed samples of the common house fly Musca domestica (Diptera: Muscidae; strain: Lei) did not yield any match with the tsetse reference database. The inclusion of additional strains of morphologically defined wild caught flies of known origin and the availability of large-scale mass spectrometry data could facilitate rapid tsetse species identification in the future. PMID:23875040

  11. Oxidation of amylose and amylopectin by hydroxyl radicals assessed by electrospray ionisation mass spectrometry.

    PubMed

    Simões, Joana; Moreira, Ana S P; da Costa, Elisabete; Evtyugin, Dmitry; Domingues, Pedro; Nunes, Fernando M; Coimbra, Manuel A; Domingues, M Rosário M

    2016-09-01

    The hydroxyl radicals (HO) are one of the most reactive oxygen species (ROS) involved in the oxidative damage of biological molecules, including carbohydrates. During the industrial processing of food, ROS can be formed. In order to identify the structural changes induced in starch by oxidation, amylose, amylopectin, and maltotriose, an oligosaccharide structurally related to these polysaccharides, were subjected to oxidation with HO generated under Fenton reaction conditions (Fe(2+)/H2O2). The oxidised polysaccharides were hydrolysed by α-amylase and the obtained oligosaccharides were fractionated by ligand-exchange/size-exclusion chromatography. Both acidic and neutral α-amylase resistant oligosaccharides were characterized by mass spectrometry. In oxidised neutral products, new keto, hydroxyl, and hydroperoxy moieties, and oxidative ring scission were observed at the reducing end of the oligosaccharides. The acid sugar residues occurred at the reducing end and included gluconic and glucuronic acid derivatives, and acids formed by oxidative ring scission, namely, arabinonic, erythronic, glyceric and glycolic acids.

  12. Determination and separation of bisphenol A, phthalate metabolites and structural isomers of parabens in human urine with conventional high-pressure liquid chromatography combined with electrospray ionisation tandem mass spectrometry.

    PubMed

    Myridakis, Antonis; Balaska, Eirini; Gkaitatzi, Christina; Kouvarakis, Antonis; Stephanou, Euripides G

    2015-03-01

    Phthalates, bisphenol A (BPA) and parabens (PBs), organic chemicals widely used in everyday products, are considered to be endocrine disruptors. We propose a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of seven phthalate metabolites, six PBs and BPA in human urine. All three categories of the above endocrine disruptors were simultaneously extracted from 1 mL of human urine using solid phase extraction. In addition, with a conventional reversed phase LC column, we achieved for the first time the separation of three pairs of structural isomers, namely iso-/n-butyl paraben, propyl paraben and monobutyl phthalate. LC-MS/MS was operated and tested in both electrospray ionisation (ESI) and atmospheric pressure chemical ionisation (APCI). ESI was selected for the analysis due to its superior stability and repeatability. The method limit of detection (mLOD), achieved for a single set of high-performance LC conditions, ranged from 0.01 to 0.84 ng/mL for phthalate metabolites, from 0.06 to 0.24 ng/mL for PBs and was 2.01 ng/mL for BPA. Derivatisation of BPA with dansyl chloride lowered its mLOD to 0.007 ng/mL. Blank contamination was non-detectable. The present method was successfully applied for the analysis of the above-mentioned compounds in 80 male human urine samples.

  13. Formation of aluminium, aluminium nitride and nitrogen clusters via laser ablation of nano aluminium nitride. Laser Desorption Ionisation and Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry.

    PubMed

    Panyala, Nagender Reddy; Prysiazhnyi, Vadym; Slavíček, Pavel; Černák, Mirko; Havel, Josef

    2011-06-30

    Laser Desorption Ionisation (LDI) and Matrix-Assisted Laser Desorption Ionisation (MALDI) Time-of-Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Al(m)(+) (m=1-3), N(n)(+) (n=4, 5), AlN(n)(+) (n=1-5, 19, 21), Al(m)N(+) (m=2-3), Al(3)N(2)(+), Al(9)N(n)(+) (n=5, 7, 9, 11 and 15), Al(11)N(n)(+) (n=4, 6, 10, 12, 19, 21, 23, and 25), and Al(13)N(n)(+) (n=25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Al(m)(-) (m=1-3), AlN(n)(-) (n=1-3, 5), Al(m)N(-) (n=2, 3), Al(2)N(n)(-) (n=2-4, 28, 30), N(n)(-) (n=2, 3), Al(4)N(7)(-) Al(8)N(n)(-) (n=1-6), and Al(13)N(n)(-) (n=9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al(10) N(10) cluster was shown to be of low abundance. On the contrary, the laser ablation of nano-AlN led mainly to the formation of nitrogen-rich Al(m)N(n) clusters in both negative and positive ion mode. The stoichiometry of the Al(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling. PMID:21598328

  14. Formation of aluminium, aluminium nitride and nitrogen clusters via laser ablation of nano aluminium nitride. Laser Desorption Ionisation and Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry.

    PubMed

    Panyala, Nagender Reddy; Prysiazhnyi, Vadym; Slavíček, Pavel; Černák, Mirko; Havel, Josef

    2011-06-30

    Laser Desorption Ionisation (LDI) and Matrix-Assisted Laser Desorption Ionisation (MALDI) Time-of-Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Al(m)(+) (m=1-3), N(n)(+) (n=4, 5), AlN(n)(+) (n=1-5, 19, 21), Al(m)N(+) (m=2-3), Al(3)N(2)(+), Al(9)N(n)(+) (n=5, 7, 9, 11 and 15), Al(11)N(n)(+) (n=4, 6, 10, 12, 19, 21, 23, and 25), and Al(13)N(n)(+) (n=25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Al(m)(-) (m=1-3), AlN(n)(-) (n=1-3, 5), Al(m)N(-) (n=2, 3), Al(2)N(n)(-) (n=2-4, 28, 30), N(n)(-) (n=2, 3), Al(4)N(7)(-) Al(8)N(n)(-) (n=1-6), and Al(13)N(n)(-) (n=9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al(10) N(10) cluster was shown to be of low abundance. On the contrary, the laser ablation of nano-AlN led mainly to the formation of nitrogen-rich Al(m)N(n) clusters in both negative and positive ion mode. The stoichiometry of the Al(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling.

  15. A miniaturised electron ionisation time-of-flight mass spectrometer that uses a unique helium ion removal pulsing technique specifically for gas analysis.

    PubMed

    Qing, Jiang; Huang, Zhengxu; Zhang, Yan; Zhu, Hui; Tan, Guobin; Gao, Wei; Yang, Peng-yuan

    2013-06-21

    A miniaturised reflectron time-of-flight mass spectrometer combined with an electron ionisation ion source has been developed for the analysis of gases. An entirely new helium ion removal pulsing technique in this mass spectrometer is used to achieve an improved performance for the first time. The helium carrier gas, which enters into the source along with the gaseous sample, is simultaneously ionised and then orthogonally introduced into the time-of-fight mass analyser. Once the relatively light helium ions in the ion packet become extremely close to the reflectron plate (B-plate for short in this article), a modulated pulse is instantaneously applied on the B-plate and a negative reflectron voltage is set to the B-plate and lasts for a very short period, during which all the helium ions are directly bumped into the B-plate and subsequently removed. The helium ion removal pulsing technique can efficiently avoid saturation of the micro-channel plate caused by too many helium ions. A compact and durable instrument is designed, which has a mass resolving resolution greater than 400 FWHM for online gas analysis. The technology may also be further developed to remove other ions for TOF mass spectrometry.

  16. Identification of sulfoglycolipids from the alga Porphyridium purpureum by matrix-assisted laser desorption/ionisation quadrupole ion trap time-of-flight mass spectrometry.

    PubMed

    Naumann, Ivonne; Darsow, Kai H; Walter, Christian; Lange, Harald A; Buchholz, Rainer

    2007-01-01

    Sulfoglycolipids, isolated from different phototrophic organisms, particularly plants and algae, have already been identified as bioactive compounds. In addition to their antiviral activity their influence on the immune response in mammalian cells is the focus of many studies. For the first time it has been possible to investigate purified sulfoquinovosyldiacylglycerols (SQDGs) from the microalga Porphyridium purpureum by matrix-assisted laser desorption/ionisation (MALDI) in the negative ion reflectron mode. Thereby, different solid and ionic liquid matrices have been tested to improve signal intensity during the laser ionisation. By using the MALDI Trap time-of-flight (ToF) multiple-stage (MS(n)) hybrid mass spectrometer the fatty acid compositions of the SQDGs were analysed by MS, and confirmed by MS(2) and MS(3) experiments. Thereby, hexadecanoic acid (C16:0), octadecadienoic acid (C18:2), eicosatetraenoic acid (C20:4), and eicosapentaenoic acid (C20:5) were detected in the purified fraction of SQDGs. The localisation of hexadecanoic acid (C16:0) at the sn-2 position, and unsaturated fatty acids at the sn-1 position of the SQDGs, determined by specific enzymatic hydrolysis, marks a procaryotic biosynthesis of SQDGs in the eucaryotic alga cells.

  17. Comparative study of matrices for their use in the rapid screening of anabolic steroids by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Galesio, M; Rial-Otero, R; Capelo-Martínez, J-L

    2009-06-01

    New data on sample preparation and matrix selection for the fast screening of androgenic anabolic steroids (AAS) by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is presented. The rapid screening of 15 steroids included in the World Anti-Doping Agency (WADA) prohibited list using MALDI was evaluated. Nine organic and two inorganic matrices were assessed in order to determine the best matrix for steroid identification in terms of ionisation yield and interference by characteristic matrix ions. The best results were achieved for the organic matrices 2-(4-hydroxyphenylazo)benzoic acid (HABA) and trans-3-indoleacrylic acid (IAA). Good signals for all the steroids studied were obtained for concentrations as low as 0.010 and 0.050 microg/mL on the MALDI sample plate for the HABA and IAA matrices, respectively. For these two matrices, the sensitivity achieved by MALDI is comparable with the sensitivity achieved by gas chromatography/mass spectrometry (GC/MS), which is the conventional technique used for AAS detection. Furthermore, the accuracy and precision obtained with MALDI are very good, since an internal mass calibration is performed with the matrix ions. For the inorganic matrices, laser fluences higher than those used with organic matrices are required to obtain good MALDI signals. When inorganic matrices were used in combination with glycerol as a dispersing agent, an important reduction of the background noise was observed. Urine samples spiked with the study compounds were processed by solid-phase extraction (SPE) and the screening was consistently positive.

  18. Method development for the determination of selected pesticides on tobacco by high-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry.

    PubMed

    Mayer-Helm, Bernhard; Hofbauer, Ludwig; Müller, Jutta

    2008-02-15

    A method was developed for the quantitative determination of alachlor, benalaxyl, clomazone, diflubenzuron, dimethomorph, diphenamid, ethofumesate, metalaxyl, methoprene, metobromuron and piperonyl butoxide on tobacco. The pesticides were extracted with water and methanol from five different types of tobacco. The extracts were purified by partition on an extraction cartridge containing diatomaceous earth. The purified extracts were analysed by reversed-phase high-performance liquid chromatography connected to an atmospheric pressure ionisation-electrospray-triple quadrupole mass spectrometer operating in the positive ion mode. Two different transitions and their relative intensities were monitored for unambiguous identification. All pesticides presented overall recovery rates between 35% and 110%. The trueness is near 100% and the interday precision is below 15%. The limits of quantifications are equal or below the guidance residue levels proposed by the Agrochemical Advisory Committee of CORESTA, an association of organisations having scientific research relative to tobacco.

  19. Characterisation of legumes by enzymatic hydrolysis, microdialysis sampling, and micro-high-performance anion-exchange chromatography with electrospray ionisation mass spectrometry.

    PubMed

    Okatch, Harriet; Torto, Nelson; Armateifio, Joan

    2003-04-11

    An assay based on enzymatic hydrolysisand microdialysis sampling, micro-high-performance anion-exchange chromatography (micro-HPAEC) with electrospray ionisation mass spectrometry (ESI-MS) for the characterisation of legumes is presented. Characterisation of two bean varieties; Phaseolus mungo and P. acutifilous was based upon enzymatic hydrolysis using an endo-beta-mannanase from Aspergillus niger with subsequent analysis of the hydrolysates with HPAEC-MS. The hydrolysates were detected in the positive ionisation mode after desalting the chromatographic effluent, employing a cation-exchange membrane desalting device with water as the regenerating liquid. Mass chromatograms, acquiredafter hydrolysis of both bean samples for 12 h, showed two different profiles of hydrolysates. The P. mungo bean hydrolysate showed the presence of saccharides with a degree of polymerisation (DP) in the range of 2-6, whereas that of P. acutifilous showed only DPs of 2-5. Both bean samples had one type of DP 2, but showed different types of DPs 3, 4 and 5. Only the P. mungo sample showed the presence of DP 6. The most abundant fraction for P. mungo was DP 4, whereas that for P. acutifilous was DP 5. Tandem MS of the hydrolysates showed that the DP 2 hydrolysates observed for the samples were of the same type, having a 1,6 linkage. Also tandem MS data for DPs 3, 4, and 5 showed that similar hydrolysates were present within the same sample as well as among the two samples. The data also showed the existence of 1,6 linkages for DP 3, 4, and 5 hydrolysates. The single enzymatic hydrolysis in combination with microdialysis and HPAEC with ESI-MS proved to be sufficient and reproducible for profiling and showing the difference between the two bean samples. PMID:12735463

  20. Time-resolved analysis of the emission of sidestream smoke (SSS) from cigarettes during smoking by photo ionisation/time-of-flight mass spectrometry (PI-TOFMS): towards a better description of environmental tobacco smoke.

    PubMed

    Streibel, T; Mitschke, S; Adam, T; Zimmermann, R

    2013-09-01

    In this study, the chemical composition of sidestream smoke (SSS) emissions of cigarettes are characterised using a laser-based single-photon ionisation time-of-flight mass spectrometer. SSS is generated from various cigarette types (2R4F research cigarette; Burley, Oriental and Virginia single-tobacco-type cigarettes) smoked on a single-port smoking machine and collected using a so-called fishtail chimney device. Using this setup, a puff-resolved quantification of several SSS components was performed. Investigations of the dynamics of SSS emissions show that concentration profiles of various substances can be categorised into several groups, either depending on the occurrence of a puff or uninfluenced by the changes in the burning zone during puffing. The SSS emissions occurring directly after a puff strongly resemble the composition of mainstream smoke (MSS). In the smouldering phase, clear differences between MSS and SSS are observed. The changed chemical profiles of SSS and MSS might be also of importance on environmental tobacco smoke which is largely determined by SSS. Additionally, the chemical composition of the SSS is strongly affected by the tobacco type. Hence, the higher nitrogen content of Burley tobacco leads to the detection of increased amounts of nitrogen-containing substances in SSS.

  1. Characterisation of ship diesel primary particulate matter at the molecular level by means of ultra-high-resolution mass spectrometry coupled to laser desorption ionisation--comparison of feed fuel, filter extracts and direct particle measurements.

    PubMed

    Rüger, Christopher P; Sklorz, Martin; Schwemer, Theo; Zimmermann, Ralf

    2015-08-01

    In this study, positive-mode laser desorption-ionisation ultra-high-resolution mass spectrometry (LDI-FT-ICR-MS) was applied to study combustion aerosol samples obtained from a ship diesel engine as well as the feed fuel, used to operate the engine. Furthermore, particulate matter was sampled from the exhaust tube using an impactor and analysed directly from the impaction foil without sample treatment. From the high percentage of shared sum formula as well as similarities in the chemical spread of aerosol and heavy fuel oil, results indicate that the primary aerosol mainly consists of survived, unburned species from the feed fuel. The effect of pyrosynthesis could be observed and was slightly more pronounced for the CH-class compared to other compound classes, but in summary not dominant. Alkylation pattern as well as the aromaticity distribution, using the double bond equivalent, revealed a shift towards lower alkylation state for the aerosol. The alkylation pattern of the most dominant series revealed a higher correlation between different aerosol samples than between aerosol and feed samples. This was confirmed by cluster analysis. Overall, this study shows that LDI-FT-ICR-MS can be successfully applied for the analysis of combustion aerosol at the molecular level and that sum formula information can be used to identify chemical differences between aerosol and fuel as well as between different size fractions of the particulate matter.

  2. A study of the analytical behaviour of selected synthetic and naturally occurring quinolines using electrospray ionisation ion trap mass spectrometry, liquid chromatography and gas chromatography and the construction of an appropriate database for quinoline characterisation.

    PubMed

    O'Donnell, F; Ramachandran, V N; Smyth, W F; Hack, C J; Patton, E

    2006-07-14

    Mass spectral fragmentation of quinoline alkaloids of significance in plants has been investigated using electrospray ionisation ion trap mass spectrometry (ESI-MS(n)) with a view to characterisation of molecules of unknown structure isolated from these natural sources. This investigation has led to the generation of an appropriate database incorporating data from ESI-MS(n) and also from gas liquid chromatography (GLC) and liquid chromatography (HPLC) for these low molecular mass quinolines. This has been put to practical application in the identification of quinoline alkaloids in a plant extract. Thus, an acid extraction of the leaves of Choisya ternata containing such tertiary alkaloids was analysed by liquid chromatography-electrospray ionisation mass spectrometry (HPLC-ESI-MS) and the resulting behaviour of the quinolines was compared with that of the quinoline alkaloids in the database.

  3. The simultaneous determination of selected flavonol glycosides and aglycones in Ginkgo biloba oral dosage forms by high-performance liquid chromatography-electrospray ionisation-mass spectrometry.

    PubMed

    Dubber, M-J; Sewram, V; Mshicileli, N; Shephard, G S; Kanfer, I

    2005-04-01

    An accurate, precise and sensitive liquid chromatography-tandem mass spectrometric (LC-MS-MS) method was developed for the determination of two flavonol glycosides, rutin and quercitrin, together with the algycone markers, quercetin, kaempferol and isorhamnetin in several Ginkgo biloba solid oral dosage forms. In addition, a novel quercetin glycoside, not yet reported in Ginkgo extracts, was identified. Liquid chromatography was performed using a minibore high-performance liquid chromatography (HPLC) column (150 mm x 2.0mm i.d.) and a one step gradient of acetonitrile-formic acid (0.3%) at a flow rate of 0.5 ml/min. Baseline separation of the five selected flavonol marker compounds was achieved within 20 min at 45 degrees C. Tandem mass spectrometry was performed using electrospray ionisation (ESI) in the negative ion mode. The marker compounds exhibited linearity over the range of 3-26 microg/ml and intra- and inter-day standard deviations were better than 7% and 16%, respectively. All Ginkgo products investigated were found to contain varying amounts of target analytes.

  4. Rapid characterisation and comparison of saponin profiles in the seeds of Korean Leguminous species using ultra performance liquid chromatography with photodiode array detector and electrospray ionisation/mass spectrometry (UPLC-PDA-ESI/MS) analysis.

    PubMed

    Ha, Tae Joung; Lee, Byong Won; Park, Ki Hun; Jeong, Seong Hun; Kim, Hyun-Tae; Ko, Jong-Min; Baek, In-Youl; Lee, Jin Hwan

    2014-03-01

    The present work was reported on investigation of saponin profiles in nine different legume seeds, including soybean, adzuki bean, cowpea, common bean, scarlet runner bean, lentil, chick pea, hyacinth bean, and broad bean using ultra performance liquid chromatography with photodiode array detector and electrospray ionisation/mass spectrometry (UPLC-PDA-ESI/MS) technique. A total of twenty saponins were characterised under rapid and simple conditions within 15min by the 80% methanol extracts of all species. Their chemical structures were elucidated as soyasaponin Ab (1), soyasaponin Ba (2), soyasaponin Bb (3), soyasaponin Bc (4), soyasaponin Bd (5), soyasaponin αg (6), soyasaponin βg (7), soyasaponin βa (8), soyasaponin γg (9), soyasaponin γa (10), azukisaponin VI (11), azukisaponin IV (12), azukisaponin II (13), AzII (14), AzIV (15), lablaboside E (16), lablaboside F (17), lablaboside D (18), chikusetusaponin IVa (19), and lablab saponin I (20). The individual and total saponin compositions exhibited remarkable differences in all legume seeds. In particular, soyasaponin βa (8) was detected the predominant composition in soybean, cowpea, and lentil with various concentrations. Interestingly, soybean, adzuki bean, common bean, and scarlet runner bean had high saponin contents, while chick pea and broad bean showed low contents. PMID:24176342

  5. Mass Conservation and Chemical Kinetics.

    ERIC Educational Resources Information Center

    Barbara, Thomas M.; Corio, P. L.

    1980-01-01

    Presents a method for obtaining all mass conservation conditions implied by a given mechanism in which the conditions are used to simplify integration of the rate equations and to derive stoichiometric relations. Discusses possibilities of faulty inference of kinetic information from a given stoichiometry. (CS)

  6. A novel matrix-assisted laser desorption/ionisation mass spectrometry imaging based methodology for the identification of sexual assault suspects.

    PubMed

    Bradshaw, Robert; Wolstenholme, Rosalind; Blackledge, Robert D; Clench, Malcolm R; Ferguson, Leesa S; Francese, Simona

    2011-02-15

    An increase in the use of condoms by sexual offenders has been observed. This is likely to be due both to the risk of sexually transmitted diseases and to prevent the transfer of DNA evidence. In this scenario the detection of condom lubricants at a crime scene could aid in proving corpus delicti. Here we show a novel application of Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry Imaging (MALDI MSI) for mapping the fingermark ridge pattern simultaneously to the detection of the condom lubricant within the fingermark itself. Two condom brands have been investigated to prove the concept. Condoms were handled producing lubricant-contaminated fingermarks. Images of the ridge pattern were obtained simultaneously to the detection of two lubricants, even several weeks after the fingermark deposition. The results therefore show the potential of MALDI MSI to link the suspect (identification through fingermark ridge pattern) to the crime (detection of condom lubricant) in one analysis. This would enable forensic scientists to provide evidence with stronger support in alleged cases of sexual assault. PMID:21213360

  7. Fractionation and analysis of lipopolysaccharide-derived oligosaccharides by zwitterionic-type hydrophilic interaction liquid chromatography coupled with electrospray ionisation mass spectrometry.

    PubMed

    Man-Kupisinska, Aleksandra; Bobko, Ewelina; Gozdziewicz, Tomasz K; Maciejewska, Anna; Jachymek, Wojciech; Lugowski, Czeslaw; Lukasiewicz, Jolanta

    2016-06-01

    Lipopolysaccharide (LPS, endotoxin) is a main surface antigen and virulence factor of Gram-negative bacteria. Regardless of the source of LPS, this molecule, isolated from the smooth forms of bacteria, is characterised by a general structural layout encompassing three regions: (i) an O-specific polysaccharide (O-PS) - a polymer of repeating oligosaccharide units, (ii) core oligosaccharide (OS), and (iii) the lipid A anchoring LPS in the outer membrane of the cell envelope of Gram-negative bacteria. Structural analysis usually requires degradation of LPS and further efficient separation of various poly- and oligosaccharide glycoforms. The hydrophilic interaction liquid chromatography (HILIC) was shown as an efficient technique for separation of labelled or native neutral and acidic glycans, glycopeptides, sialylated glycans, glycosylated and nonglycosylated peptides. Herein we adopted ZIC(®) (zwitterionic stationary phase covalently attached to porous silica)-HILIC technology in combination with electrospray ionisation mass spectrometry to separate different LPS-derived oligosaccharides. As a result three effective procedures have been developed: (i) to separate different core oligosaccharides of Escherichia coli R1 LOS, (ii) to separate RU-[Hep]-Kdo oligosaccharides from core OS glycoforms of Hafnia alvei PCM 1200 LPS, and (iii) to separate Hep and Kdo-containing mono, di-, tri- and tetrasaccharides of H. alvei PCM 1200 LPS. Moreover, some of developed analytical procedures were scaled to semi-preparative protocols and used to obtain highly-purified fractions of the interest in larger quantities required for future evaluation, analysis, and biological applications. PMID:27085741

  8. Adsorption of ionisable pesticides in soils.

    PubMed

    Kah, M; Brown, C D

    2006-01-01

    Understanding the fate of a pesticide in soil is fundamental to the accurate assessment of its environmental behaviour and vital in ensuring the safe use of new and existing products. Ionisable pesticides comprise a significant proportion of both existing and new active substances registered for use in agriculture worldwide. This group of pesticides includes chemicals that are frequently found in groundwater and surface waters in many different countries. Despite this, approaches to predict the influence of soil properties on the behaviour of ionisable pesticides in soils are poorly developed. Current regulatory assessments frequently default to methods developed for nonionic chemicals, although it is evident that ionisable compounds do not often react like neutral molecules. This review presents the state of knowledge on the adsorption of ionisable pesticides in soils. It first introduces the issues concerning adsorption and the characteristics of this particular kind of chemical. The mechanisms postulated for the adsorption of ionisable pesticides are then described: these are hydrophobic partitioning, ionic exchange, charge transfer, ligand exchange, cation or water bridging, and the formation of bound residues. Relatively little experimental evidence is available, and we are still unable to determine the quantitative contribution of each process in a particular situation. Knowledge is still lacking concerning phenomena occurring at the surfaces of soil particles. Measurements do not allow determination of the operative pH at the surface of soil particles or in microenvironments, and the influence of ionic strength or competition effects is difficult to assess. Subsequently, the review focuses on the influence of soil properties on adsorption and on potential to predict the behaviour of ionisable pesticides in soils. Unlike hydrophobic compounds, adsorption of ionisable pesticides is highly sensitive to variation in pH. This relationship mainly derives from the

  9. First field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer for the on-line detection of particle-bound polycyclic aromatic hydrocarbons.

    PubMed

    Oster, Markus; Elsasser, Michael; Schnelle-Kreis, Jürgen; Zimmermann, Ralf

    2011-12-01

    The on-line analysis of single aerosol particles with mass spectrometrical methods is an important tool for the investigation of aerosols. Often, a single laser pulse is used for one-step laser desorption/ionisation of aerosol particles. Resulting ions are detected with time-of-flight mass spectrometry. With this method, the detection of inorganic compounds is possible. The detection of more fragile organic compounds and carbon clusters can be accomplished by separating the desorption and the ionisation in two steps, e.g. by using two laser pulses. A further method is, using a heated metal surface for thermal desorption of aerosol particles. If an ultraviolet laser is used for ionisation, a selective ionisation of polycyclic aromatic hydrocarbons (PAH) and alkylated PAH is possible via a resonance-enhanced multiphoton-ionisation process. Laser velocimetry allows individual laser triggering for single particles and additionally delivers information on aerodynamic particle diameters. It was shown that particles deriving from different combustion sources can be differentiated according to their PAH patterns. For example, retene, a C(4)-alkylated phenanthrene derivative, is a marker for the combustion of coniferous wood. In this paper, the first field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer during a measurement campaign in Augsburg, Germany in winter 2010 is presented. Larger PAH-containing particles (i.e. with aerodynamic diameters larger than 1 μm), which are suspected to be originated by re-suspension processes of agglomerated material, were in the focus of the investigation. Due to the low concentration of these particles, an on-line virtual impactor enrichment system was used. The detection of particle-bound PAH in ambient particles in this larger size region was possible and in addition, retene could be detected on several particles, which allows to identify wood combustion as

  10. Histidine-containing host-defence skin peptides of anurans bind Cu2+. An electrospray ionisation mass spectrometry and computational modelling study.

    PubMed

    Wang, Tianfang; Andreazza, Hayley J; Pukala, Tara L; Sherman, Patrick J; Calabrese, Antonio N; Bowie, John H

    2011-05-15

    Anuran peptides which contain His, including caerin 1.8 (GLFKVLGSVAKHLLPHVVPVIAEKL-NH(2)), caerin 1.2 (GLLGVLGSVAKHVLPHVVPVIAEHL-NH(2)), Ala(15) maculatin 1.1 (GLFGVLAKVAAHVVAIEHF-NH(2)), fallaxidin 4.1 (GLLSFLPKVIGHLIHPPS-OH), riparin 5.1 (IVSYPDDAGEHAHKMG-NH(2)) and signiferin 2.1 (IIGHLIKTALGMLGL-NH(2)), all form MMet(2+) and (M + Met(2+)-2H(+))(2+) cluster ions (where Met is Cu, Mg and Zn) following electrospray ionisation (ESI) in a Waters QTOF 2 mass spectrometer. Peaks due to Cu(II) complexes are always the most abundant relative to other metal complexes. Information concerning metal(2+) connectivity in a complex has been obtained (at least in part) using b and y fragmentation data from ESI collision-induced dissociation tandem mass spectrometry (CID MS/MS). Theoretical calculations, using AMBER version 10, show that MCu(2+) complexes with the membrane active caerin 1.8, Ala(15) maculatin 1.1 and fallaxidin 4.1 are four-coordinate and approximating square planar, with ligands including His and Lys, together with the carbonyl oxygens of particular backbone amide groups. When binding can occur through two His, or one His and one Lys, the His/Lys ligand structure is the more stable for the studied systems. The three-dimensional (3D) structures of the complexes are always different from the previously determined structures of the uncomplexed model peptides (using 2D nuclear magnetic resonance (NMR) spectroscopy in membrane-mimicking solvents like trifluoroethanol/water). PMID:21488120

  11. Rapid typing of bacteria using matrix-assisted laser desorption ionisation time-of-flight mass spectrometry and pattern recognition software.

    PubMed

    Bright, John J; Claydon, Martin A; Soufian, Majeed; Gordon, Derek B

    2002-02-01

    Matrix-assisted laser desorption ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) of intact microorganisms, also known as intact cell MALDI-TOF-MS (ICM-MS), has been shown to produce characteristic mass spectral fingerprints of moieties desorbed from the cell surface. ICM-MS spectra can be obtained in minutes after removal of a colony from a culture plate. The similarity of ICM-MS spectra of replicate samples and of two different batches of the same bacterial strain demonstrates, in this study, the reproducibility of the technique. We have developed the Manchester Metropolitan University Search Engine (MUSE) to rapidly build and search databases of ICM-MS spectra. A database of 35 strains, representing 20 species and 12 genera, was built with MUSE and used to identify 212 isolates. The database was created in 26 s and loaded in 10 s, ready for searching, which took less than 1 s per isolate. Correct matches were made in 79%, 84% and 89% of the 212 samples at strain, species and genus levels, respectively. At least 50% of the replicates of 42 of the 45 isolates matched the correct strain, and the most commonly identified species for 43 of the 45 isolates was the correct one. The close match of the Escherichia coli strains containing the O157 antigen and the E. coli strains containing the K1 antigen suggests that these antigens may have a dominating influence on the ICM-MS fingerprints of these strains. We now have the ability to acquire ICM-MS fingerprints of bacteria and to search a database of these fingerprints within minutes, so that the rapid identification of bacteria to the strain level can be realised.

  12. A quick and easy method to identify bacteria by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Pennanec, Xaviera; Dufour, Alain; Haras, Dominique; Réhel, Karine

    2010-02-01

    Concerns with water quality have increased in recent years, in part due to the more frequent contamination of water by pathogens like E. coli and L. pneumophila. Current methods for the typing of bacteria in water samples are based on culture of samples on specific media. These techniques are time-consuming, subject to the impact of interferents and do not totally meet all the requirements of prevention. There is a need for accurate and rapid identification of these microorganisms. This report deals with the detection of bacteria, more precisely of Legionella spp., and the development of an analytical strategy for a rapid and unambiguous identification of these pathogens in water from diverse origins. Therefore, a protein mass mapping using matrix-assisted laser desorption/ionisation mass spectrometry (MALDI MS) of whole bacteria combined with a home-made database of bacteria spectra is applied. A large variety of different bacteria and microorganisms is used to approach the actual composition of samples with numerous interferents. The objective is to propose a universal method for sampling preparation before MALDI MS analysis and optimised spectrometric conditions for reproducible intense peaks. Several experimental factors known to influence signal quality such as time and media of culture have been studied. The proposed method gives promising results for a sure differentiation of Legionella species and subspecies and a rapid identification of bacteria which are the most dangerous or difficult to eradicate. This method is easy to perform with an excellent reproducibility. The analytical protocol and the corresponding database were validated on samples from different origins (cooling tower, plumbing hot water). PMID:20049880

  13. Airborne laser-spark for ambient desorption/ionisation.

    PubMed

    Bierstedt, Andreas; Riedel, Jens

    2016-01-01

    A novel direct sampling ionisation scheme for ambient mass spectrometry is presented. Desorption and ionisation are achieved by a quasi-continuous laser induced plasma in air. Since there are no solid or liquid electrodes involved the ion source does not suffer from chemical interferences or fatigue originating from erosive burning or from electrode consumption. The overall plasma maintains electro-neutrality, minimising charge effects and accompanying long term drift of the charged particles trajectories. In the airborne plasma approach the ambient air not only serves as the plasma medium but at the same time also slows down the nascent ions via collisional cooling. Ionisation of the analyte molecules does not occur in the plasma itself but is induced by interaction with nascent ionic fragments, electrons and/or far ultraviolet photons in the plasma vicinity. At each individual air-spark an audible shockwave is formed, providing new reactive species, which expands concentrically and, thus, prevents direct contact of the analyte with the hot region inside the plasma itself. As a consequence the interaction volume between plasma and analyte does not exceed the threshold temperature for thermal dissociation or fragmentation. Experimentally this indirect ionisation scheme is demonstrated to be widely unspecific to the chemical nature of the analyte and to hardly result in any fragmentation of the studied molecules. A vast ensemble of different test analytes including polar and non-polar hydrocarbons, sugars, low mass active ingredients of pharmaceuticals as well as natural biomolecules in food samples directly out of their complex matrices could be shown to yield easily accessible yet meaningful spectra. Since the plasma medium is humid air, the chemical reaction mechanism of the ionisation is likely to be similar to other ambient ionisation techniques. Wir stellen hier eine neue Ionisationsmethode für die Umgebungsionisation (ambient ionisation) vor. Sowohl die

  14. Airborne laser-spark for ambient desorption/ionisation.

    PubMed

    Bierstedt, Andreas; Riedel, Jens

    2016-01-01

    A novel direct sampling ionisation scheme for ambient mass spectrometry is presented. Desorption and ionisation are achieved by a quasi-continuous laser induced plasma in air. Since there are no solid or liquid electrodes involved the ion source does not suffer from chemical interferences or fatigue originating from erosive burning or from electrode consumption. The overall plasma maintains electro-neutrality, minimising charge effects and accompanying long term drift of the charged particles trajectories. In the airborne plasma approach the ambient air not only serves as the plasma medium but at the same time also slows down the nascent ions via collisional cooling. Ionisation of the analyte molecules does not occur in the plasma itself but is induced by interaction with nascent ionic fragments, electrons and/or far ultraviolet photons in the plasma vicinity. At each individual air-spark an audible shockwave is formed, providing new reactive species, which expands concentrically and, thus, prevents direct contact of the analyte with the hot region inside the plasma itself. As a consequence the interaction volume between plasma and analyte does not exceed the threshold temperature for thermal dissociation or fragmentation. Experimentally this indirect ionisation scheme is demonstrated to be widely unspecific to the chemical nature of the analyte and to hardly result in any fragmentation of the studied molecules. A vast ensemble of different test analytes including polar and non-polar hydrocarbons, sugars, low mass active ingredients of pharmaceuticals as well as natural biomolecules in food samples directly out of their complex matrices could be shown to yield easily accessible yet meaningful spectra. Since the plasma medium is humid air, the chemical reaction mechanism of the ionisation is likely to be similar to other ambient ionisation techniques. Wir stellen hier eine neue Ionisationsmethode für die Umgebungsionisation (ambient ionisation) vor. Sowohl die

  15. The detection of iron protoporphyrin (heme b) in phytoplankton and marine particulate material by electrospray ionisation mass spectrometry - comparison with diode array detection.

    PubMed

    Gledhill, Martha

    2014-09-01

    A mass spectrometric (MS) method for the identification of iron protoporphyrin (IX) (FePTP, heme b) in marine particulate material and phytoplankton is described. Electrospray ionisation of FePTP produced the molecular Fe(III)PTP(+) ion (m/z=616) or the pseudomolecular [Fe(II)PTP + H](+) ion (m/z=617), depending on the oxidation state of the central iron ion. Collision induced dissociation (CID) in the ion trap mass spectrometer resulted in a single detected product ion (m/z=557) indicative of loss of ethanoic acid from a carboxylic acid side chain. Widening the isolation width to 616±3 resulted in production of a mass spectrum demonstrating the distinctive isotopic ratio of the iron containing fragment, further increasing the specificity of the analysis. Selective reactant monitoring (SRM) of the fragment ion (m/z=557) was applied to the detection of FePTP after chromatography of ammoniacal OGP extracts of marine samples. The detection limit for FePTP analysed by SRM after chromatography was 1.2±0.5fmol. For phytoplankton samples, reasonably good agreement was achieved between results obtained with SRM and those obtained by monitoring absorbance at λ=400nm using a diode array detector (DAD). Use of SRM for analysis of particulate material obtained from the high latitude North Atlantic allowed for the analysis of FePTP in the presence of a co-eluting compound that interfered with detection by DAD. Simultaneous collection of mass spectra from m/z=300 to 1500 resulted in identification of the pseudomolecular ion for the interfering compound. The CID fragmentation pattern and UV-visible mass spectra indicated that the interfering compound was a previously unidentified chlorin type compound. Comparison of FePTP determined by SRM and DAD on samples where this compound could not be detected showed that results collected using the two methods correlated. The use of both MS and DAD results in a powerful tool for quantifying this important biogenic component of the

  16. Simultaneous determination of tanshinone IIA and cryptotanshinone in rat plasma by liquid chromatography-electrospray ionisation-mass spectrometry.

    PubMed

    Li, Jing; Wang, Guangji; Li, Peng; Hao, Haiping

    2005-11-01

    Tanshinone IIA (TS) and cryptotanshinone (CT) are the major active constituents contained in Radix salvia miltiorrhiza. This paper described a rapid, sensitive and specific assay for the simultaneous quantitative determination of TS and CT in rat plasma. After a single step of liquid-liquid extraction, plasma samples were analyzed by high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) using a reversed-phase C18 column (150 mmx2.0 mm, 5 microm, Shim-pack VP-ODS column). The assay was linear in the concentration range of 2-200 ng/ml. The lower limits of quantification of TS and CT were 1 and 0.2 ng/ml, respectively. Recoveries of TS and CT were greater than 80%. The precisions and accuracies determined from 5 days were all within 12%. The assay was applied to a pharmacokinetic study in rats after an oral administration of total tanshinones with a dose of 150 mg/kg (containing 12% of TS and CT). Results showed that this simple and rapid method was sensitive enough to follow the plasma levels of TS and CT in rats, even though the concentration maximums of both were below 20 ng/ml after an oral administration of total tanshinones. PMID:16140046

  17. Identification of prenylated pterocarpans and other isoflavonoids in Rhizopus spp. elicited soya bean seedlings by electrospray ionisation mass spectrometry.

    PubMed

    Simons, Rudy; Vincken, Jean-Paul; Bohin, Maxime C; Kuijpers, Tomas F M; Verbruggen, Marian A; Gruppen, Harry

    2011-01-15

    Phytoalexins from soya are mainly characterised as prenylated pterocarpans, the glyceollins. Extracts of non-soaked and soaked soya beans, as well as that of soya seedlings, grown in the presence of Rhizopus microsporus var. oryzae, were screened for the presence of prenylated flavonoids with a liquid chromatography/mass spectrometry (LC/MS)-based screening method. The glyceollins I-III and glyceollidins I-II, belonging to the isoflavonoid subclass of the pterocarpans, were tentatively assigned. The formation of these prenylated pterocarpans was accompanied by that of other prenylated isoflavonoids of the subclasses of the isoflavones and the coumestans. It was estimated that approx. 40% of the total isoflavonoid content in Rhizopus-challenged soya bean seedlings were prenylated pterocarpans, whereas 7% comprised prenylated isoflavones and prenylated coumestans. The site of prenylation (A-ring or B-ring) of the prenylated isoflavones was tentatively annotated using positive-ion mode MS by comparing the (1,3) A(+) retro-Diels-Alder (RDA) fragments of prenylated and non-prenylated isoflavones. Furthermore, the fragmentation pathways of the five pterocarpans in negative-ion (NI) mode were proposed, which involved the cleavage of the C-ring and/or D-ring. The absence of the ring-closed prenyl (pyran or furan) gave exclusively -H(2) O(x,y) RDA fragments, whereas its presence gave predominantly the common RDA fragments.

  18. Feasibility of matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) networking in university hospitals in Brussels.

    PubMed

    Martiny, D; Cremagnani, P; Gaillard, A; Miendje Deyi, V Y; Mascart, G; Ebraert, A; Attalibi, S; Dediste, A; Vandenberg, O

    2014-05-01

    The mutualisation of analytical platforms might be used to address rising healthcare costs. Our study aimed to evaluate the feasibility of networking a unique matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) system for common use in several university hospitals in Brussels, Belgium. During a one-month period, 1,055 successive bacterial isolates from the Brugmann University Hospital were identified on-site using conventional techniques; these same isolates were also identified using a MALDI-TOF MS system at the Porte de Hal Laboratory by sending target plates and identification projects via transportation and the INFECTIO_MALDI software (Infopartner, Nancy, France), respectively. The occurrence of transmission problems (<2 %) and human errors (<1 %) suggested that the system was sufficiently robust to be implemented in a network. With a median time-to-identification of 5 h and 11 min (78 min, min-max: 154-547), MALDI-TOF MS networking always provided a faster identification result than conventional techniques, except when chromogenic culture media and oxidase tests were used (p < 0.0001). However, the limited clinical benefits of the chromogenic culture media do not support their extra cost. Our financial analysis also suggested that MALDI-TOF MS networking could lead to substantial annual cost savings. MALDI-TOF MS networking presents many advantages, and few conventional techniques (optochin and oxidase tests) are required to ensure the same quality in patient care from the distant laboratory. Nevertheless, such networking should not be considered unless there is a reorganisation of workflow, efficient communication between teams, qualified technologists and a reliable IT department and helpdesk to manage potential connectivity problems.

  19. Rapid identification of Burkholderia mallei and Burkholderia pseudomallei by intact cell Matrix-assisted Laser Desorption/Ionisation mass spectrometric typing

    PubMed Central

    2012-01-01

    Background Burkholderia (B.) pseudomallei and B. mallei are genetically closely related species. B. pseudomallei causes melioidosis in humans and animals, whereas B. mallei is the causative agent of glanders in equines and rarely also in humans. Both agents have been classified by the CDC as priority category B biological agents. Rapid identification is crucial, because both agents are intrinsically resistant to many antibiotics. Matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-TOF MS) has the potential of rapid and reliable identification of pathogens, but is limited by the availability of a database containing validated reference spectra. The aim of this study was to evaluate the use of MALDI-TOF MS for the rapid and reliable identification and differentiation of B. pseudomallei and B. mallei and to build up a reliable reference database for both organisms. Results A collection of ten B. pseudomallei and seventeen B. mallei strains was used to generate a library of reference spectra. Samples of both species could be identified by MALDI-TOF MS, if a dedicated subset of the reference spectra library was used. In comparison with samples representing B. mallei, higher genetic diversity among B. pseudomallei was reflected in the higher average Eucledian distances between the mass spectra and a broader range of identification score values obtained with commercial software for the identification of microorganisms. The type strain of B. pseudomallei (ATCC 23343) was isolated decades ago and is outstanding in the spectrum-based dendrograms probably due to massive methylations as indicated by two intensive series of mass increments of 14 Da specifically and reproducibly found in the spectra of this strain. Conclusions Handling of pathogens under BSL 3 conditions is dangerous and cumbersome but can be minimized by inactivation of bacteria with ethanol, subsequent protein extraction under BSL 1 conditions and MALDI-TOF MS analysis being faster than

  20. Some critical aspects in the determination of binding constants by electrospray ionisation mass spectrometry at the example of arsenic bindings to sulphur-containing biomolecules.

    PubMed

    Schmidt, Anne-Christine; Steier, Sandra

    2010-08-01

    The influences of reactant concentrations, solvent type, acid strength, pH conditions and ionic strength on the determination of apparent gas-phase equilibrium constants K using electrospray ionisation mass spectrometry (ESI-MS) were elucidated. As example serves the interaction of the tripeptide glutathione (GSH) with phenylarsine oxide (PAO). It was shown that rising initial concentrations of both reactants were not adequately compensated by increasing signal intensities of the reaction products in the mass spectra. The equilibrium constant for the formation of the phenylarsenic-substituted peptide species decreased from 1.42 x 10(5) +/- 1.81 x 10(4) l micromol(-1) to 1.54 x 10(4) +/- 1.5 x 10(3) l micromol(-1) with rising initial GSH concentrations from 1 to 10 microM at fixed PAO molarity of 50 microM. K values resulting from a series with a fixed GSH molarity of 5 microM and a PAO molarity varied from 10 to 100 microM remained in a narrower range between 4.59 x 10(4) +/- 2.15 x 10(4) l micromol(-1) and 1.07 x 10(4) +/- 4.0 x 10(3) l micromol(-1). In contrast, consumption numbers calculated from the ion intensity ratios of reaction products to the unreacted peptide were not influenced by the initial reactant concentrations. In a water-acetonitrile-acetic acid mixture (48:50:2, v:v), the consumption of 5 micro M GSH increased from 8.3 +/- 1.4% to 39.6 +/- 1.6% with increased molar excess of PAO from 2 to 20, respectively. The GSH consumption was considerably enhanced in a changed solvent system consisting of 25% acetonitrile and 75% 10 mM ammonium formate, pH 5.0 (v:v) up to 80% of the original peptide amount at an only threefold molar arsenic excess.

  1. European Code against Cancer 4th Edition: Ionising and non-ionising radiation and cancer.

    PubMed

    McColl, Neil; Auvinen, Anssi; Kesminiene, Ausrele; Espina, Carolina; Erdmann, Friederike; de Vries, Esther; Greinert, Rüdiger; Harrison, John; Schüz, Joachim

    2015-12-01

    Ionising radiation can transfer sufficient energy to ionise molecules, and this can lead to chemical changes, including DNA damage in cells. Key evidence for the carcinogenicity of ionising radiation comes from: follow-up studies of the survivors of the atomic bombings in Japan; other epidemiological studies of groups that have been exposed to radiation from medical, occupational or environmental sources; experimental animal studies; and studies of cellular responses to radiation. Considering exposure to environmental ionising radiation, inhalation of naturally occurring radon is the major source of radiation in the population - in doses orders of magnitude higher than those from nuclear power production or nuclear fallout. Indoor exposure to radon and its decay products is an important cause of lung cancer; radon may cause approximately one in ten lung cancers in Europe. Exposures to radon in buildings can be reduced via a three-step process of identifying those with potentially elevated radon levels, measuring radon levels, and reducing exposure by installation of remediation systems. In the 4th Edition of the European Code against Cancer it is therefore recommended to: "Find out if you are exposed to radiation from naturally high radon levels in your home. Take action to reduce high radon levels". Non-ionising types of radiation (those with insufficient energy to ionise molecules) - including extremely low-frequency electric and magnetic fields as well as radiofrequency electromagnetic fields - are not an established cause of cancer and are therefore not addressed in the recommendations to reduce cancer risk. PMID:26126928

  2. European Code against Cancer 4th Edition: Ionising and non-ionising radiation and cancer.

    PubMed

    McColl, Neil; Auvinen, Anssi; Kesminiene, Ausrele; Espina, Carolina; Erdmann, Friederike; de Vries, Esther; Greinert, Rüdiger; Harrison, John; Schüz, Joachim

    2015-12-01

    Ionising radiation can transfer sufficient energy to ionise molecules, and this can lead to chemical changes, including DNA damage in cells. Key evidence for the carcinogenicity of ionising radiation comes from: follow-up studies of the survivors of the atomic bombings in Japan; other epidemiological studies of groups that have been exposed to radiation from medical, occupational or environmental sources; experimental animal studies; and studies of cellular responses to radiation. Considering exposure to environmental ionising radiation, inhalation of naturally occurring radon is the major source of radiation in the population - in doses orders of magnitude higher than those from nuclear power production or nuclear fallout. Indoor exposure to radon and its decay products is an important cause of lung cancer; radon may cause approximately one in ten lung cancers in Europe. Exposures to radon in buildings can be reduced via a three-step process of identifying those with potentially elevated radon levels, measuring radon levels, and reducing exposure by installation of remediation systems. In the 4th Edition of the European Code against Cancer it is therefore recommended to: "Find out if you are exposed to radiation from naturally high radon levels in your home. Take action to reduce high radon levels". Non-ionising types of radiation (those with insufficient energy to ionise molecules) - including extremely low-frequency electric and magnetic fields as well as radiofrequency electromagnetic fields - are not an established cause of cancer and are therefore not addressed in the recommendations to reduce cancer risk.

  3. Hydrogen/deuterium exchange on aromatic rings during atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Davies, Noel W; Smith, Jason A; Molesworth, Peter P; Ross, John J

    2010-04-15

    It has been demonstrated that substituted indoles fully labelled with deuterium on the aromatic ring can undergo substantial exchange back to partial and even fully protonated forms during atmospheric pressure chemical ionisation (APCI) liquid chromatography/mass spectrometry (LC/MS). The degree of this exchange was strongly dependent on the absolute quantity of analyte, the APCI desolvation temperature, the nature of the mobile phase, the mobile phase flow rate and the instrument used. Hydrogen/deuterium (H/D) exchange on several other aromatic ring systems during APCI LC/MS was either undetectable (nitrobenzene, aniline) or extremely small (acetanilide) compared to the effect observed for substituted indoles. This observation has major implications for quantitative assays using deuterium-labelled internal standards and for the detection of deuterium-labelled products from isotopically labelled feeding experiments where there is a risk of back exchange to the protonated form during the analysis. PMID:20213724

  4. Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time-of-flight mass spectrometry.

    PubMed

    Panyala, Nagender Reddy; Peña-Méndez, Eladia María; Havel, Josef

    2012-05-15

    Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m = 1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n = 2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m = 1-12), P(n)(+) (n = 2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n = 1, 2-88 (even numbers)), Au(2)P(n)(+) (n = 1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n = 1-6, 8, 9, 14), Au(4)P(n)(+) (n = 1-9, 14-16), Au(5)P(n)(+) (n = 1-6, 14, 16), Au(6)P(n)(+) (n = 1-6), Au(7)P(n)(+) (n = 1-7), Au(8)P(n)(+) (n = 1-6, 8), Au(9)P(n)(+) (n = 1-10), Au(10)P(n)(+) (n = 1-8, 15), Au(11)P(n)(+) (n = 1-6), and Au(12)P(n)(+) (n = 1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m = 1-5), P(n)(-) (n = 2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n = 4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n = 2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n = 6-11, 32), Au(4)P(n)(-) (n = 1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n = 1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of

  5. Laser-based mass spectrometry for in situ chemical composition analysis of planetary surfaces

    NASA Astrophysics Data System (ADS)

    Frey, Samira; Neuland, Maike B.; Grimaudo, Valentine; Moreno-García, Pavel; Riedo, Andreas; Tulej, Marek; Broekmann, Peter; Wurz, Peter

    2016-04-01

    Mass spectrometry is an important analytical technique in space research. The chemical composition of planetary surface material is a key scientific question on every space mission to a planet, moon or asteroid. Chemical composition measurements of rocky material on the surface are of great importance to understand the origin and evolution of the planetary body.[1] A miniature laser ablation/ionisation reflectron- type time-of-flight mass spectrometer (instrument name LMS) was designed and built at the University of Bern for planetary research.[2] Despite its small size and light weight, the LMS instrument still maintains the same capabilities as large laboratory systems, which makes it suitable for its application on planetary space missions.[3-5] The high dynamic range of about eight orders of magnitude, high lateral (μm-level) and vertical (sub-nm level) resolution and high detection sensitivity for almost all elements (10 ppb, atomic fraction) make LMS a versatile instrument for various applications. LMS is a suitable instrument for in situ measurements of elemental and isotope composition with high precision and accuracy. Measurements of Pb- isotope abundances can be used for dating of planetary material. Measurements of bio-relevant elements allow searching for past or present life on a planetary surface. The high spatial resolution, both in lateral and vertical direction, is of considerable interest, e.g. for analysis of inhomogeneous, extraterrestrial samples as well as weathering processes of planetary material. References [1] P. Wurz, D. Abplanalp, M. Tulej, M. Iakovleva, V.A. Fernandes, A. Chumikov, and G. Managadze, "Mass Spectrometric Analysis in Planetary Science: Investigation of the Surface and the Atmosphere", Sol. Sys. Res., 2012, 46, 408. [2] U. Rohner, J.A. Whitby, P. Wurz, "A miniature laser ablation time of flight mass spectrometer for in situ planetary exploration" Meas. Sci. Tch., 2003, 14, 2159. [3] M. Tulej, A. Riedo, M.B. Neuland, S

  6. Real-time analysis of aromatics in combustion engine exhaust by resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOF-MS): a robust tool for chassis dynamometer testing.

    PubMed

    Adam, T W; Clairotte, M; Streibel, T; Elsasser, M; Pommeres, A; Manfredi, U; Carriero, M; Martini, G; Sklorz, M; Krasenbrink, A; Astorga, C; Zimmermann, R

    2012-07-01

    Resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOF-MS) is a robust method for real-time analysis of monocyclic and polycyclic aromatic hydrocarbons in complex emissions. A mobile system has been developed which enables direct analysis on site. In this paper, we utilize a multicomponent calibration scheme based on the analytes' photo-ionisation cross-sections relative to a calibrated species. This allows semi-quantification of a great number of components by only calibrating one compound of choice, here toluene. The cross-sections were determined by injecting nebulised solutions of aromatic compounds into the TOF-MS ion source with the help of a HPLC pump. Then, REMPI-TOF-MS was implemented at various chassis dynamometers and test cells and the exhaust of the following vehicles and engines investigated: a compression ignition light-duty (LD) passenger car, a compression ignition LD van, two spark ignition LD passenger cars, 2 two-stroke mopeds, and a two-stroke engine of a string gas trimmer. The quantitative time profiles of benzene are shown. The results indicate that two-stroke engines are a significant source for toxic and cancerogenic compounds. Air pollution and health effects caused by gardening equipment might still be underestimated.

  7. Positron impact ionisation phenomena

    NASA Astrophysics Data System (ADS)

    Moxom, J.

    A magnetically guided beam of nearly-monoenergetic slow positrons has been used to study positron impact ionisation phenomena in gases. A novel hemispherical scattering cell incorporating an efficient ion extraction and detection system has been developed and has been utilised throughout this work. The energy spectra for the electrons ejected around 0° relative to the incident beam, following positron impact ionisation of Ar, have been measured by a time-of-flight method and a retarding electric field analyzer. The angular acceptance of the electron detection system has been estimated and used to compare the measured spectra with the double differential cross-sections calculated by Mandal et al (1986), Sil et al (1991) and Schultz and Reinhold (1990). The importance of the electron-capture-to-the-continuum process is discussed in this context and found to be minor at small forward angles, in contrast to the case of heavy positively charged projectiles. The apparatus was modified to produce a pulsed beam of slow positrons and utilised to measure in detail the total ionisation cross-section (Qt+) for a variety of atomic and molecular targets. For Ar, He and H2, Qt+ which includes contributions from Ps formation, has been subtracted from corresponding total cross-sections, in order to deduce the behaviour of the elastic scattering cross-section (Qel) in the vicinity of the Ps formation threshold (Eps). Here a small change in the gradient of Qel, has been found. The energy dependencies of the Qt+ for He, Ne and Ar, close to Eps have been interpreted in terms of threshold theory. In the case of Ar the outgoing Ps appears to be predominantly s-wave in character. For He and Ne the analysis suggests that the Ps contains significant contributions from a number of partial waves. In the case of O 2, structure in Qt+ has been found, which is attributed to coupling between two inelastic channels, namely Ps formation and excitation to the Schuman-Runge continuum.

  8. Cosmic-ray ionisation in collapsing clouds

    NASA Astrophysics Data System (ADS)

    Padovani, M.; Hennebelle, P.; Galli, D.

    2013-12-01

    Context. Cosmic rays play an important role in dense molecular cores, affecting their thermal and dynamical evolution and initiating the chemistry. Several studies have shown that the formation of protostellar discs in collapsing clouds is severely hampered by the braking torque exerted by the entrained magnetic field on the infalling gas, as long as the field remains frozen to the gas. Aims: In this paper we examine the possibility that the concentration and twisting of the field lines in the inner region of collapse can produce a significant reduction of the ionisation fraction. Methods: To check whether the cosmic-ray ionisation rate can fall below the critical value required to maintain good coupling, we first study the propagation of cosmic rays in a model of a static magnetised cloud varying the relative strength of the toroidal/poloidal components and the mass-to-flux ratio. We then follow the path of cosmic rays using realistic magnetic field configurations generated by numerical simulations of a rotating collapsing core with different initial conditions. Results: We find that an increment of the toroidal component of the magnetic field, or, in general, a more twisted configuration of the field lines, results in a decrease in the cosmic-ray flux. This is mainly due to the magnetic mirroring effect that is stronger where larger variations in the field direction are present. In particular, we find a decrease of the cosmic-ray ionisation rate below 10-18 s-1 in the central 300-400 AU, where density is higher than about 109 cm-3. This very low value of the ionisation rate is attained in the cases of intermediate and low magnetisation (mass-to-flux ratio λ = 5 and 17, respectively) and for toroidal fields larger than about 40% of the total field. Conclusions: Magnetic field effects can significantly reduce the ionisation fraction in collapsing clouds. We provide a handy fitting formula to compute approximately the attenuation of the cosmic-ray ionisation rate

  9. Profile of phenolic compounds of Brazilian virgin olive oils by rapid resolution liquid chromatography coupled to electrospray ionisation time-of-flight mass spectrometry (RRLC-ESI-TOF-MS).

    PubMed

    Ballus, Cristiano Augusto; Quirantes-Piné, Rosa; Bakhouche, Abdelhakim; da Silva, Luiz Fernando de Oliveira; de Oliveira, Adelson Francisco; Coutinho, Enilton Fick; da Croce, Dorli Mario; Segura-Carretero, Antonio; Godoy, Helena Teixeira

    2015-03-01

    In recent years, agronomical researchers began to cultivate several olive varieties in different regions of Brazil to produce virgin olive oil (VOO). Because there has been no reported data regarding the phenolic profile of the first Brazilian VOO, the aim of this work was to determine phenolic contents of these samples using rapid-resolution liquid chromatography coupled to electrospray ionisation time-of-flight mass spectrometry. 25 VOO samples from Arbequina, Koroneiki, Arbosana, Grappolo, Manzanilla, Coratina, Frantoio and MGS Mariense varieties from three different Brazilian states and two crops were analysed. It was possible to quantify 19 phenolic compounds belonging to different classes. The results indicated that Brazilian VOOs have high total phenolic content because the values were comparable with those from high-quality VOOs produced in other countries. VOOs from Coratina, Arbosana and Grappolo presented the highest total phenolic content. These data will be useful in the development and improvement of Brazilian VOO. PMID:25306359

  10. Gas chromatography/flame ionisation detection mass spectrometry for the detection of endogenous urine metabolites for metabonomic studies and its use as a complementary tool to nuclear magnetic resonance spectroscopy.

    PubMed

    Fancy, Sally-Ann; Beckonert, Olaf; Darbon, Gareth; Yabsley, Warren; Walley, Rosalind; Baker, David; Perkins, George L; Pullen, Frank S; Rumpel, Klaus

    2006-01-01

    Metabonomics is a relatively new field of research in which the total pool of metabolites in body fluids or tissues from different patient groups is subjected to comparative analysis. Nuclear magnetic resonance (NMR) spectroscopy is the technology that is currently most widely used for the analysis of these highly complex metabolite mixtures, and hundreds of metabolites can be detected without any upfront separation. We have investigated in this study whether gas chromatography (GC) separation in combination with flame ionisation detection (FID) and mass spectrometry (MS) detection can be used for metabolite profiling from urine. We show that although GC sample preparation is much more involved than for NMR, hundreds of metabolites can reproducibly be detected and analysed by GC. We show that the data quality is sufficiently high--particularly if appropriate baseline correction and time-warping methods are applied--to allow for data comparison by chemometrics methods. A sample set of urines from eleven healthy human volunteers was analysed independently by GC and NMR, and subsequent chemometrics analysis of the two datasets showed some similar features. As judged by NIST database searches of the GC/MS data some of the major metabolites that are detected by NMR are also visible by GC/MS. Since in contrast to NMR every peak in GC corresponds to a single metabolite, the electron ionisation spectra can be used to quickly identify metabolites of interest if their reference spectra are present in a searchable database. In summary, we show that GC is a method that can be used as a complementary tool to NMR for metabolite profiling of urine samples.

  11. Cosmic-ray ionisation of dense molecular clouds

    NASA Astrophysics Data System (ADS)

    Vaupre, Solenn

    2015-07-01

    Cosmic rays (CR) are of tremendous importance in the dynamical and chemical evolution of interstellar molecular clouds, where stars and planets form. CRs are likely accelerated in the shells of supernova remnants (SNR), thus molecular clouds nearby can be irradiated by intense fluxes of CRs. CR protons have two major effects on dense molecular clouds: 1) when they encounter the dense medium, high-energy protons (>280 MeV) create pions that decay into gamma-rays. This process makes SNR-molecular cloud associations intense GeV and/or TeV sources whose spectra mimic the CR spectrum. 2) at lower energies, CRs penetrate the cloud and ionise the gas, leading to the formation of molecular species characteristic of the presence of CRs, called tracers of the ionisation. Studying these tracers gives information on low-energy CRs that are unaccessible to any other observations. I studied the CR ionisation of molecular clouds next to three SNRs: W28, W51C and W44. These SNRs are known to be interacting with the nearby clouds, from the presence of shocked gas, OH masers and pion-decay induced gamma-ray emission. My work includes millimeter observations and chemical modeling of tracers of the ionisation in these dense molecular clouds. In these three regions, we determined an enhanced CR ionisation rate, supporting the hypothesis of an origin of the CRs in the SNR nearby. The evolution of the CR ionisation rate with the distance to the SNR brings valuable constraints on the propagation properties of low-energy CRs. The method used relies on observations of the molecular ions HCO+ and DCO+, which shows crucial limitations at high ionisation. Therefore, I investigated, both through modeling and observations, the chemical abundances of several other species to try and identity alternative tracers of the ionisation. In particular, in the W44 region, observations of N2H+ bring additional constraints on the physical conditions, volatile abundances in the cloud, and the ionisation

  12. A study of the analytical behaviour of selected psycho-active drugs using liquid chromatography, ion trap mass spectrometry, gas chromatography and polarography and the construction of an appropriate database for drug characterisation.

    PubMed

    Doherty, Bernadette; O'Donnell, Fionnuala; Smyth, W Franklin; Leslie, Julian C; Ramachandran, Venkataraman N; Boyd, Neil S; Hack, Catherine J; O'Kane, Edmund; McClean, Stephen

    2007-04-30

    This paper provides analytical chemical information on a range of psycho-active drugs. This analytical chemical information on liquid chromatography-electrospray ionisation-mass spectrometry (HPLC-ESI-MS), ion trap mass spectrometry (ESI-MS(n)), gas chromatography-flame ionisation detection (GLC-FID) and polarographic behaviour is then incorporated into a database which is of use in drug characterisation. Application is found in the determination of selected drug compounds in hair samples.

  13. Comparison of phenotypic methods and matrix-assisted laser desorption ionisation time-of-flight mass spectrometry for the identification of aero-tolerant Actinomyces spp. isolated from soft-tissue infections.

    PubMed

    Ng, L S Y; Sim, J H C; Eng, L C; Menon, S; Tan, T Y

    2012-08-01

    Aero-tolerant Actinomyces spp. are an under-recognised cause of cutaneous infections, in part because identification using conventional phenotypic methods is difficult and may be inaccurate. Matrix-assisted laser desorption ionisation time-of-flight mass spectrometry (MALDI-TOF MS) is a promising new technique for bacterial identification, but with limited data on the identification of aero-tolerant Actinomyces spp. This study evaluated the accuracy of a phenotypic biochemical kit, MALDI-TOF MS and genotypic identification methods for the identification of this problematic group of organisms. Thirty aero-tolerant Actinomyces spp. were isolated from soft-tissue infections over a 2-year period. Species identification was performed by 16 s rRNA sequencing and genotypic results were compared with results obtained by API Coryne and MALDI-TOF MS. There was poor agreement between API Coryne and genotypic identification, with only 33% of isolates correctly identified to the species level. MALDI-TOF MS correctly identified 97% of isolates to the species level, with 33% of identifications achieved with high confidence scores. MALDI-TOF MS is a promising new tool for the identification of aero-tolerant Actinomyces spp., but improvement of the database is required in order to increase the confidence level of identification.

  14. Differentiation of vanA-positive Enterococcus faecium from vanA-negative E. faecium by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Nakano, Satoshi; Matsumura, Yasufumi; Kato, Karin; Yunoki, Tomoyuki; Hotta, Go; Noguchi, Taro; Yamamoto, Masaki; Nagao, Miki; Ito, Yutaka; Takakura, Shunji; Ichiyama, Satoshi

    2014-09-01

    Vancomycin-resistant enterococci are important nosocomial pathogens that require rapid and accurate detection for infection control. Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF/MS) has begun to be used in many clinical laboratories because it is a rapid, simple and inexpensive method for identifying micro-organisms. In this study, the performance of MALDI-TOF/MS to differentiate vanA-positive Enterococcus faecium (VPEF) from vanA-negative E. faecium (VNEF) was evaluated. A total of 61 VPEF isolates collected during regional surveillance in Kyoto (Japan) and 71 VNEF isolates collected from bacteraemia patients were analysed using MALDI-TOF/MS with three ClinProTools models. All of the isolates were correctly identified as E. faecium using the MALDI Biotyper system. To discriminate between VPEF and VNEF, all three ClinProTools models yielded >90% recognition capability (basic sensitivity) and cross-validation (reliability of the models); the genetic algorithm model exhibited the highest performance (99.18% and 92.40%, respectively). The high detection performance of MALDI-TOF/MS for VPEF offers the potential for routine laboratory use. PMID:25104134

  15. Differentiation of vanA-positive Enterococcus faecium from vanA-negative E. faecium by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Nakano, Satoshi; Matsumura, Yasufumi; Kato, Karin; Yunoki, Tomoyuki; Hotta, Go; Noguchi, Taro; Yamamoto, Masaki; Nagao, Miki; Ito, Yutaka; Takakura, Shunji; Ichiyama, Satoshi

    2014-09-01

    Vancomycin-resistant enterococci are important nosocomial pathogens that require rapid and accurate detection for infection control. Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF/MS) has begun to be used in many clinical laboratories because it is a rapid, simple and inexpensive method for identifying micro-organisms. In this study, the performance of MALDI-TOF/MS to differentiate vanA-positive Enterococcus faecium (VPEF) from vanA-negative E. faecium (VNEF) was evaluated. A total of 61 VPEF isolates collected during regional surveillance in Kyoto (Japan) and 71 VNEF isolates collected from bacteraemia patients were analysed using MALDI-TOF/MS with three ClinProTools models. All of the isolates were correctly identified as E. faecium using the MALDI Biotyper system. To discriminate between VPEF and VNEF, all three ClinProTools models yielded >90% recognition capability (basic sensitivity) and cross-validation (reliability of the models); the genetic algorithm model exhibited the highest performance (99.18% and 92.40%, respectively). The high detection performance of MALDI-TOF/MS for VPEF offers the potential for routine laboratory use.

  16. Determination of quinolones and fluoroquinolones in fish tissue and seafood by high-performance liquid chromatography with electrospray ionisation tandem mass spectrometric detection.

    PubMed

    Johnston, Lesley; Mackay, Lindsey; Croft, Meg

    2002-12-20

    A reversed-phase high-performance liquid chromatographic method with tandem mass-spectrometric detection was developed and validated for the simultaneous analysis of eight quinolones and fluoroquinolones (oxolinic acid, flumequine, piromidic acid, enrofloxacin, ciprofloxacin, danofloxacin, sarafloxacin and orbifloxacin) in trout tissue, prawns and abalone. The analytes were extracted from homogenised tissue using acetonitrile and the extracts subjected to an automated two-stage solid-phase extraction process involving polymeric reversed-phase and anion-exchange cartridges. Good recoveries were obtained for all analytes and the limit of quantification was 5 microg/kg (10 microg/kg for ciprofloxacin). The limit of detection was 1-3 microg/kg, depending on the analyte and matrix. Confirmation of the identity of a residue was achieved by further tandem mass-spectrometric analysis. A procedure for estimating the uncertainty associated with the measurement is presented.

  17. Potential of mass spectrometry metabolomics for chemical food safety.

    PubMed

    Gallart-Ayala, Hector; Chéreau, Sylvain; Dervilly-Pinel, Gaud; Le Bizec, Bruno

    2015-01-01

    This review aims to describe the most significant applications of mass spectrometry-based metabolomics in the field of chemical food safety. A particular discussion of all the different analytical steps involved in the metabolomics workflow (sample preparation, mass spectrometry analytical platform and data processing) will be addressed.

  18. Genotyping for Glycophorin GYP(B-A-B) Hybrid Genes Using a Single Nucleotide Polymorphism-Based Algorithm by Matrix-Assisted Laser Desorption/Ionisation, Time-of-Flight Mass Spectrometry.

    PubMed

    Wei, Ling; Lopez, Genghis H; Ji, Yanli; Condon, Jennifer A; Irwin, Darryl L; Luo, Guangping; Hyland, Catherine A; Flower, Robert L

    2016-10-01

    The genetic basis for five GP(B-A-B) MNS system hybrid glycophorin blood group antigens results from rearrangement between the homologous GYPA and GYPB genes. Each hybrid glycophorin displays a characteristic profile of antigens. Currently, no commercial serological reagents are currently available to serologically type for these antigens. The aim of this study was to develop a single nucleotide polymorphism (SNP) mapping genotyping technique to allow characterisation of various GYP(B-A-B) hybrid alleles. Matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) mass spectrometry (MS) assays were designed to genotype five GYP(B-A-B) hybrid alleles. Eight nucleotide positions were targeted and incorporated into the SNP mapping protocol. The allelic frequencies were calculated using peak areas. Sanger sequencing was performed to resolve a GYP*Hop 3' breakpoint. Observed allelic peak area ratios either coincided with the expected ratio or were skewed (above or below) from the expected ratio with switching occurring at and after the expected break point to generate characteristic mass spectral plots for each hybrid. Sequencing showed that the GYP*Hop crossover in the intron 3 region, for this example, was identical to that for GYP*Bun reference sequence. An analytical algorithm using MALDI-TOF MS genotyping platform defined GYPA inserts for five GYP(B-A-B) hybrids. The SNP mapping technique described here demonstrates proof of concept that this technology is viable for genotyping hybrid glycophorins, GYP(A-B-A), GYP(A-B) and GYP(B-A), and addresses the gap in current typing technologies.

  19. Selective solid-phase isolation of methionine-containing peptides and subsequent matrix-assisted laser desorption/ionisation mass spectrometric detection of methionine- and of methionine-sulfoxide-containing peptides.

    PubMed

    Grunert, Tom; Pock, Katharina; Buchacher, Andrea; Allmaier, Günter

    2003-01-01

    Methionine residues and the oxidised forms in proteins are becoming more and more important in view of their biological function. In particular, methionine sulfoxide seems to have a regulatory function. This paper presents a fast strategy for simultaneous determination of methionine- and methionine-sulfoxide-containing peptides, involving application of methionine-specific solid-phase reagent chemistry combined with matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS). In the first step, methionine-containing peptides are covalently bound as sulfonium salts to glass beads, whereas methionine-sulfoxide-containing peptides and other methionine-free peptides are not bound and are washed out. The wash solution is used for MALDI-MS analysis to determine the molecular masses of these peptides and to perform, if necessary, seamless post-source decay (PSD) fragment ion analysis. Methionine-sulfoxide-containing peptides can be identified due to the characteristic metastable loss of methanesulfenic acid from the protonated molecules. In the second step, the bound peptides are cleaved from the matrix of the beads by addition of 2-mercaptoethanol at pH 8.5-8.8. The resulting peptides, mainly methionine-containing peptides, are analysed in a straightforward manner by MALDI-MS and seamless PSD. The strategy allows the fast identification of methionine- and methionine-sulfoxide-containing peptides even in complex tryptic digests, as demonstrated here for the glycoprotein antithrombin. These results show that sometimes methionine-containing tryptic peptides are not detected due to steric restrictions (e.g. glycosylation near the methionine residue) on the binding reaction, and that, on the other hand, some methionine-free peptides can be quite strongly bound non-covalently to the matrix of the beads. The latter observation indicates the necessity of seamless PSD fragment ion analysis for unambiguous identification. Furthermore, there are indications that

  20. Simultaneous determination of amiloride and hydrochlorothiazide in human plasma by liquid chromatography/tandem mass spectrometry with positive/negative ion-switching electrospray ionisation.

    PubMed

    Song, Min; Hang, Taijun; Zhao, Hua; Wang, Li; Ge, Ping; Ma, Pengcheng

    2007-01-01

    A new method for simultaneous determination of amiloride and hydrochlorothiazide by liquid chromatography/electrospray tandem mass spectrometry (LC/MS/MS) operated in positive and negative ionization switching mode was developed and validated. Protein precipitation with acetonitrile was selected for sample preparation. The analytes were separated on a Phenomenex Curosil-PFP (250x4.6 mm, 5 microm) column by a gradient elution with a mobile phase consisting of 0.15% formic acid solution containing 0.23% ammonium acetate and methanol pumped at a flow rate of 1.0 mL.min(-1). Rizatriptan was used as the internal standard (IS) for quantification. The determination was carried out on a Waters Quattro-micro triple-quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode using the following transitions monitored simultaneously: positive m/z 230-->171 for amiloride, m/z 270-->158 for rizatriptan, and negative m/z 296-->205 for hydrochlorothiazide. The lower limits of quantification (LLOQs) were 0.1 and 1.0 ng.mL(-1) for amiloride and hydrochlorothiazide, respectively, which were lower than other published methods by using ultraviolet (UV), fluorimetric or mass spectrometric detection. The intra- and inter-day precision and accuracy were studied at three different concentration levels and were always better than 15% (n=5). This simple and robust LC/MS/MS method was successfully applied to the pharmacokinetic study of compound amiloride and hydrochlorothiazide tablets in healthy male Chinese volunteers. PMID:17902196

  1. Sizing up large protein complexes by electrospray ionisation-based electrophoretic mobility and native mass spectrometry: morphology selective binding of Fabs to hepatitis B virus capsids.

    PubMed

    Bereszczak, Jessica Z; Havlik, Marlene; Weiss, Victor U; Marchetti-Deschmann, Martina; van Duijn, Esther; Watts, Norman R; Wingfield, Paul T; Allmaier, Guenter; Steven, Alasdair C; Heck, Albert J R

    2014-02-01

    The capsid of hepatitis B virus (HBV) is a major viral antigen and important diagnostic indicator. HBV capsids have prominent protrusions ('spikes') on their surface and are unique in having either T = 3 or T = 4 icosahedral symmetry. Mouse monoclonal and also human polyclonal antibodies bind either near the spike apices (historically the 'α-determinant') or in the 'floor' regions between them (the 'β-determinant'). Native mass spectrometry (MS) and gas-phase electrophoretic mobility molecular analysis (GEMMA) were used to monitor the titration of HBV capsids with the antigen-binding domain (Fab) of mAb 3120, which has long defined the β-determinant. Both methods readily distinguished Fab binding to the two capsid morphologies and could provide accurate masses and dimensions for these large immune complexes, which range up to ~8 MDa. As such, native MS and GEMMA provide valuable alternatives to a more time-consuming cryo-electron microscopy analysis for preliminary characterisation of virus-antibody complexes.

  2. Validation of a method for the analysis of quinolones residues in bovine muscle by liquid chromatography with electrospray ionisation tandem mass spectrometry detection.

    PubMed

    Rubies, A; Vaquerizo, R; Centrich, F; Compañó, R; Granados, M; Prat, M D

    2007-04-15

    A liquid chromatography-tandem mass spectrometry method for the determination and confirmation of nine quinolones was optimised and validated according to Commission Decision 2002/657/EC. Analytes were extracted from veal muscle with water and extracts purified with 96-well plates Oasis HLB cartridges. Separation was carried out in a silica-based C(18) column (50mmx2.1mm) with mobile phases consisting of water/acetonitrile mixtures containing acetic acid. Linear calibration curves in the ranges 4-400 and 50-800ngg(-1), with correlation coefficients at least 0.995, were obtained for all the analytes. At concentration levels above 10ngg(-1), quantification errors were lower than 10% and repeatability and within-laboratory reproducibility standard deviations below 6% and 10%, respectively. Decision limits and detection capabilities are reported.

  3. Validation of a method for the analysis of quinolones residues in bovine muscle by liquid chromatography with electrospray ionisation tandem mass spectrometry detection.

    PubMed

    Rubies, A; Vaquerizo, R; Centrich, F; Compañó, R; Granados, M; Prat, M D

    2007-04-15

    A liquid chromatography-tandem mass spectrometry method for the determination and confirmation of nine quinolones was optimised and validated according to Commission Decision 2002/657/EC. Analytes were extracted from veal muscle with water and extracts purified with 96-well plates Oasis HLB cartridges. Separation was carried out in a silica-based C(18) column (50mmx2.1mm) with mobile phases consisting of water/acetonitrile mixtures containing acetic acid. Linear calibration curves in the ranges 4-400 and 50-800ngg(-1), with correlation coefficients at least 0.995, were obtained for all the analytes. At concentration levels above 10ngg(-1), quantification errors were lower than 10% and repeatability and within-laboratory reproducibility standard deviations below 6% and 10%, respectively. Decision limits and detection capabilities are reported. PMID:19071613

  4. Non ionising radiation as a non chemical strategy in regenerative medicine: Ca(2+)-ICR "In Vitro" effect on neuronal differentiation and tumorigenicity modulation in NT2 cells.

    PubMed

    Ledda, Mario; Megiorni, Francesca; Pozzi, Deleana; Giuliani, Livio; D'Emilia, Enrico; Piccirillo, Sara; Mattei, Cristiana; Grimaldi, Settimio; Lisi, Antonella

    2013-01-01

    In regenerative medicine finding a new method for cell differentiation without pharmacological treatment or gene modification and minimal cell manipulation is a challenging goal. In this work we reported a neuronal induced differentiation and consequent reduction of tumorigenicity in NT2 human pluripotent embryonal carcinoma cells exposed to an extremely low frequency electromagnetic field (ELF-EMF), matching the cyclotron frequency corresponding to the charge/mass ratio of calcium ion (Ca(2+)-ICR). These cells, capable of differentiating into post-mitotic neurons following treatment with Retinoic Acid (RA), were placed in a solenoid and exposed for 5 weeks to Ca(2+)-ICR. The solenoid was installed in a μ-metal shielded room to avoid the effect of the geomagnetic field and obtained totally controlled and reproducible conditions. Contrast microscopy analysis reveled, in the NT2 exposed cells, an important change in shape and morphology with the outgrowth of neuritic-like structures together with a lower proliferation rate and metabolic activity alike those found in the RA treated cells. A significant up-regulation of early and late neuronal differentiation markers and a significant down-regulation of the transforming growth factor-α (TGF-α) and the fibroblast growth factor-4 (FGF-4) were also observed in the exposed cells. The decreased protein expression of the transforming gene Cripto-1 and the reduced capability of the exposed NT2 cells to form colonies in soft agar supported these last results. In conclusion, our findings demonstrate that the Ca(2+)-ICR frequency is able to induce differentiation and reduction of tumorigenicity in NT2 exposed cells suggesting a new potential therapeutic use in regenerative medicine.

  5. Characterisation of intact recombinant human erythropoietins applied in doping by means of planar gel electrophoretic techniques and matrix-assisted laser desorption/ionisation linear time-of-flight mass spectrometry.

    PubMed

    Stübiger, Gerald; Marchetti, Martina; Nagano, Marietta; Reichel, Christian; Gmeiner, Günter; Allmaier, Günter

    2005-01-01

    Our experiments show that it is possible to detect different types of recombinant human erythropoietins (rhEPOs), EPO-alpha, EPO-beta and novel erythropoesis stimulating protein (NESP), based on exact molecular weight (MW) determination by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) applying a high-resolution time-of-flight (TOF) mass analyser in the linear mode. Detection limits for the highly purified, intact glycoproteins were achievable in the low fmol range (25-50 fmol) using a sample preparation method applying a hydrophobic sample support (DropStop) as MALDI target surface. These results are very promising for the development of highly sensitive detection methods for a direct identification of rhEPO after enrichment from human body fluids. During our investigation we were able to differentiate EPO-alpha, EPO-beta and NESP based on distinct molecular substructures at the protein level by specific enzymatic reactions. MW determination of the intact molecules by high resolving one-dimensional sodium dodecyl sulfate /polyacrylamide gel electrophoresis (1D SDS-PAGE) and isoform separation by planar isoelectric focusing (IEF) was compared with MALDI-MS data. Migration differences between the rhEPOs were observed from gel electrophoresis, whereby MWs of 38 kDa in the case of EPO-alpha/beta and 49 kDa for NESP could be estimated. In contrast, an exact MW determination by MALDI-MS based on internal calibration revealed average MWs of 29.8 +/- 0.3 kDa for EPO-alpha/beta and 36.8 +/- 0.4 kDa for NESP. IEF separation of the intact rhEPOs revealed the presence of four to eight distinct isoforms in EPO-alpha and EPO-beta, while four isoforms, which appeared in the more acidic area of the gels, were detected by immunostaining in NESP. A direct detection of the different N- or O-glycoform pattern from rhEPOs using MALDI-MS was possible by de-sialylation of the glycan structures and after de-N-glycosylation of the intact molecules. Thereby, the

  6. Development and optimisation of a dopant assisted liquid chromatographic-atmospheric pressure photo ionisation-tandem mass spectrometric method for the determination of 15+1 EU priority PAHs in edible oils.

    PubMed

    Hollosi, Laszlo; Wenzl, Thomas

    2011-01-01

    European food legislation defines a set of 16 polycyclic aromatic hydrocarbons (PAHs) as of high concern for human health. The EU set contains structurally very similar PAHs with ring numbers between 4 and 6, and so raises some separation aspects and problems, which were not experienced with traditionally analysed PAHs. Many of the currently applied gas chromatographic mass spectrometric (GC-MS) methods suffer from separation problems, while high performance liquid chromatography with fluorescence detection (HPLC-FLD) is neither capable of detecting the whole set of EU priority PAHs nor does it (compared to GC-MS) allow structural identification. In addition HPLC-FLD shows limitations with difficult matrices due to interferences. The aim of this paper is to fill this gap by describing a liquid chromatographic dopant assisted atmospheric pressure photo ionisation tandem mass spectrometric (LC-DA-APPI-MS/MS) method for the determination of 15+1 EU priority PAHs in edible oil, which complies with the requirements set by European food legislation. Measurements were performed in positive ion mode. Anisole at a flow rate of 30 μl/min was used as dopant. Sample preparation was performed offline by donor-acceptor complex chromatography (DACC). Compared to HPLC-FLD methods the presented method enables the determination of all 15+1 EU priority PAHs at the low μg/kg concentration range including less fluorescence active compounds like benzo[j]fluoranthene and indeno[1,2,3-cd]pyrene. By analysing four reference materials it could be demonstrated that this method provides accurate results and is sufficiently sensitive for food control purposes. Statistically significant differences between the reference values and the measured analyte contents were not found. The method performs well also for very complex samples. Repeatability relative standard deviations (RSDr) of the determination of the target PAHs in olive oil were for most analytes below 5%. The limit of detection (LOD

  7. Ionisers in the management of bronchial asthma.

    PubMed Central

    Nogrady, S G; Furnass, S B

    1983-01-01

    Because of recent interest in the possible benefits to asthmatic patients of negative ion generators and the largely uncontrolled and inconclusive nature of earlier studies a double blind crossover study of this treatment was carried out in 20 subjects with stable asthma over six months. After an initial two week period without an ioniser, active or placebo ionisers were installed in subjects' bedrooms for two eight week periods separated by a four week "washout" period when no ioniser was present. The study was completed by a final four week period when no ioniser was present. Subjects were randomly allocated to receive an active or a placebo ioniser first. Subjects recorded their peak expiratory flow rate (PEFR) twice daily, completed a daily symptom score questionnaire, and noted any treatment they took on a diary card. Recordings were completed throughout the trial. Ion counts and dust concentrations were measured in subjects' bedrooms during the study. Mean ion counts rose considerably when ionisers were activated (p less than 0.001). There were no significant differences in PEFR, symptom score, or consumption of medication between the periods that active ionisers and either no ionisers or placebo ionisers were in operation. This study has failed to show a statistically significant benefit in asthmatic subjects from the use of negative ion generators. PMID:6364442

  8. CHEMICAL MASS BALANCE MODEL: EPA-CMB8.2

    EPA Science Inventory

    The Chemical Mass Balance (CMB) method has been a popular approach for receptor modeling of ambient air pollutants for over two decades. For the past few years the U.S. Environmental Protection Agency's Office of Research and Development (ORD) and Office of Air Quality Plannin...

  9. Vertical profile measurements of lower troposphere ionisation

    NASA Astrophysics Data System (ADS)

    Harrison, R. G.; Nicoll, K. A.; Aplin, K. L.

    2014-11-01

    Vertical soundings of the atmospheric ion production rate have been obtained from Geiger counters integrated with conventional meteorological radiosondes. In launches made from Reading (UK) during 2013-2014, the Regener-Pfotzer ionisation maximum was at an altitude equivalent to a pressure of (63.1±2.4) hPa, or, expressed in terms of the local air density, (0.101±0.005) kg m-3. The measured ionisation profiles have been evaluated against the Usoskin-Kovaltsov model and, separately, surface neutron monitor data from Oulu. Model ionisation rates agree well with the observed cosmic ray ionisation below 20 km altitude. Above 10 km, the measured ionisation rates also correlate well with simultaneous neutron monitor data, although, consistently with previous work, measured variability at the ionisation maximum is greater than that found by the neutron monitor. However, in the lower atmosphere (below 5 km altitude), agreement between the measurements and simultaneous neutron monitor data is poor. For studies of transient lower atmosphere phenomena associated with cosmic ray ionisation, this indicates the need for in situ ionisation measurements and improved lower atmosphere parameterisations.

  10. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Spencer, K. M.; Beaver, M. R.; St. Clair, J. M.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2011-08-01

    Chemical ionization mass spectrometry (CIMS) enables online, fast, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are capable of the measurement of hydroxyacetone, an analyte with minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. Measurement of hydroxyacetone and glycolaldehyde by these methods was demonstrated during the ARCTAS-CARB 2008 campaign and the BEARPEX 2009 campaign. Enhancement ratios of these compounds in ambient biomass burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  11. Identification and Quantitative Measurements of Chemical Species by Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Zondlo, Mark A.; Bomse, David S.

    2005-01-01

    The development of a miniature gas chromatograph/mass spectrometer system for the measurement of chemical species of interest to combustion is described. The completed system is a fully-contained, automated instrument consisting of a sampling inlet, a small-scale gas chromatograph, a miniature, quadrupole mass spectrometer, vacuum pumps, and software. A pair of computer-driven valves controls the gas sampling and introduction to the chromatographic column. The column has a stainless steel exterior and a silica interior, and contains an adsorbent of that is used to separate organic species. The detection system is based on a quadrupole mass spectrometer consisting of a micropole array, electrometer, and a computer interface. The vacuum system has two miniature pumps to maintain the low pressure needed for the mass spectrometer. A laptop computer uses custom software to control the entire system and collect the data. In a laboratory demonstration, the system separated calibration mixtures containing 1000 ppm of alkanes and alkenes.

  12. Miniature mass spectrometer for chemical sensing in homeland defense applications

    NASA Astrophysics Data System (ADS)

    Sinha, Mahadeva P.; Houseman, John

    2003-07-01

    A Miniature Mass Spectrometer (MMS) with an array detector has been developed at the Jet Propulsion Laboratory (JPL). The spectrometer has a focal plane geometry, and an array detector that can measure the intensities of different masses simultaneously after their separation along the focal plane. In the past, the large mass, size and the lack of an array detector with high gain (such as an electron multiplier) did not allow the application of focal plane mass spectrometer to the measurement that required high sensitivity and portability. In the JPL developed-MMS, miniaturization has been accomplished by using rare earth magnet material and novelties in the design of the magnetic and electric sectors. A new ion detector was developed for the measurement of the intensities of different mass ions. The array detector is based on the conversion sequence of ions into electrons into photons and their final measurement by a photon array detector. MMS possesses high sensitivity, specificity, and fast response time and can be used as a universal chemical analyzer. It will find application in a variety of Home Defense tasks. MMS is presently being applied for the detection of propellants (hydrazine and its derivatives). The instrument will have a mass of 1-2 kg and consume a power of 2-4 W for operation

  13. Oxalate Mass Balance During Chemical Cleaning in Tank 5F

    SciTech Connect

    Poirier, M.; Fink, S.

    2011-07-08

    The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 5F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate.

  14. OXALATE MASS BALANCE DURING CHEMICAL CLEANING IN TANK 6F

    SciTech Connect

    Poirier, M.; Fink, S.

    2011-07-22

    The Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRR personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 6F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate. Some conclusions from this work are: (1) Approximately 65% of the oxalate added as oxalic acid was removed with the decanted liquid. (2) Approximately 1% of the oxalate (added to the tank as oxalic acid) formed precipitates with compounds such as nickel, manganese, sodium, and iron (II), and was dissolved with nitric acid. (3) As much as 30% of the oxalate may have decomposed forming carbon dioxide. The balance does not fully account for all the oxalate added. The offset represents the combined uncertainty in the analyses and sampling.

  15. Characterization of glycosphingolipids by direct inlet chemical ionization mass spectrometry.

    PubMed

    Ariga, T; Murata, T; Oshima, M; Maezawa, M; Miyatake, T

    1980-09-01

    Permethylated derivatives of cerebrosides and ceramide di-, tri-, tetra-, and penta-hexosides were analyzed by the direct inlet ammonia chemical ionization (CI) mass spectrometry. In the CI mass spectra, the fragment ions produced by the loss of methanol from the protonated molecular ion were observed in all of the glycosphingolipids. Other fragment ions due to the cleavage of glycosidic moiety were major ones under the CI conditions. These ions provide information on the molecular species of glycosphingolipids and the sugar sequence of their oligosaccharides. Glycosphingolipids with hydroxy fatty acids could also be differentiated from those with nonhydroxy fatty acids by comparing the intensities of characteristic fragment ions. The CI method should be particularly useful in structural studies of glycosphingolipids from natural sources. PMID:7441059

  16. Chemical separations by bubble-assisted interphase mass-transfer.

    PubMed

    Boyd, David A; Adleman, James R; Goodwin, David G; Psaltis, Demetri

    2008-04-01

    We show that when a small amount of heat is added close to a liquid-vapor interface of a captive gas bubble in a microchannel, interphase mass-transfer through the bubble can occur in a controlled manner with only a slight change in the temperature of the fluid. We demonstrate that this method, which we refer to as bubble-assisted interphase mass-transfer (BAIM), can be applied to interphase chemical separations, e.g., simple distillation, without the need for high temperatures, vacuum, or active cooling. Although any source of localized heating could be used, we illustrate BAIM with an all-optical technique that makes use of the plasmon resonance in an array of nanoscale metal structures that are incorporated into the channel to produce localized heating of the fluid when illuminated by a stationary low-power laser.

  17. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    St. Clair, J. M.; Spencer, K. M.; Beaver, M. R.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2014-04-01

    Chemical ionization mass spectrometry (CIMS) enables online, rapid, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are generally capable of the measurement of hydroxyacetone, an analyte with known but minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. The single quadrupole CIMS measurement of glycolaldehyde was demonstrated during the ARCTAS-CARB (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites - California Air Resources Board) 2008 campaign, while triple quadrupole CIMS measurements of glycolaldehyde and hydroxyacetone were demonstrated during the BEARPEX (Biosphere Effects on Aerosols and Photochemistry Experiment) 2009 campaign. Enhancement ratios of glycolaldehyde in ambient biomass-burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  18. Constraining Anthropogenic and Biogenic Emissions Using Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Spencer, Kathleen M.

    Numerous gas-phase anthropogenic and biogenic compounds are emitted into the atmosphere. These gases undergo oxidation to form other gas-phase species and particulate matter. Whether directly or indirectly, primary pollutants, secondary gas-phase products, and particulate matter all pose health and environmental risks. In this work, ambient measurements conducted using chemical ionization mass spectrometry are used as a tool for investigating regional air quality. Ambient measurements of peroxynitric acid (HO2NO2) were conducted in Mexico City. A method of inferring the rate of ozone production, PO3, is developed based on observations of HO2NO 2, NO, and NO2. Comparison of this observationally based PO3 to a highly constrained photochemical box model indicates that regulations aimed at reducing ozone levels in Mexico City by reducing NOx concentrations may be effective at higher NO x levels than predicted using accepted photochemistry. Measurements of SO2 and particulate sulfate were conducted over the Los Angeles basin in 2008 and are compared to measurements made in 2002. A large decrease in SO2 concentration and a change in spatial distribution are observed. Nevertheless, only a modest reduction in sulfate concentration is observed at ground sites within the basin. Possible explanations for these trends are investigated. Two techniques, single and triple quadrupole chemical ionization mass spectrometry, were used to quantify ambient concentrations of biogenic oxidation products, hydroxyacetone and glycolaldehyde. The use of these techniques demonstrates the advantage of triple quadrupole mass spectrometry for separation of mass analogues, provided the collision-induced daughter ions are sufficiently distinct. Enhancement ratios of hydroxyacetone and glycolaldehyde in Californian biomass burning plumes are presented as are concentrations of these compounds at a rural ground site downwind of Sacramento.

  19. THE INFLUENCE OF SALTS UPON THE IONISATION OF EGG ALBUMIN

    PubMed Central

    Sørensen, S. P. L.; Linderstrøm-Lang, K.; Lund, Ellen

    1927-01-01

    Linderstrøm-Lang's theory for the ionisation of polyvalent ampholytes of simple type. It is shown that the salt effect, in accordance with the theory, and in qualitative agreement with the experiments, consists in a turning of the ionisation curves, indicating the relation between the quantity of combined acid (specific hydrogen ionisation) and paH, and the turning of the curves, which leaves the isoelectric reaction unaltered, tends in such a direction that the quantity of combined acid at constant ampholyte concentration and constant pan increases with increasing salt concentration. The possibility of chemical combining of other ions than the hydrogen ion is discussed. 2). Following on 1), a brief survey of the experimental results is given. 3). The isoionic reaction is found from the experimental material and proved to be independent of the ammonium chloride concentration. As the mean of all determinations we have paH0 = 4.898 (isoionic reaction). The difference between this value and that formerly found for ammonium sulphate solutions (4.844) is discussed. 4). Finally, on the basis of the theory in Section 1), some simple calculations of the ionisation curves for egg albumin are made, and it appears that the theory can reproduce the experimental results in a rough quantitative way when we assume that the egg albumin has a radius of 2.21·10–7 cm. (answering to a molecular weight of 35,000 in aqueous solution), and contains 30 acid and base groups. PMID:19872215

  20. The ram accelerator - A chemically driven mass launcher

    NASA Technical Reports Server (NTRS)

    Kaloupis, P.; Bruckner, A. P.

    1988-01-01

    The ram accelerator, a chemically propelled mass driver, is presented as a viable new approach for directly launching acceleration-insensitive payloads into low earth orbit. The propulsion principle is similar to that of a conventional air-breathing ramjet. The cargo vehicle resembles the center-body of a ramjet and travels through a tube filled with a pre-mixed fuel and oxidizer mixture. The launch tube acts as the outer cowling of the ramjet and the combustion process travels with the vehicle. Two drive modes of the ram accelerator propulsion system are described, which when used in sequence are capable of accelerating the vehicle to as high as 10 km/sec. The requirements are examined for placing a 2000 kg vehicle into a 500 km orbit with a minimum of on-board rocket propellant for circularization maneuvers. It is shown that aerodynamic heating during atmospheric transit results in very little ablation of the nose. An indirect orbital insertion scenario is selected, utilizing a three step maneuver consisting of two burns and aerobraking. An on-board propulsion system using storable liquid propellants is chosen in order to minimize propellant mass requirements, and the use of a parking orbit below the desired final orbit is suggested as a means to increase the flexibility of the mass launch concept. A vehicle design using composite materials is proposed that will best meet the structural requirements, and a preliminary launch tube design is presented.

  1. Solid-phase microextraction low temperature plasma mass spectrometry for the direct and rapid analysis of chemical warfare simulants in complex mixtures.

    PubMed

    Dumlao, Morphy C; Jeffress, Laura E; Gooding, J Justin; Donald, William A

    2016-06-21

    Solid-phase microextraction (SPME) is directly integrated with low temperature plasma ionisation mass spectrometry to rapidly detect organophosphate chemical warfare agent simulants and their hydrolysis products in chemical mixtures, including urine. In this sampling and ionization method, the fibre serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME surface. By use of a custom fabricated SPME fibre consisting of a stainless steel needle coated with a Linde Type A (LTA) zeolitic microporous material and low temperature plasma mass spectrometry, protonated dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP) and pinacolyl methylphosphonic acid (PinMPA) can be detected at less than 100 ppb directly in water and urine. Organophosphates were not readily detected by this approach using an uncoated needle in negative control experiments. The use of the LTA coating significantly outperformed the use of a high alumina Zeolite Socony Mobil-5 (ZSM-5) coating of comparable thickness that is significantly less polar than LTA. By conditioning the LTA probe by immersion in an aqueous CuSO4 solution, the ion abundance for protonated DMMP increased by more than 300% compared to that obtained without any conditioning. Sample recovery values were between 96 and 100% for each analyte. The detection of chemical warfare agent analogues and hydrolysis products required less than 2 min per sample. A key advantage of this sampling and ionization method is that analyte ions can be directly and rapidly sampled from chemical mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove beneficial for portable mass spectrometry applications because relatively low detection limits can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the

  2. Solid-phase microextraction low temperature plasma mass spectrometry for the direct and rapid analysis of chemical warfare simulants in complex mixtures.

    PubMed

    Dumlao, Morphy C; Jeffress, Laura E; Gooding, J Justin; Donald, William A

    2016-06-21

    Solid-phase microextraction (SPME) is directly integrated with low temperature plasma ionisation mass spectrometry to rapidly detect organophosphate chemical warfare agent simulants and their hydrolysis products in chemical mixtures, including urine. In this sampling and ionization method, the fibre serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME surface. By use of a custom fabricated SPME fibre consisting of a stainless steel needle coated with a Linde Type A (LTA) zeolitic microporous material and low temperature plasma mass spectrometry, protonated dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP) and pinacolyl methylphosphonic acid (PinMPA) can be detected at less than 100 ppb directly in water and urine. Organophosphates were not readily detected by this approach using an uncoated needle in negative control experiments. The use of the LTA coating significantly outperformed the use of a high alumina Zeolite Socony Mobil-5 (ZSM-5) coating of comparable thickness that is significantly less polar than LTA. By conditioning the LTA probe by immersion in an aqueous CuSO4 solution, the ion abundance for protonated DMMP increased by more than 300% compared to that obtained without any conditioning. Sample recovery values were between 96 and 100% for each analyte. The detection of chemical warfare agent analogues and hydrolysis products required less than 2 min per sample. A key advantage of this sampling and ionization method is that analyte ions can be directly and rapidly sampled from chemical mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove beneficial for portable mass spectrometry applications because relatively low detection limits can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the

  3. [Determination of homocysteine by tandem mass spectrometry with chemical ionization].

    PubMed

    Miroshnichenko, I I; Platova, A I; Safarova, T P; Iakovleva, O B

    2014-01-01

    Homocysteine (Hcy) is an intermediate of methionine metabolism. High plasma Hcy concentrations are an independent risk factor for stroke, peripheral vascular disease, deep venous thrombosis, coronary disease, and cognitive deficiency. Apparently, it is a great importance to measure Hcy levels in human blood. A new method for the quantification of Hcy by means of reversed-phase LC/atmospheric pressure chemical ionization mass spectrometry has been developed. The MRM ion transition, m/z 136.0 ® 90.0 was used for Hcy quantification. The limit of detection was 0.4 mM, quantification was performed from 1 mM to 40 mM with coefficient of determination of R2=0,997. The method was applied successfully to Hcy determination in human blood.

  4. Mass transport measurements and modeling for chemical vapor infiltration

    SciTech Connect

    Starr, T.L.; Chiang, D.Y.; Fiadzo, O.G.; Hablutzel, N.

    1997-12-01

    This project involves experimental and modeling investigation of densification behavior and mass transport in fiber preforms and partially densified composites, and application of these results to chemical vapor infiltration (CVI) process modeling. This supports work on-going at ORNL in process development for fabrication of ceramic matrix composite (CMC) tubes. Tube-shaped composite preforms are fabricated at ORNL with Nextel{trademark} 312 fiber (3M Corporation, St. Paul, MN) by placing and compressing several layers of braided sleeve on a tubular mandrel. In terms of fiber architecture these preforms are significantly different than those made previously with Nicalon{trademark} fiber (Nippon Carbon Corp., Tokyo, Japan) square weave cloth. The authors have made microstructure and permeability measurements on several of these preforms and a few partially densified composites so as to better understand their densification behavior during CVI.

  5. Tissue proteomics using chemical immobilization and mass spectrometry.

    PubMed

    Shah, Punit; Zhang, Bai; Choi, Caitlin; Yang, Shuang; Zhou, Jianying; Harlan, Robert; Tian, Yuan; Zhang, Zhen; Chan, Daniel W; Zhang, Hui

    2015-01-15

    Proteomics analysis is important for characterizing tissues to gain biological and pathological insights, which could lead to the identification of disease-associated proteins for disease diagnostics or targeted therapy. However, tissues are commonly embedded in optimal cutting temperature medium (OCT) or are formalin-fixed and paraffin-embedded (FFPE) in order to maintain tissue morphology for histology evaluation. Although several tissue proteomic analyses have been performed on FFPE tissues using advanced mass spectrometry (MS) technologies, high-throughput proteomic analysis of OCT-embedded tissues has been difficult due to the interference of OCT in the MS analysis. In addition, molecules other than proteins present in tissues further complicate tissue proteomic analysis. Here, we report the development of a method using chemical immobilization of proteins for peptide extraction (CIPPE). In this method, proteins are chemically immobilized onto a solid support; interferences from tissues and OCT embedding are removed by extensive washing of proteins conjugated on the solid support. Peptides are then released from the solid phase by proteolysis, enabling MS analysis. This method was first validated by eliminating OCT interference from a standard protein, human serum albumin, where all of the unique peaks contributed by OCT contamination were eradicated. Finally, this method was applied for the proteomic analysis of frozen and OCT-embedded tissues using iTRAQ (isobaric tag for relative and absolute quantitation) labeling and two-dimensional liquid chromatography tandem mass spectrometry. The data showed reproducible extraction and quantitation of 10,284 proteins from 3996 protein groups and a minimal impact of OCT embedding on the analysis of the global proteome of the stored tissue samples. PMID:25283129

  6. Tissue proteomics using chemical immobilization and mass spectrometry.

    PubMed

    Shah, Punit; Zhang, Bai; Choi, Caitlin; Yang, Shuang; Zhou, Jianying; Harlan, Robert; Tian, Yuan; Zhang, Zhen; Chan, Daniel W; Zhang, Hui

    2015-01-15

    Proteomics analysis is important for characterizing tissues to gain biological and pathological insights, which could lead to the identification of disease-associated proteins for disease diagnostics or targeted therapy. However, tissues are commonly embedded in optimal cutting temperature medium (OCT) or are formalin-fixed and paraffin-embedded (FFPE) in order to maintain tissue morphology for histology evaluation. Although several tissue proteomic analyses have been performed on FFPE tissues using advanced mass spectrometry (MS) technologies, high-throughput proteomic analysis of OCT-embedded tissues has been difficult due to the interference of OCT in the MS analysis. In addition, molecules other than proteins present in tissues further complicate tissue proteomic analysis. Here, we report the development of a method using chemical immobilization of proteins for peptide extraction (CIPPE). In this method, proteins are chemically immobilized onto a solid support; interferences from tissues and OCT embedding are removed by extensive washing of proteins conjugated on the solid support. Peptides are then released from the solid phase by proteolysis, enabling MS analysis. This method was first validated by eliminating OCT interference from a standard protein, human serum albumin, where all of the unique peaks contributed by OCT contamination were eradicated. Finally, this method was applied for the proteomic analysis of frozen and OCT-embedded tissues using iTRAQ (isobaric tag for relative and absolute quantitation) labeling and two-dimensional liquid chromatography tandem mass spectrometry. The data showed reproducible extraction and quantitation of 10,284 proteins from 3996 protein groups and a minimal impact of OCT embedding on the analysis of the global proteome of the stored tissue samples.

  7. Molecular secondary ion mass spectrometry: New dimensions in chemical characterization

    NASA Astrophysics Data System (ADS)

    Colton, Richard J.; Campana, Joseph E.; Kidwell, David A.; Ross, Mark M.; Wyatt, Jeffrey R.

    1985-04-01

    Secondary ion mass spectrometry (SIMS) has become a diverse tool for the study of many substances other than metals and semiconductors. This paper discusses the emission of polyatomic and molecular ions from surfaces that contain various inorganic and organic compounds including polymers and biomolecules. The mass and abundance distribution of cluster ions emitted from various solids — Van der Waals, metallic, ionic and covalent — are compared. Trends in the emission patterns are discussed in terms of a recombination or direct emission mechanism. The emission of molecular ions is also discussed with respect to the method of ionization and the various sample preparation and matrix-assisted procedures used. The matrices include various solid-state and liquid matrices such as ammonium chloride, charcoal, glycerol and gallium. Various chemical derivatization procedures have been developed to enhance the sensitivity of molecular SIMS and to detect selectively components in mixtures. The procedures are demonstrated for the low-level detection of airborne contaminants from paints, for the analysis of drugs in biological fluids, and for the sequencing of biomolecules such as peptides and sugars. The emission of characteristic fragment ions from the surfaces of polymers is also described for thick, insulating films.

  8. Estimating nutrient loadings using chemical mass balance approach.

    PubMed

    Jain, C K; Singhal, D C; Sharma, M K

    2007-11-01

    The river Hindon is one of the important tributaries of river Yamuna in western Uttar Pradesh (India) and carries pollution loads from various municipal and industrial units and surrounding agricultural areas. The main sources of pollution in the river include municipal wastes from Saharanpur, Muzaffarnagar and Ghaziabad urban areas and industrial effluents of sugar, pulp and paper, distilleries and other miscellaneous industries through tributaries as well as direct inputs. In this paper, chemical mass balance approach has been used to assess the contribution from non-point sources of pollution to the river. The river system has been divided into three stretches depending on the land use pattern. The contribution of point sources in the upper and lower stretches are 95 and 81% respectively of the total flow of the river while there is no point source input in the middle stretch. Mass balance calculations indicate that contribution of nitrate and phosphate from non-point sources amounts to 15.5 and 6.9% in the upper stretch and 13.1 and 16.6% in the lower stretch respectively. Observed differences in the load along the river may be attributed to uncharacterized sources of pollution due to agricultural activities, remobilization from or entrainment of contaminated bottom sediments, ground water contribution or a combination of these sources. PMID:17616829

  9. Estimating nutrient loadings using chemical mass balance approach.

    PubMed

    Jain, C K; Singhal, D C; Sharma, M K

    2007-11-01

    The river Hindon is one of the important tributaries of river Yamuna in western Uttar Pradesh (India) and carries pollution loads from various municipal and industrial units and surrounding agricultural areas. The main sources of pollution in the river include municipal wastes from Saharanpur, Muzaffarnagar and Ghaziabad urban areas and industrial effluents of sugar, pulp and paper, distilleries and other miscellaneous industries through tributaries as well as direct inputs. In this paper, chemical mass balance approach has been used to assess the contribution from non-point sources of pollution to the river. The river system has been divided into three stretches depending on the land use pattern. The contribution of point sources in the upper and lower stretches are 95 and 81% respectively of the total flow of the river while there is no point source input in the middle stretch. Mass balance calculations indicate that contribution of nitrate and phosphate from non-point sources amounts to 15.5 and 6.9% in the upper stretch and 13.1 and 16.6% in the lower stretch respectively. Observed differences in the load along the river may be attributed to uncharacterized sources of pollution due to agricultural activities, remobilization from or entrainment of contaminated bottom sediments, ground water contribution or a combination of these sources.

  10. MEMS device for mass market gas and chemical sensors

    NASA Astrophysics Data System (ADS)

    Kinkade, Brian R.; Daly, James T.; Johnson, Edward A.

    2000-08-01

    Gas and chemical sensors are used in many applications. Industrial health and safety monitors allow companies to meet OSHA requirements by detecting harmful levels of toxic or combustible gases. Vehicle emissions are tested during annual inspections. Blood alcohol breathalizers are used by law enforcement. Refrigerant leak detection ensures that the Earth's ozone layer is not being compromised. Industrial combustion emissions are also monitored to minimize pollution. Heating and ventilation systems watch for high levels of carbon dioxide (CO2) to trigger an increase in fresh air exchange. Carbon monoxide detectors are used in homes to prevent poisoning from poor combustion ventilation. Anesthesia gases are monitored during a patients operation. The current economic reality is that two groups of gas sensor technologies are competing in two distinct existing market segments - affordable (less reliable) chemical reaction sensors for consumer markets and reliable (expensive) infrared (IR) spectroscopic sensors for industrial, laboratory, and medical instrumentation markets. Presently high volume mass-market applications are limited to CO detectros and on-board automotive emissions sensors. Due to reliability problems with electrochemical sensor-based CO detectors there is a hesitancy to apply these sensors in other high volume applications. Applications such as: natural gas leak detection, non-invasive blood glucose monitoring, home indoor air quality, personal/portable air quality monitors, home fire/burnt cooking detector, and home food spoilage detectors need a sensor that is a small, efficient, accurate, sensitive, reliable, and inexpensive. Connecting an array of these next generation gas sensors to wireless networks that are starting to proliferate today creates many other applications. Asthmatics could preview the air quality of their destinations as they venture out into the day. HVAC systems could determine if fresh air intake was actually better than the air

  11. The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

    SciTech Connect

    Osborne, David L.; Zou, Peng; Johnsen, Howard; Hayden, Carl C.; Taatjes, Craig A.; Knyazev, Vadim D.; North, Simon W.; Peterka, Darcy S.; Ahmed, Musahid; Leone, Stephen R.

    2008-08-28

    We have developed a multiplexed time- and photon-energy?resolved photoionizationmass spectrometer for the study of the kinetics and isomeric product branching of gasphase, neutral chemical reactions. The instrument utilizes a side-sampled flow tubereactor, continuously tunable synchrotron radiation for photoionization, a multi-massdouble-focusing mass spectrometer with 100percent duty cycle, and a time- and positionsensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed 3-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.

  12. Chemical Mass Balance of the Earth's Crust: The Calcium Dilemma (?) and the Role of Pelagic Sediments.

    PubMed

    Sibley, D F; Vogel, T A

    1976-05-01

    Chemical mass balance between igneous and sedimentary rocks is calculated by using a linear least squares method in which all chemical variables are evaluated simultaneously. Previous estimates of the average chemical composition of sedimentary rocks have shown excess calcium because of failure to accurately represent the composition and mass of pelagic sediments.

  13. Large Scale Chemical Cross-linking Mass Spectrometry Perspectives.

    PubMed

    Zybailov, Boris L; Glazko, Galina V; Jaiswal, Mihir; Raney, Kevin D

    2013-02-01

    The spectacular heterogeneity of a complex protein mixture from biological samples becomes even more difficult to tackle when one's attention is shifted towards different protein complex topologies, transient interactions, or localization of PPIs. Meticulous protein-by-protein affinity pull-downs and yeast-two-hybrid screens are the two approaches currently used to decipher proteome-wide interaction networks. Another method is to employ chemical cross-linking, which gives not only identities of interactors, but could also provide information on the sites of interactions and interaction interfaces. Despite significant advances in mass spectrometry instrumentation over the last decade, mapping Protein-Protein Interactions (PPIs) using chemical cross-linking remains time consuming and requires substantial expertise, even in the simplest of systems. While robust methodologies and software exist for the analysis of binary PPIs and also for the single protein structure refinement using cross-linking-derived constraints, undertaking a proteome-wide cross-linking study is highly complex. Difficulties include i) identifying cross-linkers of the right length and selectivity that could capture interactions of interest; ii) enrichment of the cross-linked species; iii) identification and validation of the cross-linked peptides and cross-linked sites. In this review we examine existing literature aimed at the large-scale protein cross-linking and discuss possible paths for improvement. We also discuss short-length cross-linkers of broad specificity such as formaldehyde and diazirine-based photo-cross-linkers. These cross-linkers could potentially capture many types of interactions, without strict requirement for a particular amino-acid to be present at a given protein-protein interface. How these shortlength, broad specificity cross-linkers be applied to proteome-wide studies? We will suggest specific advances in methodology, instrumentation and software that are needed to make

  14. Cosmic ray induced ionisation of a molecular cloud shocked by the W28 supernova remnant

    NASA Astrophysics Data System (ADS)

    Vaupré, S.; Hily-Blant, P.; Ceccarelli, C.; Dubus, G.; Gabici, S.; Montmerle, T.

    2014-08-01

    Cosmic rays are an essential ingredient in the evolution of the interstellar medium, as they dominate the ionisation of the dense molecular gas, where stars and planets form. However, since they are efficiently scattered by the galactic magnetic fields, many questions remain open, such as where exactly they are accelerated, what is their original energy spectrum, and how they propagate into molecular clouds. In this work we present new observations and discuss in detail a method that allows us to measure the cosmic ray ionisation rate towards the molecular clouds close to the W28 supernova remnant. To perform these measurements, we use CO, HCO+, and DCO+ millimetre line observations and compare them with the predictions of radiative transfer and chemical models away from thermodynamical equilibrium. The CO observations allow us to constrain the density, temperature, and column density towards each observed position, while the DCO+/HCO+ abundance ratios provide us with constraints on the electron fraction and, consequently, on the cosmic ray ionisation rate. Towards positions located close to the supernova remnant, we find cosmic ray ionisation rates much larger (≳100) than those in standard galactic clouds. Conversely, towards one position situated at a larger distance, we derive a standard cosmic ray ionisation rate. Overall, these observations support the hypothesis that the γ rays observed in the region have a hadronic origin. In addition, based on CR diffusion estimates, we find that the ionisation of the gas is likely due to 0.1-1 GeV cosmic rays. Finally, these observations are also in agreement with the global picture of cosmic ray diffusion, in which the low-energy tail of the cosmic ray population diffuses at smaller distances than the high-energy counterpart.

  15. Comprehensive Mass Analysis for Chemical Processes, a Case Study on L-Dopa Manufacture

    EPA Science Inventory

    To evaluate the “greenness” of chemical processes in route selection and process development, we propose a comprehensive mass analysis to inform the stakeholders from different fields. This is carried out by characterizing the mass intensity for each contributing chemical or wast...

  16. Highly efficient, selective and sensitive molecular screening of acetylcholinesterase inhibitors of natural origin by solid-phase extraction-liquid chromatography/electrospray ionisation-octopole-orthogonal acceleration time-of-flight-mass spectrometry and novel thin-layer chromatography-based bioautography.

    PubMed

    Mroczek, Tomasz

    2009-03-20

    Highly efficient, selective and sensitive molecular screening of natural acetylcholinesterase (AChE) inhibitors was developed and comprised optimized pressurized liquid extraction (PLE) of plant materials followed by highly selective solid-phase extraction (SPE) using Oasis HLB cartridges. Pure alkaloidal fractions were analyzed by a newly developed high-performance liquid-chromatography (HPLC) on a 3 microm Atlantis HILIC silica stationary phase combined with recently introduced electrospray ionisation (ESI) octopole-orthogonal acceleration time-of-flight (oa TOF)-mass spectrometry (MS) with high mass accuracy (about 2 ppm) and high sensitivity (absolute limit of detection (LOD) for galanthamine was about 43 fg at signal-to-noise 13:1). Moreover, a newly developed and validated TLC-bioautography permit galanthamine sensitivities at pg levels. In this way, more potent than galanthamine AChE inhibitor namely 1,2-dihydrogalanthamine in Narcissus jonquilla 'Pipit' extract could be found (with IC(50) value 0.19 microM lower of about 42% than that of galanthamine).

  17. Electron impact ionisation cross sections of iron hydrogen clusters

    NASA Astrophysics Data System (ADS)

    Huber, Stefan E.; Sukuba, Ivan; Urban, Jan; Limtrakul, Jumras; Probst, Michael

    2016-09-01

    We computed electron impact ionisation cross sections (EICSs) of iron hydrogen clusters, FeH n with n = 1,2, ...,10, from the ionisation threshold to 10 keV using the Deutsch-Märk (DM) and the binary-encounter-Bethe (BEB) formalisms. The maxima of the cross sections for the iron hydrogen clusters range from 6.13 × 10-16 cm2 at 60 eV to 8.76 × 10-16 cm2 at 76 eV for BEB-AE (BEB method based on quantum-chemical data from all-electron basis sets) calculations, from 4.15 × 10-16 cm2 at 77 eV to 7.61 × 10-16 cm2 at 80 eV for BEB-ECP (BEB method based on quantum-chemical data from effective-core potentials for inner-core electrons) calculations and from 2.49 × 10-16 cm2 at 43.5 eV to 7.04 × 10-16 cm2 at 51 eV for the DM method. Cross sections calculated via the BEB method are substantially higher than the ones obtained via the DM method, up to a factor of about two for FeH and FeH2. The formation of Fe-H bonds depopulates the iron 4 s orbital, causing significantly lower cross sections for the small iron hydrides compared to atomic iron. Both the DM and BEB cross sections can be fitted perfectly against a simple expression used in modelling and simulation codes in the framework of nuclear fusion research. The energetics of the iron hydrogen clusters change substantially when exact exchange is present in the density functional, while the cluster geometries do not depend on this choice.

  18. IN-SITU CHEMICAL OXIDATION - DNAPL MASS REDUCTION TECHNOLOGY

    EPA Science Inventory

    In-situ chemical oxidation (ISCO) is a rapidly developing technology used at hazardous waste sites where oxidants and complimentary reagents are injected into the subsurface to transform organic contaminants into less toxic byproducts. This technology is being used at new sites ...

  19. New Polymer Coatings for Chemically Selective Mass Sensors

    NASA Technical Reports Server (NTRS)

    Sims, S. C.; Wright, Cassandra; Cobb, J.; McCalla, T.; Revelle, R.; Morris, V. R.; Pollack, S. K.

    1997-01-01

    There is a current need to develop sensitive and chemically specific sensors for the detection of nitric acid for in-situ measurements in the atmosphere. Polymer coatings have been synthesized and tested for their sensitivity and selectivity to nitric acid. A primary requirement for these polymers is detectability down to the parts per trillion range. The results of studies using these polymers as coatings for quartz crystal microbalances (QCM) and surface acoustic wave (SAW) devices will be presented.

  20. Chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry (A0187-2)

    NASA Technical Reports Server (NTRS)

    Foote, J. H.; Swan, P. D.; Walker, R. M.; Zinner, E. K.; Bahr, D.; Fechtig, H.; Jessberger, E.; Igenbergs, E.; Kreitmayr, U.; Kuczera, H.

    1984-01-01

    The objective of this experiment is to measure the chemical and isotopic composition of interplanetary dust particles of mass greater than 10 to the minus 10 power G for most of thermator elements expected to be present.

  1. Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes

    PubMed Central

    Liu, Xiao-Ming; Rudnick, Roberta L.

    2011-01-01

    Chemical weathering, as well as physical erosion, changes the composition and shapes the surface of the continental crust. However, the amount of continental material that has been lost over Earth’s history due to chemical weathering is poorly constrained. Using a mass balance model for lithium inputs and outputs from the continental crust, we find that the mass of continental crust that has been lost due to chemical weathering is at least 15% of the original mass of the juvenile continental crust, and may be as high as 60%, with a best estimate of approximately 45%. Our results suggest that chemical weathering and subsequent subduction of soluble elements have major impacts on both the mass and the compositional evolution of the continental crust. PMID:22184221

  2. Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes.

    PubMed

    Liu, Xiao-Ming; Rudnick, Roberta L

    2011-12-27

    Chemical weathering, as well as physical erosion, changes the composition and shapes the surface of the continental crust. However, the amount of continental material that has been lost over Earth's history due to chemical weathering is poorly constrained. Using a mass balance model for lithium inputs and outputs from the continental crust, we find that the mass of continental crust that has been lost due to chemical weathering is at least 15% of the original mass of the juvenile continental crust, and may be as high as 60%, with a best estimate of approximately 45%. Our results suggest that chemical weathering and subsequent subduction of soluble elements have major impacts on both the mass and the compositional evolution of the continental crust.

  3. High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization of Organic Aerosols

    SciTech Connect

    Laskin, Julia; Laskin, Alexander; Roach, Patrick J.; Slysz, Gordon W.; Anderson, Gordon A.; Nizkorodov, Serguei; Bones, David L.; Nguyen, Lucas

    2010-03-01

    Characterization of the chemical composition and chemical transformations of secondary organic aerosol (SOA) is both a major challenge and the area of greatest uncertainty in current aerosol research. This study presents the first application of desorption electrospray ionization combined with high-resolution mass spectrometry (DESI-MS) for detailed chemical characterization and studies of chemical aging of OA collected on Teflon substrates. DESI-MS offers unique advantages both for detailed characterization of chemically labile components in OA that cannot be detected using more traditional electrospray ionization mass spectrometry (ESI-MS) and for studying chemical aging of OA. DESI-MS enables rapid characterization of OA samples collected on substrates by eliminating the sample preparation stage. In addition, it enables detection and structural characterization of chemically labile molecules in OA samples by minimizing the residence time of analyte in the solvent. SOA produced by the ozonolysis of limonene (LSOA) was allowed to react with gaseous ammonia. Chemical aging resulted in measurable changes in the optical properties of LSOA observed using UV- visible spectroscopy. DESI-MS combined with tandem mass spectrometry experiments (MS/MS) enabled identification of species in aged LSOA responsible for absorption of the visible light. Detailed analysis of the experimental data allowed us to identify chemical changes induced by reactions of LSOA constituents with ammonia and distinguish between different mechanisms of chemical aging.

  4. A mass casualty incident involving children and chemical decontamination.

    PubMed

    Timm, Nathan; Reeves, Scott

    2007-01-01

    Mass casualty incidents involving contaminated children are a rare but ever-present possibility. In this article we outline one such event that resulted in 53 pediatric patients and 3 adults presenting to the emergency department of a children's hospital for decontamination and treatment. We pay special attention to the training that allowed this responses to occur. We also outline the institutional response with emphasis on incident command, communication, and resource utilization. Specific lessons learned are explored in detail. Finally, we set forth a series of recommendations to assist other institutions should they be called upon to care for and decontaminate pediatric patients.

  5. The mass balance approach: application to interpreting the chemical evolution of hydrologic systems.

    USGS Publications Warehouse

    Plummer, L.N.; Back, W.

    1980-01-01

    Mass balance calculations are applied to observed chemical and isotopic data of three natural water systems involving carbonate reactions in order to define mineral stoichiometry of reactants and products, relative rates of reactions, and mass transfer. One study evaluates reactions in a lagoon on the east coast of the Yucatan Peninsula, Mexico.- from Authors

  6. Upper limit to the mass of pulsationally stable stars with uniform chemical composition

    NASA Technical Reports Server (NTRS)

    Stothers, Richard B.

    1992-01-01

    Nuclear-energized pulsational instability is a well-known feature of models of chemically homogeneous stars above a critical mass. With the Rogers-Iglesias opacities, the instability occurs above 120-150 solar mass for normal Galactic Population I chemical compositions, and above approximately 90 solar mass for stars in metal-poor environments like the outer Galaxy and the Small Magellanic Cloud. Models of homogeneous helium-burning stars are unstable above masses of 19 and 14 solar mass, respectively. These significant increases of the critical masses, in the normal metallicity cases, over the values derived previously with the Los Alamos opacities can explain the stability of the brightest observed O-type stars, but they do not exclude the possibility that the most luminous hydrogen-deficient Wolf-Rayet stars are experiencing this type of instability.

  7. Implementation of the chemical reaction interface mass spectrometry technique on a Hewlett-Packard mass-selective detector.

    PubMed

    Song, H; Kusmierz, J; Abramson, F; McLean, M

    1994-08-01

    A microwave-powered chemical reaction interface has been installed in a Hewlett-Packard gas chromatograph-mass spectrometer (GC-MS) system (5890 IT gas chromatograph-S971 mass-selective detector). The technical details and optimization strategies are discussed. The evaluation of this new setup is presented, showing detection limits of 1 ng of (13)C-, (15)N-, and Cl-containing compounds with signal-to-noise ratios greater than or egual to 3. Selective detection was evaluated with a urine sample from a dog dosed with (15)N3-midazolam that had been previously analyzed by using a differentially pumped research-level quadrupole mass spectrometer. The results show that the detection of (15)N and Cl remains highly selective and the mass-selective detector gives comparable sensitivity to the larger instrument when the latter is operating over a conventional mass range. The capability for chemical reaction interface mass spectrometry can be easily accomplished with an inexpensive GC-MS system.

  8. Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes

    NASA Astrophysics Data System (ADS)

    Rudnick, R. L.; Liu, X. M.

    2012-04-01

    The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" that is the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems point to the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 1×10^10 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

  9. Chemical Mass Production of Graphene Nanoplatelets in ∼100% Yield.

    PubMed

    Dimiev, Ayrat M; Ceriotti, Gabriel; Metzger, Andrew; Kim, Nam Dong; Tour, James M

    2016-01-26

    Successful application of graphene is hampered by the lack of cost-effective methods for its production. Here, we demonstrate a method of mass production of graphene nanoplatelets (GNPs) by exfoliation of flake graphite in the tricomponent system made by a combination of ammonium persulfate ((NH4)2S2O8), concentrated sulfuric acid, and fuming sulfuric acid. The resulting GNPs are tens of microns in diameter and 10-35 nm in thickness. When in the liquid phase of the tricomponent media, graphite completely loses its interlayer registry. This provides a ∼100% yield of GNPs from graphite in 3-4 h at room temperature or in 10 min at 120 °C. PMID:26580092

  10. A novel method for the analysis of the substitution pattern of O-methyl-[alpha]- and [beta]-1,4-glucans by means of electrospray ionisation-mass spectrometry/collision induced dissociation

    NASA Astrophysics Data System (ADS)

    Adden, Roland; Mischnick, Petra

    2005-03-01

    The substitution pattern of O-methyl amylose and O-methyl cellulose was analysed after per-O-methylation (Me-d3), and partial hydrolysis by subsequent ESI-MS/CID of the sodium (MS2) and the lithium adducts (MS3). Based on previous studies about the influence of regioselective O-methylation on the fragmentation pathways of malto- and cello-oligosaccharides, we could calculate the contribution of a certain methyl pattern to a distinct signal in the reproducible ESI-MS2 daughter spectrum. Signal intensities obtained from each O-methyl-O-methyl-d3 disaccharide were distributed on the corresponding methyl patterns and accumulated for all peaks of the mother mass spectrum. Data from ESI-MS2 were not sufficient for disaccharides bearing methyl and deuteromethyl groups in the combination 2 and 4, 3 and 3, or 4 and 2. Further independent information was obtained by ESI-MS3 of the lithium adducts. Monomer composition of methyl celluloses and methyl amyloses obtained by this novel approach were in very good agreement with reference data from GLC of the partially methylated glucitol acetates after complete hydrolysis, reduction and acetylation.

  11. Differential analysis of camphor wood products by desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhu, Liang; Yan, Jianping; Zhu, Zhiqiang; Ouyang, Yongzhong; Zhang, Xinglei; Zhang, Wenjun; Dai, Ximo; Luo, Liping; Chen, Huanwen

    2013-01-23

    In the course of this study, desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS) was applied to readily acquire the mass spectral fingerprints of camphor wood and other wood samples under ambient conditions. Characteristic natural analytes, such as camphor and geraniol, were successfully detected in their protonated form and then identified by tandem mass spectrometry (MS(n)). Further principal component analysis (PCA) and cluster analysis (CA) of the mass spectrometric results allow a confident discrimination of camphor wood products from inferior/fake ones. These experimental findings demonstrate that DAPCI-MS is a valuable tool for differential analysis of untreated camphor wood products with sufficient sensitivity and high throughput.

  12. Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

    PubMed

    Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

    2014-01-01

    Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions.

  13. Rapid screening of anabolic steroids in horse urine with ultra-high-performance liquid chromatography/tandem mass spectrometry after chemical derivatisation.

    PubMed

    Wong, Colton H F; Leung, David K K; Tang, Francis P W; Wong, Jenny K Y; Yu, Nola H; Wan, Terence S M

    2012-04-01

    Liquid chromatography/mass spectrometry (LC/MS) has been successfully applied to the detection of anabolic steroids in biological samples. However, the sensitive detection of saturated hydroxysteroids, such as androstanediols, by electrospray ionisation (ESI) is difficult because of their poor ability to ionise. In view of this, chemical derivatisation has been used to enhance the detection sensitivity of hydroxysteroids by LC/MS. This paper describes the development of a sensitive ultra-high-performance liquid chromatography/tandem mass spectrometry (UHPLC/MS/MS) method for the screening of anabolic steroids in horse urine by incorporating a chemical derivatisation step, using picolinic acid as the derivatisation reagent. The method involved solid-phase extraction (SPE) of both free and conjugated anabolic steroids in horse urine using a polymer-based SPE cartridge (Abs Elut Nexus). The conjugated steroids in the eluate were hydrolysed by methanolysis and the resulting extract was further cleaned up by liquid-liquid extraction. The resulting free steroids in the extract were derivatised with picolinic acid to form the corresponding picolinoyl esters and analysed by UHPLC/MS/MS in the positive ESI mode with selected-reaction-monitoring. Separation of the targeted steroids was performed on a C18 UHPLC column. The instrument turnaround time was 10.5 min inclusive of post-run equilibration. A total of thirty-three anabolic steroids (including 17β-estradiol, 5(10)-estrene-3β,17α-diol, 5α-estrane-3β,17α-diol, 17α-ethyl-5α-estran-3α,17β-diol, 17α-methyl-5α-androstan-3,17β-diols, androstanediols, nandrolone and testosterone) spiked in negative horse urine at the QC levels (ranging from 0.75 to 30 ng/mL) could be consistently detected. The intra-day and inter-day precisions (% RSD) for the peak area ratios were around 7-51% and around 1-72%, respectively. The intra-day and inter-day precisions (% RSD) for the relative retention times were both less than 1% for

  14. Electron impact ionisation cross sections of iron hydrogen clusters

    NASA Astrophysics Data System (ADS)

    Huber, Stefan E.; Sukuba, Ivan; Urban, Jan; Limtrakul, Jumras; Probst, Michael

    2016-09-01

    We computed electron impact ionisation cross sections (EICSs) of iron hydrogen clusters, FeHn with n = 1,2,...,10, from the ionisation threshold to 10 keV using the Deutsch-Märk (DM) and the binary-encounter-Bethe (BEB) formalisms. The maxima of the cross sections for the iron hydrogen clusters range from 6.13 × 10-16 cm2 at 60 eV to 8.76 × 10-16 cm2 at 76 eV for BEB-AE (BEB method based on quantum-chemical data from all-electron basis sets) calculations, from 4.15 × 10-16 cm2 at 77 eV to 7.61 × 10-16 cm2 at 80 eV for BEB-ECP (BEB method based on quantum-chemical data from effective-core potentials for inner-core electrons) calculations and from 2.49 × 10-16 cm2 at 43.5 eV to 7.04 × 10-16 cm2 at 51 eV for the DM method. Cross sections calculated via the BEB method are substantially higher than the ones obtained via the DM method, up to a factor of about two for FeH and FeH2. The formation of Fe-H bonds depopulates the iron 4s orbital, causing significantly lower cross sections for the small iron hydrides compared to atomic iron. Both the DM and BEB cross sections can be fitted perfectly against a simple expression used in modelling and simulation codes in the framework of nuclear fusion research. The energetics of the iron hydrogen clusters change substantially when exact exchange is present in the density functional, while the cluster geometries do not depend on this choice. Supplementary material in the form of one pdf file available from the Journal web page athttp://dx.doi.org/10.1140/epjd/e2016-70292-4

  15. Non-equilibrium calcium ionisation in the solar atmosphere

    NASA Astrophysics Data System (ADS)

    Wedemeyer-Böhm, S.; Carlsson, M.

    2011-04-01

    Context. The chromosphere of the Sun is a temporally and spatially very varying medium for which the assumption of ionisation equilibrium is questionable. Aims: Our aim is to determine the dominant processes and timescales for the ionisation equilibrium of calcium under solar chromospheric conditions. Methods: The study is based on numerical simulations with the RADYN code, which combines hydrodynamics with a detailed solution of the radiative transfer equation. The calculations include a detailed non-equilibrium treatment of hydrogen, calcium, and helium. Next to an hour long simulation sequence, additional simulations are produced, for which the stratification is slightly perturbed so that a ionisation relaxation timescale can be determined. The simulations are characterised by upwards propagating shock waves, which cause strong temperature fluctuations and variations of the (non-equilibrium) ionisation degree of calcium. Results: The passage of a hot shock front leads to a strong net ionisation of Ca II, rapidly followed by net recombination. The relaxation timescale of the calcium ionisation state is found to be of the order of a few seconds at the top of the photosphere and 10 to 30 s in the upper chromosphere. At heights around 1 Mm, we find typical values around 60 s and in extreme cases up to ~150 s. Generally, the timescales are significantly reduced in the wakes of ubiquitous hot shock fronts. The timescales can be reliably determined from a simple analysis of the eigenvalues of the transition rate matrix. The timescales are dominated by the radiative recombination from Ca III into the metastable Ca II energy levels of the 4d 2D term. These transitions depend strongly on the density of free electrons and therefore on the (non-equilibrium) ionisation degree of hydrogen, which is the main electron donor. Conclusions: The ionisation/recombination timescales derived here are too long for the assumption of an instantaneous ionisation equilibrium to be valid

  16. Differentiation of microorganisms based on pyrolysis-ion trap mass spectrometry using chemical ionization.

    PubMed

    Barshick, S A; Wolf, D A; Vass, A A

    1999-02-01

    The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonstrated for five Gram-negative disease-causing organisms: Brucella melitensis, Brucella suis, Vibrio cholera, Yersinia pestis, and Francisella tularensis. Bacterial profiles were generated for gamma-irradiated bacterial samples using pyrolytic methylation and compared for electron ionization and chemical ionization using several liquid reagents with increasing proton affinities. Electron ionization combined with pyrolysis caused extensive fragmentation, resulting in a high abundance of lower mass ions and diminishing the diagnostic value of the technique for compound identification and bacterial profiling. Chemical ionization reduced the amount of fragmentation due to ionization while enhancing the molecular ion region of the fatty acids. As the proton affinity of the reagent increased, the protonated molecular ions of the fatty acids became the predominant ions observed in the mass spectrum. As a result, chemical ionization was shown to be more effective than electron ionization in bacterial profiling. Whereas the bacteria could be distinguished at the Genera level using electron ionization, further differentiation to the subspecies level was possible using chemical ionization. The greatest separation among the five test organisms, in terms of Euclidean distances, was obtained using ethanol as the chemical ionization reagent and using pooled masses representing specific fatty acid biomarkers rather than total ion profiles. PMID:9989380

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

    PubMed

    Lebedev, Albert T

    2005-09-01

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

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

    SciTech Connect

    Lebedev, Albert T. . E-mail: lebedev@org.chem.msu.ru

    2005-09-01

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

  19. Meta-Analysis of Mass Balances Examining Chemical Fate during Wastewater Treatment

    PubMed Central

    2008-01-01

    Mass balances are an instructive means for investigating the fate of chemicals during wastewater treatment. In addition to the aqueous-phase removal efficiency (Φ), they can inform on chemical partitioning, transformation, and persistence, as well as on the chemical loading to streams and soils receiving, respectively, treated effluent and digested sewage sludge (biosolids). Release rates computed on a per-capita basis can serve to extrapolate findings to a larger scale. This review examines over a dozen mass balances conducted for various organic wastewater contaminants, including prescription drugs, estrogens, fragrances, antimicrobials, and surfactants of differing sorption potential (hydrophobicity), here expressed as the 1-octanol−water partition coefficient (KOW) and the organic carbon normalized sorption coefficient (KOC). Major challenges to mass balances are the collection of representative samples and accurate quantification of chemicals in sludge. A meta-analysis of peer-reviewed data identified sorption potential as the principal determinant governing chemical persistence in biosolids. Occurrence data for organic wastewater compounds detected in digested sludge followed a simple nonlinear model that required only KOW or KOC as the input and yielded a correlation coefficient of 0.9 in both instances. The model predicted persistence in biosolids for the majority (>50%) of the input load of organic wastewater compounds featuring a log10KOW value of greater than 5.2 (log10KOC > 4.4). In contrast, hydrophobicity had no or only limited value for estimating, respectively, Φ and the overall persistence of a chemical during conventional wastewater treatment. PMID:18800497

  20. A miniaturised laser ablation/ionisation analyser for investigation of elemental/isotopic composition with the sub-ppm detection sensitivity

    NASA Astrophysics Data System (ADS)

    Tulej, M.; Riedo, A.; Meyer, S.; Iakovleva, M.; Neuland, M.; Wurz, P.

    2012-04-01

    Detailed knowledge of the elemental and isotopic composition of solar system objects imposes critical constraints on models describing the origin of our solar system and can provide insight to chemical and physical processes taking place during the planetary evolution. So far, the investigation of chemical composition of planetary surfaces could be conducted almost exclusively by remotely controlled spectroscopic instruments from orbiting spacecraft, landers or rovers. With some exceptions, the sensitivity of these techniques is, however, limited and often only abundant elements can be investigated. Nevertheless, the spectroscopic techniques proved to be successful for global chemical mapping of entire planetary objects such as the Moon, Mars and asteroids. A combined afford of the measurements from orbit, landers and rovers can also yield the determination of local mineralogy. New instruments including Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation/Ionisation Mass Spectrometer (LIMS), have been recently included for several landed missions. LIBS is thought to improve flexibility of the investigations and offers a well localised chemical probing from distances up to 10-13 m. Since LIMS is a mass spectrometric technique it allows for very sensitive measurements of elements and isotopes. We will demonstrate the results of the current performance tests obtained by application of a miniaturised laser ablation/ionisation mass spectrometer, a LIMS instrument, developed in Bern for the chemical analysis of solids. So far, the only LIMS instrument on a spacecraft is the LAZMA instrument. This spectrometer was a part of the payload for PHOBOS-GRUNT mission and is also currently selected for LUNA-RESURCE and LUNA-GLOB missions to the lunar south poles (Managadze et al., 2011). Our LIMS instrument has the dimensions of 120 x Ø60 mm and with a weight of about 1.5 kg (all electronics included), it is the lightest mass analyser designed for in situ chemical

  1. Chromogenic chemical probe for protein structural characterization via ultraviolet photodissociation mass spectrometry.

    PubMed

    O'Brien, John P; Pruet, Jeff M; Brodbelt, Jennifer S

    2013-08-01

    A chemical probe/ultraviolet photodissociation (UVPD) mass spectrometry strategy for evaluating structures of proteins and protein complexes is reported, as demonstrated for lysozyme and beta-lactoglobulin with and without bound ligands. The chemical probe, NN, incorporates a UV chromophore that endows peptides with high cross sections at 351 nm, a wavelength not absorbed by unmodified peptides. Thus, NN-modified peptides can readily be differentiated from nonmodified peptides in complex tryptic digests created upon proteolysis of proteins after their exposure to the NN chemical probe. The NN chemical probe also affords two diagnostic reporter ions detected upon UVPD of the NN-modified peptide that provides a facile method for the identification of NN peptides within complex mixtures. Quantitation of the modified and unmodified peptides allows estimation of the surface accessibilities of lysine residues based on their relative reactivities with the NN chemical probe.

  2. Ionisation and discharge in cloud-forming atmospheres of brown dwarfs and extrasolar planets

    NASA Astrophysics Data System (ADS)

    Helling, Ch; Rimmer, P. B.; Rodriguez-Barrera, I. M.; Wood, Kenneth; Robertson, G. B.; Stark, C. R.

    2016-07-01

    Brown dwarfs and giant gas extrasolar planets have cold atmospheres with rich chemical compositions from which mineral cloud particles form. Their properties, like particle sizes and material composition, vary with height, and the mineral cloud particles are charged due to triboelectric processes in such dynamic atmospheres. The dynamics of the atmospheric gas is driven by the irradiating host star and/or by the rotation of the objects that changes during its lifetime. Thermal gas ionisation in these ultra-cool but dense atmospheres allows electrostatic interactions and magnetic coupling of a substantial atmosphere volume. Combined with a strong magnetic field \\gg {{B}\\text{Earth}} , a chromosphere and aurorae might form as suggested by radio and x-ray observations of brown dwarfs. Non-equilibrium processes like cosmic ray ionisation and discharge processes in clouds will increase the local pool of free electrons in the gas. Cosmic rays and lighting discharges also alter the composition of the local atmospheric gas such that tracer molecules might be identified. Cosmic rays affect the atmosphere through air showers in a certain volume which was modelled with a 3D Monte Carlo radiative transfer code to be able to visualise their spacial extent. Given a certain degree of thermal ionisation of the atmospheric gas, we suggest that electron attachment to charge mineral cloud particles is too inefficient to cause an electrostatic disruption of the cloud particles. Cloud particles will therefore not be destroyed by Coulomb explosion for the local temperature in the collisional dominated brown dwarf and giant gas planet atmospheres. However, the cloud particles are destroyed electrostatically in regions with strong gas ionisation. The potential size of such cloud holes would, however, be too small and might occur too far inside the cloud to mimic the effect of, e.g. magnetic field induced star spots.

  3. Fast Differential Analysis of Propolis Using Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Huang, Xue-yong; Guo, Xia-li; Luo, Huo-lin; Fang, Xiao-wei; Zhu, Teng-gao; Zhang, Xing-lei; Chen, Huan-wen; Luo, Li-ping

    2015-01-01

    Mass spectral fingerprints of 24 raw propolis samples, including 23 from China and one from the United States, were directly obtained using surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without sample pretreatment. Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively. Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated. Analytes such as chrysin, pinocembrin, and quercetin were detected and identified using multiple stage mass spectrometry within 3 min. Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis. PMID:26339245

  4. Computer language for identifying chemicals with comprehensive two-dimensional gas chromatography and mass spectrometry.

    PubMed

    Reichenbach, Stephen E; Kottapalli, Visweswara; Ni, Mingtian; Visvanathan, Arvind

    2005-04-15

    This paper describes a language for expressing criteria for chemical identification with comprehensive two-dimensional gas chromatography paired with mass spectrometry (GC x GC-MS) and presents computer-based tools implementing the language. The Computer Language for Indentifying Chemicals (CLIC) allows expressions that describe rules (or constraints) for selecting chemical peaks or data points based on multi-dimensional chromatographic properties and mass spectral characteristics. CLIC offers chromatographic functions of retention times, functions of mass spectra, numbers for quantitative and relational evaluation, and logical and arithmetic operators. The language is demonstrated with the compound-class selection rules described by Welthagen et al. [W. Welthagen, J. Schnelle-Kreis, R. Zimmermann, J. Chromatogr. A 1019 (2003) 233-249]. A software implementation of CLIC provides a calculator-like graphical user-interface (GUI) for building and applying selection expressions. From the selection calculator, expressions can be used to select chromatographic peaks that meet the criteria or create selection chromatograms that mask data points inconsistent with the criteria. Selection expressions can be combined with graphical, geometric constraints in the retention-time plane as a powerful component for chemical identification with template matching or used to speed and improve mass spectrum library searches.

  5. 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.

  6. Mass and Metallicity Requirement in Stellar Models for Galactic Chemical Evolution Applications

    NASA Astrophysics Data System (ADS)

    Côté, Benoit; West, Christopher; Heger, Alexander; Ritter, Christian; O'Shea, Brian W.; Herwig, Falk; Travaglio, Claudia; Bisterzo, Sara

    2016-09-01

    We used a one-zone chemical evolution model to address the question of how many masses and metallicities are required in grids of massive stellar models in order to ensure reliable galactic chemical evolution predictions. We used a set of yields that includes seven masses between 13 and 30 M⊙, 15 metallicities between 0 and 0.03 in mass fraction, and two different remnant mass prescriptions. We ran several simulations where we sampled subsets of stellar models to explore the impact of different grid resolutions. Stellar yields from low- and intermediate-mass stars and from Type Ia supernovae have been included in our simulations, but with a fixed grid resolution. We compared our results with the stellar abundances observed in the Milky Way for O, Na, Mg, Si, Ca, Ti, and Mn. Our results suggest that the range of metallicity considered is more important than the number of metallicities within that range, which only affects our numerical predictions by about 0.1 dex. We found that our predictions at [Fe/H] ≲ -2 are very sensitive to the metallicity range and the mass sampling used for the lowest metallicity included in the set of yields. Variations between results can be as high as 0.8 dex. At higher [Fe/H], we found that the required number of masses depends on the element of interest and on the remnant mass prescription. With a monotonic remnant mass prescription where every model explodes as a core-collapse supernova, the mass resolution induces variations of 0.2 dex on average. But with a remnant mass prescription that includes islands of non-explodability, the mass resolution can cause variations of about 0.2 to 0.7 dex depending on the choice of the lower limit of the metallicity range. With such a remnant mass prescription, explosive or non-explosive models can be missed if not enough masses are selected, resulting in over- or under-estimations of the mass ejected by massive stars.

  7. A chemical method for flow visualization and determination of local mass transfer

    NASA Astrophysics Data System (ADS)

    Kottke, V.

    A method for measuring local mass transfer is presented, and the physical and chemical concept behind the measuring technique for reaction gases, such as ammonia or methylamine, are discussed, based on absorption, chemical reactions, and coupled-color reactions. Flow visualization at surfaces of arbitrary shape is evident by the color intensity distribution, which corresponds to the locally transferred mass rate. The technique is characterized by its simple handling, good local accuracy, and high local resolution. As an example, the effects of turbulence intensity on the formation of longitudinal vortices in stagnation flows and on the length of separation bubbles for a flat plate with a semi-circular nose section are discussed. Finally the influence of concentration and the temperature boundary layer at separation on the maximum of mass or heat transfer is described.

  8. A micro-mapping strategy to investigate mechanical and chemical mass transport in migmatite

    NASA Astrophysics Data System (ADS)

    Lanari, Pierre; Riel, Nicolas

    2016-04-01

    Migmatites are fantastic objects to study both mechanical and chemical mass transport occurring at mm to cm-scale. However, migmatitic outcrops are the result of complex space and time interactions between (i) melt producing reactions, (ii) melt gain/loss and (iii) retrograde reactions. This succession of events is recorded in the minerals and microstructures of migmatites, and accounts for their apparent complexity. In order to explore the controlling parameters of these chemico-mechanical mass transport, it is thus necessary to characterize in great details the compositional changes between the different migmatitic domains, such as between leucosome and residuum. In this contribution we show how suitable local effective bulk (LEB) compositions can be derived by means of standardized microprobe X-ray images, using the program XMapTools. For chemically heterogeneous samples, such as migmatites, these LEB allow to forward model the stable mineral assemblages for each domain. Those thermodynamic models are used to investigate the conditions of leucosome-residuum separation. The studied sample is a metapelite embedded within a metasedimentary xenolith in the Marcabeli pluton, El Oro Complex, Ecuador. The sample exhibits complex mineral patterns due to local melt redistribution (at mm to cm-scale). Such physical mass transport involves major changes that affect the local chemical composition observed today. At the same time gradients in chemical potential can be established between adjacent domains such as residuum and leucosome, thus triggering chemical interaction. Diffusive transport between domains aims to reduce such chemical potential gradients. Along a modelled P-T path the chemical and mineralogical evolution of micro-domains can be reconstructed for (at least the reactive parts of) the crystallization history.

  9. Mass spectrometry of polycyclic tetracarboxylic ('ARN') acids and tetramethyl esters.

    PubMed

    Sutton, Paul A; Smith, Benjamin E; Rowland, Steven J

    2010-11-15

    Polycyclic C(80) tetracarboxylic (so-called 'ARN') acids are found as calcium salts in deposits which form in certain oilfield pipelines and equipment. Characterisation of these acids is important for improving the prediction and hence avoidance or minimisation of oilfield deposition problems. Although several of the acids have been isolated and characterised (as regioisomeric mixtures) by nuclear magnetic resonance spectroscopy, mass spectrometric methods are likely to be much more useful for the routine analysis of oils and deposits containing the acids. A publication summarising the mass spectra of the purified acids and major derivatives might thus be a very useful source of reference for scientists and technologists studying these unusual compounds. We now report the characterisation of several of the purified acids and of the tetramethyl esters by electrospray ionisation mass spectrometry (ESI-MS) in both positive ion and negative ion modes, by multistage ESI-MS with a suggested rationalisation of the ions produced, by positive ion atmospheric solids analysis probe (ASAP) atmospheric pressure chemical ionisation (APCI), and by positive ion electron ionisation (EI)-MS. Tentative identifications of C(80) acyclic, mono-, bi- and tricylic tetraacids and the δ(13)C isotope values of a mixture of the semi-pure acids determined by MS are also reported for the first time.

  10. Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

    1995-06-01

    Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

  11. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs. PMID:17630721

  12. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs.

  13. The Influence of Environment on the Chemical Evolution in Low-mass Galaxies

    NASA Astrophysics Data System (ADS)

    Liu, Yiqing; Ho, Luis C.; Peng, Eric

    2016-10-01

    The mean alpha-to-iron abundance ratio ([α/Fe]) of galaxies is sensitive to the chemical evolution processes at early time, and it is an indicator of star formation timescale ({τ }{SF}). Although the physical reason remains ambiguous, there is a tight relation between [α/Fe] and stellar velocity dispersion (σ) among massive early-type galaxies (ETGs). However, no work has shown convincing results as to how this relation behaves at low masses. We assemble 15 data sets from the literature and build a large sample that includes 192 nearby low-mass (18\\lt σ \\lt 80 km s-1) ETGs. We find that the [α/Fe]-σ relation generally holds for low-mass ETGs, except in extreme environments. Specifically, in normal galaxy cluster environments, the [α/Fe]-σ relation and its intrinsic scatter are, within uncertainties, similar for low-mass and high-mass ETGs. However, in the most massive relaxed galaxy cluster in our sample, the zero point of the relation is higher and the intrinsic scatter is significantly larger. By contrast, in galaxy groups the zero point of the relation offsets in the opposite direction, again with substantial intrinsic scatter. The elevated [α/Fe] of low-mass ETGs in the densest environments suggests that their star formation was quenched earlier. For the low-mass ETGs in the lowest-density environments, we suggest that their more extended star formation histories suppressed their average [α/Fe]. The large scatter in [α/Fe] may reflect stochasticity in the chemical evolution of low-mass galaxies.

  14. On-line Monitoring of Continuous Flow Chemical Synthesis Using a Portable, Small Footprint Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Bristow, Tony W. T.; Ray, Andrew D.; O'Kearney-McMullan, Anne; Lim, Louise; McCullough, Bryan; Zammataro, Alessio

    2014-10-01

    For on-line monitoring of chemical reactions (batch or continuous flow), mass spectrometry (MS) can provide data to (1) determine the fate of starting materials and reagents, (2) confirm the presence of the desired product, (3) identify intermediates and impurities, (4) determine steady state conditions and point of completion, and (5) speed up process optimization. Recent developments in small footprint atmospheric pressure ionization portable mass spectrometers further enable this coupling, as the mass spectrometer can be easily positioned with the reaction system to be studied. A major issue for this combination is the transfer of a sample that is representative of the reaction and also compatible with the mass spectrometer. This is particularly challenging as high concentrations of reagents and products can be encountered in organic synthesis. The application of a portable mass spectrometer for on-line characterization of flow chemical synthesis has been evaluated by coupling a Microsaic 4000 MiD to the Future Chemistry Flow Start EVO chemistry system. Specifically, the Hofmann rearrangement has been studied using the on-line mass spectrometry approach. Sample transfer from the flow reactor is achieved using a mass rate attenuator (MRA) and a sampling make-up flow from a high pressure pump. This enables the appropriate sample dilution, transfer, and preparation for electrospray ionization. The capability of this approach to provide process understanding is described using an industrial pharmaceutical process that is currently under development. The effect of a number of key experimental parameters, such as the composition of the sampling make-up flow and the dilution factor on the mass spectrometry data, is also discussed.

  15. On-line monitoring of continuous flow chemical synthesis using a portable, small footprint mass spectrometer.

    PubMed

    Bristow, Tony W T; Ray, Andrew D; O'Kearney-McMullan, Anne; Lim, Louise; McCullough, Bryan; Zammataro, Alessio

    2014-10-01

    For on-line monitoring of chemical reactions (batch or continuous flow), mass spectrometry (MS) can provide data to (1) determine the fate of starting materials and reagents, (2) confirm the presence of the desired product, (3) identify intermediates and impurities, (4) determine steady state conditions and point of completion, and (5) speed up process optimization. Recent developments in small footprint atmospheric pressure ionization portable mass spectrometers further enable this coupling, as the mass spectrometer can be easily positioned with the reaction system to be studied. A major issue for this combination is the transfer of a sample that is representative of the reaction and also compatible with the mass spectrometer. This is particularly challenging as high concentrations of reagents and products can be encountered in organic synthesis. The application of a portable mass spectrometer for on-line characterization of flow chemical synthesis has been evaluated by coupling a Microsaic 4000 MiD to the Future Chemistry Flow Start EVO chemistry system. Specifically, the Hofmann rearrangement has been studied using the on-line mass spectrometry approach. Sample transfer from the flow reactor is achieved using a mass rate attenuator (MRA) and a sampling make-up flow from a high pressure pump. This enables the appropriate sample dilution, transfer, and preparation for electrospray ionization. The capability of this approach to provide process understanding is described using an industrial pharmaceutical process that is currently under development. The effect of a number of key experimental parameters, such as the composition of the sampling make-up flow and the dilution factor on the mass spectrometry data, is also discussed. PMID:25106707

  16. Meta-analysis of mass balances examining chemical fate during wastewater treatment.

    PubMed

    Heidler, Jochen; Halden, Rolf U

    2008-09-01

    Mass balances are an instructive means for investigating the fate of chemicals during wastewater treatment. In addition to the aqueous-phase removal efficiency (phi), they can inform on chemical partitioning, transformation, and persistence, as well as on the chemical loading to streams and soils receiving, respectively, treated effluent and digested sewage sludge (biosolids). Release rates computed on a per-capita basis can serve to extrapolate findings to a larger scale. This review examines over a dozen mass balances conducted for various organic wastewater contaminants, including prescription drugs, estrogens, fragrances, antimicrobials, and surfactants of differing sorption potential (hydrophobicity), here expressed as the 1-octanol-water partition coefficient (K(OW)) and the organic carbon normalized sorption coefficient (K(OC)). Major challengesto mass balances are the collection of representative samples and accurate quantification of chemicals in sludge. A meta-analysis of peer-reviewed data identified sorption potential as the principal determinant governing chemical persistence in biosolids. Occurrence data for organic wastewater compounds detected in digested sludge followed a simple nonlinear model that required only K(OW) or K(OC) as the input and yielded a correlation coefficient of 0.9 in both instances. The model predicted persistence in biosolids for the majority (> 50%) of the input load of organic wastewater compounds featuring a log10 K(OW) value of greater than 5.2 (log10 K(OC) > 4.4). In contrast, hydrophobicity had no or only limited value for estimating, respectively, phi and the overall persistence of a chemical during conventional wastewater treatment.

  17. Chemical characterization of the early evolutionary phases of high-mass star-forming regions

    NASA Astrophysics Data System (ADS)

    Gerner, Thomas

    2014-10-01

    The formation of high-mass stars is a very complex process and up to date no comprehensive theory about it exists. This thesis studies the early stages of high-mass star-forming regions and employs astrochemistry as a tool to probe their different physical conditions. We split the evolutionary sequence into four observationally motivated stages that are based on a classification proposed in the literature. The sequence is characterized by an increase of the temperatures and densities that strongly influences the chemistry in the different stages. We observed a sample of 59 high-mass star-forming regions that cover the whole sequence and statistically characterized the chemical compositions of the different stages. We determined average column densities of 18 different molecular species and found generally increasing abundances with stage. We fitted them for each stage with a 1D model, such that the result of the best fit to the previous stage was used as new input for the following. This is a unique approach and allowed us to infer physical properties like the temperature and density structure and yielded a typical chemical lifetime for the high-mass star-formation process of 1e5 years. The 18 analyzed molecular species also included four deuterated molecules whose chemistry is particularly sensitive to thermal history and thus is a promising tool to infer chemical ages. We found decreasing trends of the D/H ratios with evolutionary stage for 3 of the 4 molecular species and that the D/H ratio depends more on the fraction of warm and cold gas than on the total amount of gas. That indicates different chemical pathways for the different molecules and confirms the potential use of deuterated species as chemical age indicators. In addition, we mapped a low-mass star forming region in order to study the cosmic ray ionization rate, which is an important parameter in chemical models. While in chemical models it is commonly fixed, we found that it ! strongly varies with

  18. Modeling and managing toxic chemicals: The Lake Michigan mass balance study

    SciTech Connect

    Endicott, D.D.; Richardson, W.L.

    1995-12-31

    The control and management of anthropogenic chemicals in the Great Lakes is an issue of great concern for 2 nations, 9 states and provinces, and 33 million people. As loadings from identified sources have been reduced, sometimes dramatic declines in toxic chemical concentrations have been observed to follow. However, human health and ecological effects from toxic chemicals remain topics of concern. There is also scientific debate regarding what factors control current toxic chemical concentrations in biotic and abiotic components of the Great lakes ecosystem. To address this latter issue, mathematical models are being developed to simulate the sources, transport, bioavailability, and bioaccumulation of four target chemicals (atrazine, mercury, PCBs, and trans-nonachlor). Preliminary modeling assessment by the authors suggested that PCB concentrations in Lake Michigan lake trout would remain greater than 1 mg/kg, even if all point and nonpoint sources in the watershed were eliminated. 2 factors control this result: (1) atmospheric sources are the largest PCB load component, and (2) the release of PCBs from the lake sediments by resuspension represents a huge internal mass flux. However, current data does not allow accurate estimation of either quantity. Because of the major ecological and economical consequences of decisions based upon the mass balance assessment, the modeling results require scientific confirmation.

  19. [In-hospital management of victims of chemical weapons of mass destruction].

    PubMed

    Barelli, Alessandro; Gargano, Flavio; Proietti, Rodolfo

    2005-01-01

    Emergency situations caused by chemical weapons of mass destruction add a new dimension of risk to those handling and treating casualties. The fundamental difference between a hazardous materials incident and conventional emergencies is the potential for risk from contamination to health care professionals, patients, equipment and facilities of the Emergency Department. Accurate and specific guidance is needed to describe the procedures to be followed by emergency medical personnel to safely care for a patient, as well as to protect equipment and people. This review is designed to familiarize readers with the concepts, terminology and key operational considerations that affect the in-hospital management of incidents by chemical weapons.

  20. Heat and mass transfer for turbulent flow of chemically reacting gas in eccentric annular channels

    SciTech Connect

    Besedina, T.V.; Tverkovkin, B.E.; Udot, A.V.; Yakushev, A.P.

    1988-02-01

    Because of the possibility of using dissociating gases as coolants and working bodies of nuclear power plants, it is necessary to develop computational algorithms for calculating heat and mass transfer processes under conditions of nonequilibrium flow of chemically reacting gases not only in axisymmetric channels, but also in channels with a complex transverse cross section (including also in eccentric annular channels). An algorithm is proposed for calculating the velocity, temperature, and concentration fields under conditions of cooling of a cylindrical heat-releasing rod, placed off-center in a circular casing pipe, by a longitudinal flow of chemically reacting gas (N/sub 2/O/sub 4/).

  1. Study of mass consistency LES/FDF techniques for chemically reacting flows

    NASA Astrophysics Data System (ADS)

    Celis, Cesar; Figueira da Silva, Luís Fernando

    2015-07-01

    A hybrid large eddy simulation/filtered density function (LES/FDF) approach is used for studying chemically reacting flows with detailed chemistry. In particular, techniques utilised for ensuring a mass consistent coupling between LES and FDF are discussed. The purpose of these techniques is to maintain a correct spatial distribution of the computational particles representing specified amounts of fluid. A particular mass consistency technique due to Y.Z. Zhang and D.C. Haworth (A general mass consistency algorithm for hybrid particle/finite-volume PDF methods, J. Comput. Phys. 194 (2004), pp. 156-193) and their associated algorithms are implemented in a pressure-based computational fluid dynamics code suitable for the simulation of variable density flows, representative of those encountered in actual combustion applications. To assess the effectiveness of the referenced technique for enforcing LES/FDF mass consistency, two- and three-dimensional simulations of a temporal mixing layer using detailed and reduced chemistry mechanisms are carried out. The parametric analysis performed focuses on determining the influence on the level of mass consistency errors of parameters such as the initial number of particles per cell and the initial density ratio of the mixing layers. Particular emphasis is put on the computational burden that represents the use of such a mass consistency technique. The results show the suitability of this type of technique for ensuring the mass consistency required when utilising hybrid LES/FDF approaches. The level of agreement of the computed results with experimental data is also illustrated.

  2. Ultrasensitive detection of explosives and chemical warfare agents by low-pressure photoionization mass spectrometry.

    PubMed

    Sun, Wanqi; Liang, Miao; Li, Zhen; Shu, Jinian; Yang, Bo; Xu, Ce; Zou, Yao

    2016-08-15

    On-spot monitoring of threat agents needs high sensitive instrument. In this study, a low-pressure photoionization mass spectrometer (LPPI-MS) was employed to detect trace amounts of vapor-phase explosives and chemical warfare agent mimetics under ambient conditions. Under 10-s detection time, the limits of detection of 2,4-dinitrotoluene, nitrotoluene, nitrobenzene, and dimethyl methyl phosphonate were 30, 0.5, 4, and 1 parts per trillion by volume, respectively. As compared to those obtained previously with PI mass spectrometric techniques, an improvement of 3-4 orders of magnitude was achieved. This study indicates that LPPI-MS will open new opportunities for the sensitive detection of explosives and chemical warfare agents.

  3. Ultrasensitive detection of explosives and chemical warfare agents by low-pressure photoionization mass spectrometry.

    PubMed

    Sun, Wanqi; Liang, Miao; Li, Zhen; Shu, Jinian; Yang, Bo; Xu, Ce; Zou, Yao

    2016-08-15

    On-spot monitoring of threat agents needs high sensitive instrument. In this study, a low-pressure photoionization mass spectrometer (LPPI-MS) was employed to detect trace amounts of vapor-phase explosives and chemical warfare agent mimetics under ambient conditions. Under 10-s detection time, the limits of detection of 2,4-dinitrotoluene, nitrotoluene, nitrobenzene, and dimethyl methyl phosphonate were 30, 0.5, 4, and 1 parts per trillion by volume, respectively. As compared to those obtained previously with PI mass spectrometric techniques, an improvement of 3-4 orders of magnitude was achieved. This study indicates that LPPI-MS will open new opportunities for the sensitive detection of explosives and chemical warfare agents. PMID:27260452

  4. Method for the elucidation of the elemental composition of low molecular mass chemicals using exact masses of product ions and neutral losses: application to environmental chemicals measured by liquid chromatography with hybrid quadrupole/time-of-flight mass spectrometry.

    PubMed

    Suzuki, Shigeru; Ishii, Tetsuko; Yasuhara, Akio; Sakai, Shinichi

    2005-01-01

    A method for elucidating the elemental compositions of low molecular weight chemicals, based primarily on mass measurements made using liquid chromatography (LC) with time-of-flight mass spectrometry (TOFMS) and quadrupole/time-of-flight mass spectrometry (LC/QTOFMS), was developed and tested for 113 chemicals of environmental interest with molecular masses up to approximately 400 Da. As the algorithm incorporating the method is not affected by differences in the instrument used, or by the ionization method and other ionization conditions, the method is useful not only for LC/TOFMS, but also for all kinds of mass spectra measured with higher accuracy and precision (uncertainties of a few mDa) employing all ionization methods and on-line separation techniques. The method involves calculating candidate compositions for intact ionized molecules (ionized forms of the sample molecule that have lost or gained no more than a proton, i.e., [M+H](+) or [M-H](-)) as well as for fragment ions and corresponding neutral losses, and eliminating those atomic compositions for the molecules that are inconsistent with the corresponding candidate compositions of fragment ions and neutral losses. Candidate compositions were calculated for the measured masses of the intact ionized molecules and of the fragment ions and corresponding neutral losses, using mass uncertainties of 2 and 5 mDa, respectively. Compositions proposed for the ionized molecule that did not correspond to the sum of the compositions of a candidate fragment ion and its corresponding neutral loss were discarded. One, 2-5, 6-10, 11-20, and >20 candidate compositions were found for 65%, 39%, 1%, 1%, and 0%, respectively, for the 124 ionized molecules formed from the 113 chemicals tested (both positive and negative ions were obtained from 11 of the chemicals). However, no candidate composition was found for 2% of the test cases (i.e., 3 chemicals), for each of which the measured mass of one of the product ions was in

  5. Electron impact and chemical ionization mass spectral analysis of a volatile uranyl derivative

    SciTech Connect

    Reutter, D.J.; Hardy, D.R.

    1981-01-01

    Quadrupole mass spectral analysis of the volatile uranium ligand complex bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dioxouranium-di-n-butyl sulfoxide is described utilizing electron impact (EI) and methane chemical ionization (CI) ion sources. All major ions are tentatively identified and the potential usefulness of this complex for determining uranium isotope /sup 235/U//sup 238/U abundance is demonstrated.

  6. Safe management of mass fatalities following chemical, biological, and radiological incidents.

    PubMed

    Baker, David J; Jones, Kelly A; Mobbs, Shelly F; Sepai, Ovnair; Morgan, Dilys; Murray, Virginia S G

    2009-01-01

    Contaminated mass fatalities following the release of chemical, biological, or radiological agents pose a potential major health hazard. A United Kingdom government investigation has identified a number of areas of risk. This paper presents an outline of the findings of the study and describes specific pathways for the management of contaminated and non-contaminated fatalities. Factors determining the choice between cremation and burial are discussed. Effective decontamination remains a neglected area of study for both fatalities and casualties. PMID:19618352

  7. Real-time monitoring of volatile organic compounds using chemical ionization mass spectrometry

    DOEpatents

    Mowry, Curtis Dale; Thornberg, Steven Michael

    1999-01-01

    A system for on-line quantitative monitoring of volatile organic compounds (VOCs) includes pressure reduction means for carrying a gaseous sample from a first location to a measuring input location maintained at a low pressure, the system utilizing active feedback to keep both the vapor flow and pressure to a chemical ionization mode mass spectrometer constant. A multiple input manifold for VOC and gas distribution permits a combination of calibration gases or samples to be applied to the spectrometer.

  8. Safe management of mass fatalities following chemical, biological, and radiological incidents.

    PubMed

    Baker, David J; Jones, Kelly A; Mobbs, Shelly F; Sepai, Ovnair; Morgan, Dilys; Murray, Virginia S G

    2009-01-01

    Contaminated mass fatalities following the release of chemical, biological, or radiological agents pose a potential major health hazard. A United Kingdom government investigation has identified a number of areas of risk. This paper presents an outline of the findings of the study and describes specific pathways for the management of contaminated and non-contaminated fatalities. Factors determining the choice between cremation and burial are discussed. Effective decontamination remains a neglected area of study for both fatalities and casualties.

  9. Chemical composition and mass closure of ambient PM10 at urban sites

    NASA Astrophysics Data System (ADS)

    Terzi, Eleni; Argyropoulos, George; Bougatioti, Aikaterini; Mihalopoulos, Nikolaos; Nikolaou, Kostas; Samara, Constantini

    2010-06-01

    The chemical composition of PM10 was studied during summer and winter sampling campaigns conducted at two different urban sites in the city of Thessaloniki, Greece (urban-traffic, UT and urban-industrial, UI). PM10 samples were chemically analysed for minerals (Si, Al, Ca, Mg, Fe, Ti, K), trace elements (Cd, Cr, Cu, Mn, Pb, V, Zn, Te, Co, Ni, Se, Sr, As, and Sb), water-soluble ions (Cl -, NO 3-, SO 42-, Na +, K +, NH 4+, Ca 2+, Mg 2+) and carbonaceous compounds (OC, EC). Spatial variations of atmospheric concentrations showed significantly higher levels of minerals, some trace metals and TC at the UI site, while at the UT site significantly higher levels of elements like Cd, Ba, Sn, Sb and Te were observed. Crustal elements, excepting Ca at the UI site, did not exhibit significant seasonal variations at any site pointing to constant emissions throughout the year. In order to reconstruct the particle mass, the determined components were classified into six classes as follows: mineral matter (MIN), trace elements (TE), organic matter (OM), elemental carbon (EC), sea salt (SS) and secondary inorganic aerosol (SIA). Good correlations with slopes close to 1 were found between chemically determined and gravimetrically measured PM10 masses for both sites. According to the chemical mass closure obtained, the major components of PM10 at both sites were MIN (soil-derived compounds), followed by OM and SIA. The fraction unaccounted for by chemical analysis comprised on average 8% during winter and 15% during summer at the urban-industrial site, while at the urban-traffic site the percentages were 21.5% in winter and 4.8% in summer.

  10. Chemical and Physical Characterization of Collapsing Low-mass Prestellar Dense Cores

    NASA Astrophysics Data System (ADS)

    Hincelin, U.; Commerçon, B.; Wakelam, V.; Hersant, F.; Guilloteau, S.; Herbst, E.

    2016-05-01

    The first hydrostatic core, also called the first Larson core, is one of the first steps in low-mass star formation as predicted by theory. With recent and future high-performance telescopes, the details of these first phases are becoming accessible, and observations may confirm theory and even present new challenges for theoreticians. In this context, from a theoretical point of view, we study the chemical and physical evolution of the collapse of prestellar cores until the formation of the first Larson core, in order to better characterize this early phase in the star formation process. We couple a state-of-the-art hydrodynamical model with full gas-grain chemistry, using different assumptions for the magnetic field strength and orientation. We extract the different components of each collapsing core (i.e., the central core, the outflow, the disk, the pseudodisk, and the envelope) to highlight their specific physical and chemical characteristics. Each component often presents a specific physical history, as well as a specific chemical evolution. From some species, the components can clearly be differentiated. The different core models can also be chemically differentiated. Our simulation suggests that some chemical species act as tracers of the different components of a collapsing prestellar dense core, and as tracers of the magnetic field characteristics of the core. From this result, we pinpoint promising key chemical species to be observed.

  11. Real-time monitoring of volatile organic compounds using chemical ionization mass spectroscopy: Final report

    SciTech Connect

    Thornberg, S.M.; Mowry, C.D.; Keenan, M.R.; Bender, S.F.A.; Owen, T.

    1997-04-01

    Volatile organic compound (VOC) emission to the atmosphere is of great concern to semiconductor manufacturing industries, research laboratories, the public, and regulatory agencies. Some industries are seeking ways to reduce emissions by reducing VOCs at the point of use (or generation). This paper discusses the requirements, design, calibration, and use of a sampling inlet/quadrupole mass spectrometer system for monitoring VOCs in a semiconductor manufacturing production line. The system uses chemical ionization to monitor compounds typically found in the lithography processes used to manufacture semiconductor devices (e.g., acetone, photoresist). The system was designed to be transportable from tool to tool in the production line and to give the operator real-time feedback so the process(es) can be adjusted to minimize VOC emissions. Detection limits ranging from the high ppb range for acetone to the low ppm range fore other lithography chemicals were achieved using chemical ionization mass spectroscopy at a data acquisition rate of approximately 1 mass spectral scan (30 to 200 daltons) per second. A demonstration of exhaust VOC monitoring was performed at a working semiconductor fabrication facility during actual wafer processing.

  12. Evaluation of C60 secondary ion mass spectrometry for the chemical analysis and imaging of fingerprints.

    PubMed

    Sisco, Edward; Demoranville, Leonard T; Gillen, Greg

    2013-09-10

    The feasibility of using C60(+) cluster primary ion bombardment secondary ion mass spectrometry (C60(+) SIMS) for the analysis of the chemical composition of fingerprints is evaluated. It was found that C60(+) SIMS could be used to detect and image the spatial localization of a number of sebaceous and eccrine components in fingerprints. These analyses were also found to not be hindered by the use of common latent print powder development techniques. Finally, the ability to monitor the depth distribution of fingerprint constituents was found to be possible - a capability which has not been shown using other chemical imaging techniques. This paper illustrates a number of strengths and potential weaknesses of C60(+) SIMS as an additional or complimentary technique for the chemical analysis of fingerprints.

  13. Direct Measurement of Atmospheric Ammonia from an Airborne Miniature Chemical Ionization Mass Spectrometer (miniCIMS)

    NASA Astrophysics Data System (ADS)

    Casados, K.; Schill, S.; Freeman, S.; Zoerb, M.; Bertram, T. H.; Lefer, B. L.

    2015-12-01

    Ammonia is emitted into the atmosphere from a variety of sources such as trees, ocean, diary fields, biomass burning, and fuel emissions. Previous studies have investigated the environmental impacts of atmospheric ammonia which can include chemical reactivity, nucleation of fine particulate matter 2.5 (PM 2.5 ), and implications for human health, but its chemical nature and relatively short lifetime make direct measurement of atmospheric ammonia difficult. During the 2015 NASA Student Airborne Research Program (SARP) an airborne miniature Chemical Ionization Mass Spectrometer (miniCIMS) was deployed on the NASA DC-8 flying laboratory in the Southern California region. The spatial and temporal variability of measured atmospheric ammonia concentrations will be discussed.

  14. Nonequilibrium thermodynamic formalism of nonlinear chemical reaction systems with Waage-Guldberg's law of mass action

    NASA Astrophysics Data System (ADS)

    Ge, Hao; Qian, Hong

    2016-06-01

    Macroscopic entropy production rate σ (tot) in the general nonlinear isothermal chemical reaction system with mass action kinetics is decomposed into a free energy dissipation rate and a house-keeping heat dissipation rate: σ (tot) =σ (fd) +σ (hk) ; σ (fd) = -d A /d t , where A is a generalized free energy function. This yields a novel nonequilibrium free energy balance equation d A /d t = -σ (tot) +σ (hk) , which is on a par with celebrated entropy balance equation d S /d t =σ (tot) +η (ex) where η (ex) is the rate of entropy exchange with the environment. For kinetic systems with complex balance, σ (fd) and σ (hk) are the macroscopic limits of stochastic free energy dissipation rate and house-keeping heat dissipation rate, which are both nonnegative, in the Delbrück-Gillespie description of the stochastic chemical kinetics. A full kinetic and thermodynamic theory of chemical reaction systems that transcends mesoscopic and macroscopic levels emerges.

  15. The synergistic effect of ultrasound and chemical penetration enhancers on chorioamnion mass transport.

    PubMed

    Azagury, Aharon; Khoury, Luai; Adato, Yair; Wolloch, Lior; Ariel, Ilana; Hallak, Mordechai; Kost, Joseph

    2015-02-28

    In our previous study we proposed the use of chemical penetration enhancers for noninvasive detection of fetus abnormalities that can also be utilized for direct fetal drug delivery. In an attempt to further increase the mass transport rate across the amniotic membrane, thus shortening the procedure and improving the applicability of the proposed procedure, the effect and mechanism of combining ultrasound exposure with chemical penetration enhancers' application were assessed. The combined effect was evaluated in vitro on post-delivery human amniotic membrane and ex vivo on rat's whole amniotic sac. Ultrasound effect has been assessed by dye experiments using a customized image analysis program. Additional insights of ultrasound effect's mechanism on biological membranes are presented. Previously we have determined that chemical penetration enhancers affect the fetal membranes via two mechanisms termed as 'extractors' and 'fluidizers'. In this study, we found that combining ultrasound with a 'fluidizer' CPE (e.g. bupivacaine) results in a synergistic enhancement (90-fold) of fetal membrane's mass transport, while combining ultrasound with 'extractors' (e.g. ethanol and NMP) results in an antagonistic effect. The combined procedure is faster and gain greater accuracy than the applications of sole chemical penetration enhancers.

  16. Evidence-based patient decontamination: an integral component of mass exposure chemical incident planning and response.

    PubMed

    Leary, Adam D; Schwartz, Michael D; Kirk, Mark A; Ignacio, Joselito S; Wencil, Elaine B; Cibulsky, Susan M

    2014-06-01

    Decontaminating patients who have been exposed to hazardous chemicals can directly benefit the patients' health by saving lives and reducing the severity of toxicity. While the importance of decontaminating patients to prevent the spread of contamination has long been recognized, its role in improving patient health outcomes has not been as widely appreciated. Acute chemical toxicity may manifest rapidly-often minutes to hours after exposure. Patient decontamination and emergency medical treatment must be initiated as early as possible to terminate further exposure and treat the effects of the dose already absorbed. In a mass exposure chemical incident, responders and receivers are faced with the challenges of determining the type of care that each patient needs (including medical treatment, decontamination, and behavioral health support), providing that care within the effective window of time, and protecting themselves from harm. The US Department of Health and Human Services and Department of Homeland Security have led the development of national planning guidance for mass patient decontamination in a chemical incident to help local communities meet these multiple, time-sensitive health demands. This report summarizes the science on which the guidance is based and the principles that form the core of the updated approach.

  17. Influence of mass transfer and chemical reaction on ozonation of azo dyes.

    PubMed

    Choi, I S; Wiesmann, U

    2004-01-01

    Azo dyes can be only mineralised by chemical oxidation. In this paper the oxidation of Reactive Black 5 (RB 5) and Reactive Orange 96 (RO 96) with concentrations between 35 and 5,700 mgL(-1) (RB 5) and between 20 and 2,050 mgL(-1) (RO 96) was investigated in a lab-scale bubble column. The reactor was modelled for two cases, a completely mixed and a plug flow gas phase. The oxidation rate was influenced by mass transfer for all dye concentrations used. For low dye concentrations mass transfer alone was decisive for the reaction rate showing no enhancement due to chemical reaction, E approximately equal to 1. However, in the region of high dye concentrations, the slope of the ozone concentration profile inside the liquid boundary layer increases more and more with increasing dye concentration as a result of a chemical oxidation. Therefore, the enhancement factor depends on the type and concentration of the azo dyes. For RB 5, a diazo dye, an enhancement factor of E = 5.5 was observed for cd = 2,000 mgL(-1), RO 96, a mono azo dye, with a remarkably higher chemical oxidation rate shows an E = 16 for cd = 2,050 mgL(-1).

  18. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

  19. Laser Microdissection and Atmospheric Pressure Chemical Ionization Mass Spectrometry Coupled for Multimodal Imaging

    SciTech Connect

    Lorenz, Matthias; Ovchinnikova, Olga S; Kertesz, Vilmos; Van Berkel, Gary J

    2013-01-01

    This paper describes the coupling of ambient laser ablation surface sampling, accomplished using a laser capture microdissection system, with atmospheric pressure chemical ionization mass spectrometry for high spatial resolution multimodal imaging. A commercial laser capture microdissection system was placed in close proximity to a modified ion source of a mass spectrometer designed to allow for sampling of laser ablated material via a transfer tube directly into the ionization region. Rhodamine 6G dye of red sharpie ink in a laser etched pattern as well as cholesterol and phosphatidylcholine in a cerebellum mouse brain thin tissue section were identified and imaged from full scan mass spectra. A minimal spot diameter of 8 m was achieved using the 10X microscope cutting objective with a lateral oversampling pixel resolution of about 3.7 m. Distinguishing between features approximately 13 m apart in a cerebellum mouse brain thin tissue section was demonstrated in a multimodal fashion including co-registered optical and mass spectral chemical images.

  20. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    PubMed

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-01

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources.

  1. Analytical technique to address terrorist threats by chemical weapons of mass destruction

    NASA Astrophysics Data System (ADS)

    Dempsey, Patrick M.

    1997-01-01

    Terrorism is no longer an issue without effect on the American mind. We now live with the same concerns and fears that have been commonplace in other developed and third world countries for a long time. Citizens of other countries have long lived with the specter of terrorism and now the U.S. needs to be concerned and prepared for terrorist activities.T he terrorist has the ability to cause great destructive effects by focusing their effort on unaware and unprepared civilian populations. Attacks can range from simple explosives to sophisticated nuclear, chemical and biological weapons. Intentional chemical releases of hazardous chemicals or chemical warfare agents pose a great threat because of their ready availability and/or ease of production, and their ability to cause widespread damage. As this battlefront changes from defined conflicts and enemies to unnamed terrorists, we must implement the proper analytical tools to provide a fast and efficient response. Each chemical uses in a terrorists weapon leaves behind a chemical signature that can be used to identify the materials involved and possibly lead investigators to the source and to those responsible. New tools to provide fast and accurate detection for battlefield chemical and biological agent attack are emerging. Gas chromatography/mass spectrometry (GC/MS) is one of these tools that has found increasing use by the military to respond to chemical agent attacks. As the technology becomes smaller and more portable, it can be used by law enforcement personnel to identify suspected terrorist releases and to help prepare the response; define contaminated areas for evacuation and safety concerns, identify the proper treatment of exposed or affected civilians, and suggest decontamination and cleanup procedures.

  2. The effectiveness of photocatalytic ionisation disinfection of filter materials.

    PubMed

    Pietrzak, Katarzyna; Gutarowska, Beata

    2013-01-01

    The purpose of this study was to determine the effectiveness of photocatalytic ionisation as a disinfection method for filter materials contaminated by microorganisms, and to assess how air relative humidity (RH), time and microbe type influence the effectiveness of this disinfection. In the quantitative analysis of a used car air filter, bacterial contamination equalled 1.2 x 10(5) cfu/cm2, fungal contamination was 3.8 x 10(6) cfu/cm2, and the isolated microorganisms were Aspergillus niger, Bacillus megaterium, Cladosporium herbarum, Cryptococcus laurenti, Micrococcus sp., Rhodotorula glutinis and Staphylococcus cohnii. In the model experiment, three isolates (C. herbarum, R. glutinis, S. cohnii) and 3 ATCC species (A. niger, E. coli, S. aureus) were used for photocatalytic ionisation disinfection. The conditions of effective photocatalytic ionisation disinfection (R > or = 99.9%) were established as 2-3 h at RH = 77% (bacteria) and 6-24 h at RH = 53% (fungi). RH has an influence on the effectiveness of the photocatalytic disinfection process; the highest effectiveness was obtained for bacteria at RH = 77%, with results 5% higher than for RH = 49%. The studies show that the sensitivity of microorganisms to photocatalytic ionisation disinfection is ordered as follows: Gram-positive bacteria (S. cohnii, S. aureus), Gram-negative bacteria (E. coli), yeasts (R. glutinis), and moulds (C. herbarum, A. niger). Of all the mathematical models used for the description of death dynamics after photocatalytic ionisation disinfection, the Chick-Watson model is the most useful, but for more resistant microorganisms, the delayed Chick-Watson model is highly recommended. It therefore seems, that the presented disinfection method of photocatalytic ionisation can be successfully used to clean filtration materials.

  3. Ionised Iron Lines in X-ray Reflection Spectra

    NASA Astrophysics Data System (ADS)

    Ballantyne, D. R.; Ross, R. R.; Fabian, A. C.

    2000-10-01

    We present results from new calculations of the reflected X-ray spectrum from ionised accretion disks in Active Galactic Nuclei (AGN). These calculations improve on our previous models by including the condition of hydrostatic balance in the vertical direction, following the work of Nayakshin, Kazanas & Kallman (2000). Our results show that, for gas pressure dominated accretion discs, ionised iron features are found in the reflection spectrum over a range of conditions. We also explore extending our results into radiation pressure dominated discs, and discuss the limitations of the current models.

  4. Laser-modified electron scattering from a slowly ionising atom

    NASA Technical Reports Server (NTRS)

    Fiordilino, E.; Mittleman, M. H.

    1983-01-01

    When an electron scatters from an atom in the presence of a laser field which is resonant with an atomic transition, off-shell effects enter into the cross section. These only become significant at higher laser intensities where the atom may also be ionised by the laser. Cross-sections are obtained for electron-atom scattering in which these off-shell effects appear and in which the slow ionisation of the atom by the laser is included. Experiments are suggested in which simplifications can occur and which still retain these 'exotic' effects.

  5. Chemical and sediment mass transfer in the Yamuna River — A tributary of the Ganges system

    NASA Astrophysics Data System (ADS)

    Jha, P. K.; Subramanian, V.; Sitasawad, R.

    1988-12-01

    Maximum mass transfer, in the Yamuna River takes place during the monsoon season. The sediment load constitutes 58-86% of the total load carried by the river depending upon the sites. Tributaries are chemically more active than the mainstream. The total load of the river seems to be controlled by lithology. At Allahabad, the Yamuna carries 42 × 10 6t dissolved chemical load and 64 × 10 6t sediment load to the Ganges river. The TSM/TDS ratio shows that upstream physical weathering is more dominant than chemical weathering. The negative relation between basin area and total erosion rate and the positive relation between the chemical and sediment erosion in the Yamuna basin is in agreement with the global trend. The average chemical erosion rate (165 t km -2yr -1) of the Yamuna is much higher than that of the Ganges and the Indian average. The total erosion rate (973 t km -2yr -1) is 1.7 times greater than that of the Ganges. Upstream the Yamuna removes 1.04 mm yr -1 of the basin surface; the removal rate decreases downstream to 0.19 mm yr -1 at Allahabad, the point of confluence with the Ganges.

  6. In situ analysis of Titan's tholins by Laser 2 steps Desorption Ionisation

    NASA Astrophysics Data System (ADS)

    Benilan, Y.; Carrasco, N.; Cernogora, G.; Gazeau, M.; Mahjoub, A.; Szopa, C.; Schwell, M.

    2013-12-01

    The main objective of the whole project developed in collaboration (LISA/LATMOS) is to provide a better understanding of the chemical composition of Titan aerosols laboratory analogs, called tholins, and thereby of their formation pathways. The tholins are produced in the PAMPRE reactor (French acronyme for Aerosols Microgravity Production by Reactives Plasmas) developed at LATMOS. These tholins are generated in levitation (wall effects are thus limited) in a low pressure radiofrequency plasma. Up to now, the determination of the physical and chemical properties of these tholins was achieved after their collection and ex-situ analysis by several methods. Their bulk composition was then determined but their insoluble part is still unknown. Other studies were performed after the transfer of the soluble part of the aerosols to different analytical instruments. Therefore, possible artifacts could have influenced the results. We present the SMARD (a French acronym for Mass Spectrometry of Aerosols by InfraRed Laser Desorption) program. A challenging issue of our work is to perform the soluble and unsoluble parts of PAMPRE tholins' analysis in real time and in situ. The coupling of the PAMPRE reactor to a unique instrument (Single Particle Laser Ablation Mass Spectrometry) developed at LISA should allow determining in real time and in situ the characteristics (chemical composition together with granulometry) of the nanometric aerosols. The later are introduced in the analytical instrument using an aerodynamic lens device. Their detection and aerodynamic diameter are determined using two continuous diode lasers operating at λ = 403 nm. Then, the L2DI (Laser 2 steps Desorption Ionisation) technique is used in order to access to the chemical composition of individual particles: they are vaporized using a 10 μm CO2 pulsed laser and the gas produced is then ionized by a 248 nm KrF Excimer laser. Finally, the molecular ions are analyzed by a 1 m linear time-of-flight mass

  7. Highly ionised absorbers at high redshift

    NASA Astrophysics Data System (ADS)

    Bergeron, Jacqueline; Herbert-Fort, Stéphane

    2005-03-01

    We build a sample of O VI absorption systems in the redshift range 2.0 ≲ z ≲ 2.6 using high spectral resolution data of ten quasars from the VLT-UVES large programme. We investigate the existence of a metal-rich O VI population and define observational criteria for this class of absorbers under the assumption of photoionisation. The low temperatures of nearly half of all O VI absorbers, implied by their line widths, are too low for collisional ionisation to be a dominant process. We estimate the oxygen abundance under the assumption of photoionisation; a striking result is the bimodal distribution of [o/h] with median values close to 0.01 and 0.5 solar for the metal-poor and metal-rich populations, respectively. Using the line widths to fix the temperature or assuming a constant, low gas density does not drastically change the metallicities of the metal-rich population. We present the first estimate of the O VI column density distribution. Assuming a single power-law distribution, f(n) ∝ n-α, yields α ˜ 1.7 and a normalisation of f(n) =2.3× 10-13 at log n(O VI) ˜ 13.5, both with a ˜30% uncertainty. The value of α is similar to that found for C IV surveys, whereas the normalisation factor is about ten times higher. We use f(n) to derive the number density per unit z and cosmic density ωb(O VI), selecting a limited column density range not strongly affected by incompleteness or sample variance. Comparing our results with those obtained at z˜0.1 for a similar range of column densities implies some decline of dn/dz with z. The cosmic O VI density derived from f(n), ωb(O VI)≈ (3.5± 3.20.9) × 10-7, is 2.3 times higher than the value estimated using the observed O VI sample (of which the metal-rich population contributes ˜35%), easing the problem of missing metals at high z (˜ 1/4 of the produced metals) but not solving it. We find that the majori ty of the metal-rich absorbers are located within ˜ 450 km s-1 of strong Ly-α lines and show that

  8. High-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry and gas chromatography-flame ionization detection characterization of Delta5-polyenoic fatty acids in triacylglycerols from conifer seed oils.

    PubMed

    Lísa, Miroslav; Holcapek, Michal; Rezanka, Tomás; Kabátová, Nadezda

    2007-03-30

    Edible conifer seeds can serve as a source of triacylglycerols (TGs) with unusual Delta5 unsaturated polymethylene interrupted fatty acids (UPIFAs), such as cis-5,9-octadecadienoic (taxoleic), cis-5,9,12-octadecatrienoic (pinolenic), cis-5,11-eicosadienoic (keteleeronic) and cis-5,11,14-eicosatrienoic acids (sciadonic). Conifer seed oils from European Larch (Larix decidua), Norway Spruce (Picea abies) and European Silver Fir (Abies alba) have been analyzed by non-aqueous reversed-phase high-performance liquid chromatography (NARP-HPLC) with atmospheric pressure chemical ionisation (APCI)-MS detection. The influence of different positions of double bonds in Delta5-UPIFAs on the retention and fragmentation behavior is described and used for the successful identification of TGs in each oil. TGs containing Delta5-UPIFAs have a higher retention in comparison with common TGs found in plant oils with single methylene interrupted Delta6(9)-FAs and also significantly changed relative abundances of fragment ions in APCI mass spectra. Results obtained from HPLC/MS analyses are supported by validated GC/FID analyses of fatty acid methyl esters after the transesterification. The total content of Delta5-UPIFAs is about 32% for European Larch, 27% for Norway Spruce and 20% for European Silver Fir. In total, 20 FAs with acyl chain lengths from 16 to 24 carbon atoms and from 0 to 3 double bonds have been identified in 64 triacylglycerols from 3 conifer seed oils. PMID:17307191

  9. Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

    PubMed

    Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

    2016-09-01

    The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. PMID:27471991

  10. Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

    PubMed

    Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

    2016-09-01

    The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step.

  11. Aerosol chemical composition in cloud events by high resolution time-of-flight aerosol mass spectrometry.

    PubMed

    Hao, Liqing; Romakkaniemi, Sami; Kortelainen, Aki; Jaatinen, Antti; Portin, Harri; Miettinen, Pasi; Komppula, Mika; Leskinen, Ari; Virtanen, Annele; Smith, James N; Sueper, Donna; Worsnop, Douglas R; Lehtinen, Kari E J; Laaksonen, Ari

    2013-03-19

    This study presents results of direct observations of aerosol chemical composition in clouds. A high-resolution time-of-flight aerosol mass spectrometer was used to make measurements of cloud interstitial particles (INT) and mixed cloud interstitial and droplet residual particles (TOT). The differences between these two are the cloud droplet residuals (RES). Positive matrix factorization analysis of high-resolution mass spectral data sets and theoretical calculations were performed to yield distributions of chemical composition of the INT and RES particles. We observed that less oxidized hydrocarbon-like organic aerosols (HOA) were mainly distributed into the INT particles, whereas more oxidized low-volatile oxygenated OA (LVOOA) mainly in the RES particles. Nitrates existed as organic nitrate and in chemical form of NH(4)NO(3). Organic nitrates accounted for 45% of total nitrates in the INT particles, in clear contrast to 26% in the RES particles. Meanwhile, sulfates coexist in forms of acidic NH(4)HSO(4) and neutralized (NH(4))(2)SO(4). Acidic sulfate made up 64.8% of total sulfates in the INT particles, much higher than 10.7% in the RES particles. The results indicate a possible joint effect of activation ability of aerosol particles, cloud processing, and particle size effects on cloud formation.

  12. Liposome-based chemical barcodes for single molecule DNA detection using imaging mass spectrometry.

    PubMed

    Gunnarsson, Anders; Sjövall, Peter; Höök, Fredrik

    2010-02-10

    We report on a mass-spectrometry (time-of-flight secondary ion mass spectrometry, TOF-SIMS) based method for multiplexed DNA detection utilizing a random array, where the lipid composition of small unilamellar liposomes act as chemical barcodes to identify unique DNA target sequences down to the single molecule level. In a sandwich format, suspended target-DNA to be detected mediates the binding of capture-DNA modified liposomes to surface-immobilized probe-DNA. With the lipid composition of each liposome encoding a unique target-DNA sequence, TOF-SIMS analysis was used to determine the chemical fingerprint of the bound liposomes. Using high-resolution TOF-SIMS imaging, providing sub-200 nm spatial resolution, single DNA targets could be detected and identified via the chemical fingerprint of individual liposomes. The results also demonstrate the capability of TOF-SIMS to provide multiplexed detection of DNA targets on substrate areas in the micrometer range. Together with a high multiplexing capacity, this makes the concept an interesting alternative to existing barcode concepts based on fluorescence, Raman, or graphical codes for small-scale bioanalysis. PMID:20085369

  13. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

    PubMed

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  14. Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices

    NASA Astrophysics Data System (ADS)

    Liu, Chengyuan; Yang, Jiuzhong; Wang, Jian; Hu, Yonghua; Zhao, Wan; Zhou, Zhongyue; Qi, Fei; Pan, Yang

    2016-07-01

    Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS). After careful optimization and testing with pure sample solution, EAPPI was successfully applied to the fast screening of capsules, soil, natural products, and viscous compounds. Analysis was completed within a few seconds without the need for preseparation. Moreover, the quantification capability of EAPPI for matrices was evaluated by analyzing six polycyclic aromatic hydrocarbons (PAHs) in soil. The correlation coefficients (R 2 ) for standard curves of all six PAHs were above 0.99, and the detection limits were in the range of 0.16-0.34 ng/mg. In addition, EAPPI could also be used to monitor organic chemical reactions in real time.

  15. Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices

    NASA Astrophysics Data System (ADS)

    Liu, Chengyuan; Yang, Jiuzhong; Wang, Jian; Hu, Yonghua; Zhao, Wan; Zhou, Zhongyue; Qi, Fei; Pan, Yang

    2016-10-01

    Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS). After careful optimization and testing with pure sample solution, EAPPI was successfully applied to the fast screening of capsules, soil, natural products, and viscous compounds. Analysis was completed within a few seconds without the need for preseparation. Moreover, the quantification capability of EAPPI for matrices was evaluated by analyzing six polycyclic aromatic hydrocarbons (PAHs) in soil. The correlation coefficients ( R 2 ) for standard curves of all six PAHs were above 0.99, and the detection limits were in the range of 0.16-0.34 ng/mg. In addition, EAPPI could also be used to monitor organic chemical reactions in real time.

  16. Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices.

    PubMed

    Liu, Chengyuan; Yang, Jiuzhong; Wang, Jian; Hu, Yonghua; Zhao, Wan; Zhou, Zhongyue; Qi, Fei; Pan, Yang

    2016-10-01

    Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS). After careful optimization and testing with pure sample solution, EAPPI was successfully applied to the fast screening of capsules, soil, natural products, and viscous compounds. Analysis was completed within a few seconds without the need for preseparation. Moreover, the quantification capability of EAPPI for matrices was evaluated by analyzing six polycyclic aromatic hydrocarbons (PAHs) in soil. The correlation coefficients (R (2) ) for standard curves of all six PAHs were above 0.99, and the detection limits were in the range of 0.16-0.34 ng/mg. In addition, EAPPI could also be used to monitor organic chemical reactions in real time. Graphical Abstract ᅟ. PMID:27460208

  17. Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices.

    PubMed

    Liu, Chengyuan; Yang, Jiuzhong; Wang, Jian; Hu, Yonghua; Zhao, Wan; Zhou, Zhongyue; Qi, Fei; Pan, Yang

    2016-10-01

    Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS). After careful optimization and testing with pure sample solution, EAPPI was successfully applied to the fast screening of capsules, soil, natural products, and viscous compounds. Analysis was completed within a few seconds without the need for preseparation. Moreover, the quantification capability of EAPPI for matrices was evaluated by analyzing six polycyclic aromatic hydrocarbons (PAHs) in soil. The correlation coefficients (R (2) ) for standard curves of all six PAHs were above 0.99, and the detection limits were in the range of 0.16-0.34 ng/mg. In addition, EAPPI could also be used to monitor organic chemical reactions in real time. Graphical Abstract ᅟ.

  18. Chemical noise reduction via mass spectrometry and ion/ion charge inversion: amino acids.

    PubMed

    Hassell, Kerry M; LeBlanc, Yves C; McLuckey, Scott A

    2011-05-01

    Charge inversion ion/ion reactions can provide a significant reduction in chemical noise associated with mass spectra derived from complex mixtures for species composed of both acidic and basic sites, provided the ions derived from the matrix largely undergo neutralization. Amino acids constitute an important class of amphoteric compounds that undergo relatively efficient charge inversion. Precipitated plasma constitutes a relatively complex biological matrix that yields detectable signals at essentially every mass-to-charge value over a wide range. This chemical noise can be dramatically reduced using multiply charged reagent ions that can invert the charge of species amenable to the transfer of multiple charges upon a single interaction and by detecting product ions of opposite polarity. The principle is illustrated here with amino acids present in precipitated plasma subjected to ionization in the positive mode, reaction with anions derived from negative nanoelectrospray ionization of poly (amido amine) dendrimer generation 3.5, and mass analysis in the negative ion mode. PMID:21456599

  19. Modal structure of chemical mass size distribution in the high Arctic aerosol

    NASA Astrophysics Data System (ADS)

    Hillamo, Risto; Kerminen, Veli-Matti; Aurela, Minna; MäKelä, Timo; Maenhaut, Willy; Leek, Caroline

    2001-11-01

    Chemical mass size distributions of aerosol particles were measured in the remote marine boundary layer over the central Arctic Ocean as part of the Atmospheric Research Program on the Arctic Ocean Expedition 1996 (AOE-96). An inertial impaction method was used to classify aerosol particles into different size classes for subsequent chemical analysis. The particle chemical composition was determined by ion chromatography and by the particle-induced X-ray emission technique. Continuous particle size spectra were extracted from the raw data using a data inversion method. Clear and varying modal structures for aerosols consisting of primary sea-salt particles or of secondary particles related to dimethyl sulfide emissions were found. Concentration levels of all modes decreased rapidly when the distance from open sea increased. In the submicrometer size range the major ions found by ion chromatography were sulfate, methane sulfonate, and ammonium. They had most of the time a clear Aitken mode and one or two accumulation modes, with aerodynamic mass median diameters around 0.1 μm, 0.3 μm, and between 0.5-1.0 μm, respectively. The overall submicron size distributions of these three ions were quite similar, suggesting that they were internally mixed over most of this size range. The corresponding modal structure was consistent with the mass size distributions derived from the particle number size distributions measured with a differential mobility particle sizer. The Aitken to accumulation mode mass ratio for nss-sulfate and MSA was substantially higher during clear skies than during cloudy periods. Primary sea-salt particles formed a mode with an aerodynamic mass median diameter around 2 μm. In general, the resulting continuous mass size distributions displayed a clear modal structure consistent with our understanding of the two known major source mechanisms. One is the sea-salt aerosol emerging from seawater by bubble bursting. The other is related to

  20. Method to reduce chemical background interference in atmospheric pressure ionization liquid chromatography-mass spectrometry using exclusive reactions with the chemical reagent dimethyl disulfide.

    PubMed

    Guo, Xinghua; Bruins, Andries P; Covey, Thomas R

    2007-06-01

    The interference of chemical background ions (chemical noise) has been a problem since the inception of mass spectrometry. We present here a novel method to reduce the chemical noise in LC-MS based on exclusive gas-phase reactions with a reactive collision gas in a triple-quadrupole mass spectrometer. Combined with the zero neutral loss (ZNL) scan of a triple-quadrupole mass spectrometer, the reactive chemical noise ions can be removed because of shifts of mass-to-charge ratios from the original background ions. The test on various classes of compounds with different functional groups indicates a generic application of this technique in LC-MS. The preliminary results show that a reduction of the level of LC-MS base-peak chromatographic baseline by a factor up to 40 and an improvement of the signal-to-noise ratio by a factor up to 5-10 are achieved on both commercial and custom-modified triple-quadrupole LC-MS systems. Application is foreseen in both quantitative and qualitative trace analysis. It is expected that this chemical noise reduction technique can be optimized on a dedicated mass spectrometric instrumentation which incorporates both a chemical reaction cell for noise reduction and a collision stage for fragmentation.

  1. Ultrasonic nebulization extraction/low pressure photoionization mass spectrometry for direct analysis of chemicals in matrices.

    PubMed

    Liu, Chengyuan; Zhu, Yanan; Zhou, Zhongyue; Yang, Jiuzhong; Qi, Fei; Pan, Yang

    2015-09-01

    A novel ultrasonic nebulization extraction/low-pressure photoionization (UNE-LPPI) system has been designed and employed for the rapid mass spectrometric analysis of chemicals in matrices. An ultrasonic nebulizer was used to extract the chemicals in solid sample and nebulize the solvent in the nebulization cell. Aerosols formed by ultrasonic were evaporated by passing through a transferring tube, and desolvated chemicals were ionized by the emitted light (10.6 eV) from a Krypton discharge lamp at low pressure (∼68 Pa). First, a series of semi/non-volatile compounds with different polarities, such as polycyclic aromatic hydrocarbons (PAHs), amino acids, dipeptides, drugs, nucleic acids, alkaloids, and steroids were used to test the system. Then, the quantification capability of UNE-LPPI was checked with: 1) pure chemicals, such as 9,10-phenanthrenequinone and 1,4-naphthoquinone dissolved in solvent; 2) soil powder spiked with different amounts of phenanthrene and pyrene. For pure chemicals, the correlation coefficient (R(2)) for the standard curve of 9,10-phenanthrenequinone in the range of 3 ng-20 μg mL(-1) was 0.9922, and the measured limits of detection (LOD) was 1 ng ml(-1). In the case of soil powder, linear relationships for phenanthrene and pyrene from 10 to 400 ng mg(-1) were obtained with correlation coefficients of 0.9889 and 0.9893, respectively. At last, the feasibility of UNE-LPPI for the detection of chemicals in real matrices such as tablets and biological tissues (tea, Citrus aurantium peel and sage (Salvia officinalis) leaf) were successfully demonstrated. PMID:26388379

  2. Chemical evolution of a travertine-depositing stream: geochemical processes and mass transfer reactions

    SciTech Connect

    Lorah, M.M.; Herman, J.S.

    1988-09-01

    This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO/sub 2/ outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO/sub 2/ partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO/sub 2/ and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO/sub 2/ outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO/sub 2/ along the entire 5.2-km flow path. Outgassing of CO/sub 2/ drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO/sub 2/ by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO/sub 2/ outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO/sub 2/. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

  3. The global chemical properties of high-mass star forming clumps at different evolutionary stages

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Jun; Zhou, Jian-Jun; Esimbek, Jarken; He, Yu-Xin; Li, Da-Lei; Tang, Xin-Di; Ji, Wei-Guang; Yuan, Ye; Guo, Wei-Hua

    2016-06-01

    A total of 197 relatively isolated high-mass star-forming clumps were selected from the Millimeter Astronomy Legacy Team 90 GHz (MALT90) survey data and their global chemical evolution investigated using four molecular lines, N2H+ (1--0), HCO+ (1--0), HCN (1-0), and HNC (1-0). The results suggest that the global averaged integrated intensity ratios I(HCO+)/I(HNC), I(HCN)/I(HNC), I(N2H+)/I(HCO+), and I(N2H+)/ I(HCN) are promising tracers for evolution of high-mass star-forming clumps. The global averaged column densities and abundances of N2H+, HCO+, HCN, and HNC increase as clumps evolve. The global averaged abundance ratios X(HCN)/X(HNC) could be used to trace evolution of high-mass star forming clumps, X(HCO+)/X(HNC) is more suitable for distinguishing high-mass star-forming clumps in prestellar (stage A) from those in protostellar (stage B) and HII/PDR region (stage C). These results suggest that the global averaged integrated intensity ratios between HCN (1-0), HNC (1-0), HCO+ (1--0) and N2H+ (1--0) are more suitable for tracing the evolution of high-mass star forming clumps. We also studied the chemical properties of the target high-mass star-forming clumps in each spiral arm of the Galaxy, and got results very different from those above. This is probably due to the relatively small sample in each spiral arm. For high-mass star-forming clumps in Sagittarius arm and Norma-Outer arm, comparing two groups located on one arm with different Galactocentric distances, the clumps near the Galactic Center appear to be younger than those far from the Galactic center, which may be due to more dense gas concentrated near the Galactic Center, and hence more massive stars being formed there.

  4. Vadose Zone VOC Mass Transfer Testing At The SRS Miscellaneous Chemical Basin

    SciTech Connect

    Riha, B

    2005-10-30

    Active remedial activities have been ongoing since 1996 to address low levels of solvent contamination at the Miscellaneous Chemical Basin at SRS. Contaminant levels in the subsurface may be approaching levels where mass transfer limitations are impacting the efficiency of the remedial action. Rate limited mass transfer effects have been observed at other sites in the vadose zone at the SRS, however, detailed measurements and evaluation has not been undertaken. Anecdotal evidence suggests that the mass transfer rates are very slow from the fine grain sediments. This conclusion is based on the observation that measured soil gas concentrations tend to be low in permeable zones relative to the higher concentrations found in fine grain zones. Decreasing soil gas concentration with depth below the ''upland unit'' at several areas at SRS is also evidence of slow diffusion rates. In addition, due to the length of time since disposal ceased at the MCB, we hypothesize that mobile solvents have migrated downward, and the solvent remaining in the upper fine grain zone (''upland unit'') are trapped in fine grain material and are primarily released by gas diffusion (Riha and Rossabi 2004). Natural weathering and other chemical solutions disposed with the solvents can further enhance this effect by increasing the micro-porosity in the clays (kaolinite). This microporosity can result in increased entrapment of water and solvents by capillary forces (Powers, et. al., 2003). Also supporting this conclusion is the observation that active SVE has proven ineffective on VOC removal from the fine grain zones at the SRS. Adsorption and the very slow release phenomenon have been documented similarly in the literature especially for old solvent spills such as at the SRS (Pavlostathis and Mathavan 1992; Oostrom and Lenhard 2003). Mass transfer relationships need to be developed in order to optimize remediation activities and to determine actual loading rates to groundwater. These metrics

  5. Weapons of mass destruction: Overview of the CBRNEs (Chemical, Biological, Radiological, Nuclear, and Explosives).

    PubMed

    Prockop, Leon D

    2006-11-01

    The events of September 11, 2001, made citizens of the world acutely aware of disasters consequent to present-day terrorism. This is a war being waged for reasons obscure to many of its potential victims. The term "NBCs" was coined in reference to terrorist weapons of mass destruction, i.e., nuclear, biological and chemical. The currently accepted acronym is "CBRNE" which includes Chemical, Biological, Radiological, Nuclear, and Explosive weapons. Non-nuclear explosives are the most common terrorist weapon now in use. Nuclear and radiological weapons are beyond the scope of this publication, which focuses on the "CBEs", i.e. chemical, biological and explosive weapons. Although neurologists will not be the first responders to CBEs, they must know about the neurological effects in order to provide diagnosis and treatment to survivors. Neurological complications of chemical, biological and explosive weapons which have or may be used by terrorists are reviewed by international experts in this publication. Management and treatment profiles are outlined.

  6. Chemical profiling of cerebrospinal fluid by multiple reaction monitoring mass spectrometry.

    PubMed

    Ferreira, Christina R; Yannell, Karen E; Mollenhauer, Brit; Espy, Ryan D; Cordeiro, Fernanda B; Ouyang, Z; Cooks, R G

    2016-09-21

    We report an accelerated biomarker discovery workflow and results of sample screening by mass spectrometry based on multiple reaction monitoring (MRM). This methodology shows promising initial results for the currently unsolved challenge of Parkinson's disease (PD) laboratory diagnosis by biomarker screening. Small molecules present in cerebrospinal fluid (CSF) at low parts per million levels are monitored using specific transitions connecting ion pairs. A set of such transitions constitutes a multidimensional chemical profile used to distinguish and characterize different CSF samples using multivariate statistical methods. PMID:27517482

  7. Heat and mass transfer in unsteady rotating fluid flow with binary chemical reaction and activation energy.

    PubMed

    Awad, Faiz G; Motsa, Sandile; Khumalo, Melusi

    2014-01-01

    In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

  8. Heat and Mass Transfer in Unsteady Rotating Fluid Flow with Binary Chemical Reaction and Activation Energy

    PubMed Central

    Awad, Faiz G.; Motsa, Sandile; Khumalo, Melusi

    2014-01-01

    In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

  9. A miniature laser ablation mass spectrometer for in situ chemical composition investigation of lunar surface

    NASA Astrophysics Data System (ADS)

    Neuland, M. B.; Mezger, K.; Riedo, A.; Tulej, M.; Wurz, P.

    2015-10-01

    A miniature laser ablation mass spectrometer (LMS) is presented. The LMS is designed as a flight instrument for planetary and space research and optimised for in situ measurements of the chemical composition of rocks and soils on a planetary surface. By means of measure-ments standard reference materials of soil and a sample of the Allende meteorite we demonstrate that LMS is a suitable instrument for in situ measurements of elemental and isotopic composition with high precision and accuracy. Furthermore, it is shown that LMS data allows deriving of the material mineralogy and petrology with high spatial resolution, lateral and vertical, and the application of in situ age dating methods.

  10. In situ chemical composition measurements with a miniature laser ablation mass spectrometer for planetary exploration

    NASA Astrophysics Data System (ADS)

    Neuland, M. B.; Meyer, S.; Mezger, K.; Riedo, A.; Tulej, M.; Wurz, P.

    2013-09-01

    We present a miniature laser ablation mass spectrometer (LMS) for planetary and space research. For demonstrating the performance of the instrument, a sample of Allende meteorite is investigated as an analogue to a planetary surface. Investigation of a very inhomogeneous structure like the surface of a chondritic meteorite requires high spatially resolved data of chemical content, elemental and isotopic. We measure the composition of the Allende meteorite and show that by using a ns-laser for ablation, elemental analysis is accomplished with high quality allowing to study the mineralogy. The results will be compared to measurements using a fs-laser system to show improvements of the technique.

  11. Chemical profiling of cerebrospinal fluid by multiple reaction monitoring mass spectrometry.

    PubMed

    Ferreira, Christina R; Yannell, Karen E; Mollenhauer, Brit; Espy, Ryan D; Cordeiro, Fernanda B; Ouyang, Z; Cooks, R G

    2016-09-21

    We report an accelerated biomarker discovery workflow and results of sample screening by mass spectrometry based on multiple reaction monitoring (MRM). This methodology shows promising initial results for the currently unsolved challenge of Parkinson's disease (PD) laboratory diagnosis by biomarker screening. Small molecules present in cerebrospinal fluid (CSF) at low parts per million levels are monitored using specific transitions connecting ion pairs. A set of such transitions constitutes a multidimensional chemical profile used to distinguish and characterize different CSF samples using multivariate statistical methods.

  12. Formation and thermodynamics of gaseous germanium and tin vanadates: a mass spectrometric and quantum chemical study.

    PubMed

    Shugurov, S M; Panin, A I; Lopatin, S I; Emelyanova, K A

    2015-06-01

    The stabilities of gaseous germanium and tin vanadates were confirmed by high temperature mass spectrometry, and its structures were determined by quantum chemical calculations. A number of gas-phase reactions involving these gaseous salts were studied. On the basis of the equilibrium constants, the standard formation enthalpies of gaseous GeV2O6 (-1520 ± 42 kJ mol(-1)) and SnV2O6 (-1520 ± 43 kJ mol(-1)) were determined at a temperature of 298 K.

  13. Ion mobility-mass spectrometry strategies for untargeted systems, synthetic, and chemical biology

    PubMed Central

    May, Jody C.; Goodwin, Cody R.; McLean, John A.

    2014-01-01

    Contemporary strategies that concentrate on only one or a handful of molecular targets limits the utility of the information gained for diagnostic and predictive purposes. Recent advances in the sensitivity, speed, and precision of measurements obtained from ion mobility coupled to mass spectrometry (IM-MS) have accelerated the utility of IM-MS in untargeted, discovery-driven studies in biology. Perhaps most evident is the impact that such wide-scale discovery capabilities have yielded in the areas of systems, synthetic, and chemical biology, where the need for comprehensive, hypothesis-driving studies from multidimensional and unbiased data is required. PMID:25462629

  14. Development of Highly Sensitive Compact Raman Scanner for Mass Screening of Chemical Dyes

    NASA Astrophysics Data System (ADS)

    Dinish, U. S.; Fu, Chit Yaw; Olivo, Malini

    2010-08-01

    In the Raman analysis of various chemicals, it is often required to do mass screening of dyes and their derivatives. In most cases, it is impractical to screen each dye one by one on a commercial Raman system, which is catered to screen one analyte at a time. In this context, we proposed the design of simple, cost effective and compact `Raman Scanner' developed using commercial laser, detector and optical components. The high throughput screening capability of the system is demonstrated by acquiring the SERS spectra of various molecules adsorbed on to gold colloid in a 96 well plate.

  15. Mass spectrometric study of selected precursors and degradation products of chemical warfare agents.

    PubMed

    Papousková, Barbora; Bednár, Petr; Frysová, Iveta; Stýskala, Jakub; Hlavác, Jan; Barták, Petr; Ulrichová, Jitka; Jirkovský, Jaromír; Lemr, Karel

    2007-12-01

    Selected precursors and degradation products of chemical warfare agents namely N,N-dialkylaminoethane-2-ols, N,N-dialkylaminoethyl-2-chlorides and some of related N-quaternary salts were studied by means of electrospray ionization-multiple tandem mass spectrometry (ESI-MS(n)). Proposed structures were confirmed with accurate mass measurement. General fragmentation patterns of these compounds are discussed in detail and suggested processes are confirmed using deuterated standards. The typical processes are elimination of alkene, hydrogen chloride, or water, respectively. Besides, elimination of ethene from propyl chain under specific conditions was observed and unambiguously confirmed using exact mass measurement and labelled standard. The potential of mass spectrometry to distinguish the positional isomers occurring among the studied compounds is reviewed in detail using two different MS instruments (i.e. ion trap and hybrid quadrupole-time of flight (Q-TOF) analyzer). A new microcolumn liquid chromatography (microLC)/MS(n) method was designed for the cases where the resolution based solely on differences in fragmentation is not sufficient. Low retention of the derivatives on reversed phase (RP) was overcome by using addition of less typical ion pairing agent (1 mM/l, 3,5-dinitrobenzoic acid) to the mobile phase (mixture water : acetonitrile). PMID:18085550

  16. Towards smaller and faster gas chromatography-mass spectrometry systems for field chemical detection.

    PubMed

    Smith, P A; Sng, M T; Eckenrode, B A; Leow, S Y; Koch, D; Erickson, R P; Jackson Lepage, C R; Hook, G L

    2005-03-01

    Gas chromatography-mass spectrometry (GC-MS) is already an important laboratory method, but new sampling techniques and column heating approaches will expand and improve its usefulness for detection and identification of unknown chemicals in field settings. In order to demonstrate commercially-available technical advances for both sampling and column heating, we used solid phase microextraction (SPME) sampling of both water and air systems, followed by immediate analysis with a resistively heated analytical column and mass spectrometric detection. High-concern compounds ranging from 140 to 466 amu were analyzed to show the applicability of these techniques to emergency situations impacting public health. A field portable (about 35 kg) GC-MS system was used for analysis of water samples with a resistively heated analytical column externally mounted as a retrofit using the air bath oven of the original instrument design to heat transfer lines. The system used to analyze air samples included a laboratory mass spectrometer with a dedicated resistive column heating arrangement (no legacy air bath column oven). The combined sampling and analysis time was less than 10 min for both air and water sample types. By combining dedicated resistive column heating with smaller mass spectrometry systems designed specificallyfor use in the field, substantially smaller high performance field-portable instrumentation will be possible.

  17. Application of a trochoidal electron monochromator/mass spectrometer system to the study of environmental chemicals

    SciTech Connect

    Laramee, J.A.; Kocher, C.A.; Deinzer, M.L. )

    1992-10-15

    A trochoidal electron monochromator has been interfaced to a mass spectrometer to perform electron capture negative ion mass spectrometric (ECNIMS) analyses of environmentally relevant chemicals. The kinetic energy of the electron beam can be varied from 0.025 to 30 eV under computer control. No reagent gas is used to moderate the electron energies. An electron energy spread of +/- 0.1 to +/- 0.4 eV full width at half-maximum (fwhm) can readily be obtained at a transmitted current of 2 x 10(-6) A, improving to +/- 0.07 eV at 5 x 10(-7) A. Comparisons of ECNI results from the electron monochromator/mass spectrometer system with those from a standard instrument that uses a moderating gas show similar spectra for heptachlor but not for the s-triazine herbicides, as for example, atrazine. This compound shows numerous adduct ions by standard ECNIMS that are eliminated by using the electron monochromator to generate the mass spectra. Isomeric tetrachlorodibenzo-p-dioxins show distinct differences in the electron energies needed to produce the maximum amount of parent and fragment anions. Multiple resonance states resulting in stable radical anions (M.-) are easily observed for nitrobenzene and for polycyclic aromatic hydrocarbons. Ionic products of dissociative electron capture invariably occur from several resonance states.

  18. Impacts of Typhoon and Air-Mass Pathways on Rainwater Chemical Compositions

    NASA Astrophysics Data System (ADS)

    Cheng, M.; You, C.

    2006-12-01

    To assess the importance of chemical fluxes on trace elements by wet precipitation, we have collected time- series rain waters between 06/20/04 and 09/20/05 for ICPMS and IC measurements. The sampling site is located at Tainan city in southwest Taiwan and there were four typhoons, namely Mindulle, Rananim, Aere, and Haima, hit the island during this period. Combining trace element compositions with HYSPLIT model for air-mass transportation designed by NOAA, we were able to understand possible source, flux and migration pathway of pollutants in rainwater. Our results show that seasalt contribution and trace element fluxes were higher during typhoon events. The Na and Pb flux varied largely, between 0.03~1388 and 0.0002~2000 mg/m2/day respectively, depended on the pathways of air mass trajectory and wind strength. It is clear that typhoons carry not only sea spray but also major anthropogenic pollutants from south Asia. Among the four typhoons, the Mindulle carried the largest fluxes of seasalt and trace elements while Rananim was weak in strength and brought the lowest Na and Pb due to less degree of mixing with air mass on land. The calculated enriched factors normalized to seawater (EFsea) were near unity for Na and Mg, but were much larger for K and Ca possibly due to crust source contamination and biomass burning. The EFcrust or EFsea values of various trace metals (e.g., V, Cr, Mn, Co, Ni, Cu, Zn, As, Ba and Pb were all significantly larger than 10 indicating the importance of anthropogenic sources. Interestingly, the PCA results confirm that rain waters with similar chemical characteristics have shared common air mass backward trajectory history.

  19. Mass size distributions and size resolved chemical composition of fine particulate matter at the Pittsburgh supersite

    NASA Astrophysics Data System (ADS)

    Cabada, Juan C.; Rees, Sarah; Takahama, Satoshi; Khlystov, Andrey; Pandis, Spyros N.; Davidson, Cliff I.; Robinson, Allen L.

    Size-resolved aerosol mass and chemical composition were measured during the Pittsburgh Air Quality Study. Daily samples were collected for 12 months from July 2001 to June 2002. Micro-orifice uniform deposit impactors (MOUDIs) were used to collect aerosol samples of fine particulate matter smaller than 10 μm. Measurements of PM 0.056, PM 0.10, PM 0.18, PM 0.32, PM 0.56, PM 1.0, PM 1.8 and PM 2.5 with the MOUDI are available for the full study period. Seasonal variations in the concentrations are observed for all size cuts. Higher concentrations are observed during the summer and lower during the winter. Comparison between the PM 2.5 measurements by the MOUDI and other integrated PM samplers reveals good agreement. Good correlation is observed for PM 10 between the MOUDI and an integrated sampler but the MOUDI underestimates PM 10 by 20%. Bouncing of particles from higher stages of the MOUDI (>PM 2.5) is not a major problem because of the low concentrations of coarse particles in the area. The main cause of coarse particle losses appears to be losses to the wall of the MOUDI. Samples were collected on aluminum foils for analysis of carbonaceous material and on Teflon filters for analysis of particle mass and inorganic anions and cations. Daily samples were analyzed during the summer (July 2001) and the winter intensives (January 2002). During the summer around 50% of the organic material is lost from the aluminum foils as compared to a filter-based sampler. These losses are due to volatilization and bounce-off from the MOUDI stages. High nitrate losses from the MOUDI are also observed during the summer (above 70%). Good agreement between the gravimetrically determined mass and the sum of the masses of the individual compounds is obtained, if the lost mass from organics and the aerosol water content are included for the summer. For the winter no significant losses of material are detected and there exists reasonable agreement between the gravimetrical mass and the

  20. Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Newsome, G. Asher; Steinkamp, F. Lucus; Giordano, Braden C.

    2016-11-01

    As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane ( i-C4H10) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer. Analyte spectra were directly compared using methane, isobutane, and isobutane/argon mixtures. A mixture of 10% i-C4H10 in argon produced twice the positive-mode analyte signal of methane, equal to pure isobutane, and reduced spectral dependence on reagent gas pressure. Electron capture negative chemical ionization using 1% i-C4H10 in argon tripled analyte signal compared with methane and was reproducible, unlike pure isobutane. The operative lifetime of the ion source using isobutane/argon mixtures was extended exponentially compared with pure isobutane, producing stable and reproducible CI signal throughout. By diluting the reagent gas in an inert buffer gas, isobutane CI-MS experiments were made as practical to use as methane CI-MS experiments but with superior analytical performance.

  1. Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer

    NASA Technical Reports Server (NTRS)

    Niemann, H. B.; Atreya, S. K.; Carignan, G. R.; Donahue, T. M.; Haberman, J. A.; Harpold, D. N.; Hartle, R. E.; Hunten, D. M.; Kasprzak, W. T.; Mahaffy, P. R.; Owen, T. C.; Spencer, N. W.

    1998-01-01

    The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

  2. Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer.

    PubMed

    Niemann, H B; Atreya, S K; Carignan, G R; Donahue, T M; Haberman, J A; Harpold, D N; Hartle, R E; Hunten, D M; Kasprzak, W T; Mahaffy, P R; Owen, T C; Spencer, N W

    1998-01-01

    The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe. PMID:11541457

  3. Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Newsome, G. Asher; Steinkamp, F. Lucus; Giordano, Braden C.

    2016-08-01

    As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane (i-C4H10) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer. Analyte spectra were directly compared using methane, isobutane, and isobutane/argon mixtures. A mixture of 10% i-C4H10 in argon produced twice the positive-mode analyte signal of methane, equal to pure isobutane, and reduced spectral dependence on reagent gas pressure. Electron capture negative chemical ionization using 1% i-C4H10 in argon tripled analyte signal compared with methane and was reproducible, unlike pure isobutane. The operative lifetime of the ion source using isobutane/argon mixtures was extended exponentially compared with pure isobutane, producing stable and reproducible CI signal throughout. By diluting the reagent gas in an inert buffer gas, isobutane CI-MS experiments were made as practical to use as methane CI-MS experiments but with superior analytical performance.

  4. SOURCE APPORTIONMENT OF PM 2.5 AND CARBON IN SEATTLE USING CHEMICAL MASS BALANCE AND POSITIVE MATRIX FACTORIZATION

    EPA Science Inventory

    Three years of PM2.5 speciated data were collected and chemically analyzed using the IMPROVE protocol at the Beacon Hill site in Seattle. The data were analyzed by the Chemical Mass Balance Version 8 (CMB8) and Positive Matrix Factorization (PMF) source apportionment models. T...

  5. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  6. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    PubMed Central

    Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  7. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    PubMed Central

    Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit. PMID:27610289

  8. Chemical crosslinking and mass spectrometry studies of the structure and dynamics of membrane proteins and receptors.

    SciTech Connect

    Haskins, William E.; Leavell, Michael D.; Lane, Pamela; Jacobsen, Richard B.; Hong, Joohee; Ayson, Marites J.; Wood, Nichole L.; Schoeniger, Joseph S.; Kruppa, Gary Hermann; Sale, Kenneth L.; Young, Malin M.; Novak, Petr

    2005-03-01

    Membrane proteins make up a diverse and important subset of proteins for which structural information is limited. In this study, chemical cross-linking and mass spectrometry were used to explore the structure of the G-protein-coupled photoreceptor bovine rhodopsin in the dark-state conformation. All experiments were performed in rod outer segment membranes using amino acid 'handles' in the native protein sequence and thus minimizing perturbations to the native protein structure. Cysteine and lysine residues were covalently cross-linked using commercially available reagents with a range of linker arm lengths. Following chemical digestion of cross-linked protein, cross-linked peptides were identified by accurate mass measurement using liquid chromatography-fourier transform mass spectrometry and an automated data analysis pipeline. Assignments were confirmed and, if necessary, resolved, by tandem MS. The relative reactivity of lysine residues participating in cross-links was evaluated by labeling with NHS-esters. A distinct pattern of cross-link formation within the C-terminal domain, and between loop I and the C-terminal domain, emerged. Theoretical distances based on cross-linking were compared to inter-atomic distances determined from the energy-minimized X-ray crystal structure and Monte Carlo conformational search procedures. In general, the observed cross-links can be explained by re-positioning participating side-chains without significantly altering backbone structure. One exception, between C3 16 and K325, requires backbone motion to bring the reactive atoms into sufficient proximity for cross-linking. Evidence from other studies suggests that residues around K325 for a region of high backbone mobility. These findings show that cross-linking studies can provide insight into the structural dynamics of membrane proteins in their native environment.

  9. Chemical analysis and genotoxicity of high molecular mass PAH in sediment samples and biota

    SciTech Connect

    McCarry, B.E.; Marvin, C.H.; Smith, R.W.; Bryant, D.W.

    1995-12-31

    A normal phase liquid chromatography (NPLC) method was used to fractionate the organic extracts of prepared from coal tar-contaminated sediments from hamilton Harbor in Ontario and from Sydney Harbor in Nova Scotia into molecular mass classes. Each PAH fraction up to 302 amu was analyzed by GC-MS and fractions containing PAH with molecular masses greater than 302 amu were analyzed by atmospheric pressure chemical ionization (APCI) LC-MS.Each fraction was also subjected to Ames bioassays using a TA100-like strain of Salmonella typhimurium (YG1025 + S9). The 300/302 amu, 326/328 and 350/352 amu PAH fractions accounted for 25% of the total genotoxic response of the extract; these PAH constitute a substantial genotoxic burden. A number of 300, 302, 326, 350, 374 and 400 amu PAH were identified using APCI LC-MS and comparison with authentic standards. The non-polar aromatic extracts of bottom sediments, suspended sediments and zebra mussels from Hamilton Harbor were also examined by GC-MS, APCI LC-MS and genotoxicity bioassays. The profiles of the priority and high mass PAH in these samples were identical showing that all PAH up to and exceeding 400 amu were readily bioavailable to biota such as Zebra mussels. In addition, the pseudo faeces of the Zebra mussels and amphipod detritivores which fed on the pseudo faeces had chemical profiles identical to the Zebra mussels. Since many sport fish prize amphipods as food, this observation demonstrates a pathway for organic contaminants adsorbed to suspended sediments to enter the food chain of non-bottom-feeding fish in areas infested by Zebra mussels.

  10. In situ Analysis of Organic Compounds on Mars using Chemical Derivatization and Gas Chromatography Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Glavin, D. P.; Buch, A.; Cabane, M.; Coll, P.; Navarro-Gonzalez, R.; Mahaffy, P. R.

    2005-01-01

    One of the core science objectives of NASA's 2009 Mars Science Laboratory (MSL) mission is to determine the past or present habitability of Mars. The search for key organic compounds relevant to terrestrial life will be an important part of that assessment. We have developed a protocol for the analysis of amino acids and carboxylic acids in Mars analogue materials using gas chromatography mass spectrometry (GCMS). As shown, a variety of carboxylic acids were readily identified in soil collected from the Atacama Desert in Chile at part-per-billion levels by GCMS after extraction and chemical derivatization using the reagent N,N-tert.-butyl (dimethylsilyl) trifluoroacetamide (MTBSTFA). Several derivatized amino acids including glycine and alanine were also detected by GCMS in the Atacama soil at lower concentrations (chromatogram not shown). Lacking derivatization capability, the Viking pyrolysis GCMS instruments could not have detected amino acids and carboxylic acids, since these non-volatile compounds require chemical transformation into volatile species that are stable in a GC column. We are currently optimizing the chemical extraction and derivatization technique for in situ GCMS analysis on Mars. Laboratory results of analyses of Atacama Desert samples and other Mars analogue materials using this protocol will be presented.

  11. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions.

  12. Chemical imaging of latent fingerprints by mass spectrometry based on laser activated electron tunneling.

    PubMed

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Zhong, Hongying

    2015-03-01

    Identification of endogenous and exogenous chemicals contained in latent fingerprints is important for forensic science in order to acquire evidence of criminal identities and contacts with specific chemicals. Mass spectrometry has emerged as a powerful technique for such applications without any derivatization or fluorescent tags. Among these techniques, MALDI (Matrix Assisted Laser Desorption Ionization) provides small beam size but has interferences with MALDI matrix materials, which cause ion suppressions as well as limited spatial resolution resulting from uneven distribution of MALDI matrix crystals with different sizes. LAET (Laser Activated Electron Tunneling) described in this work offers capabilities for chemical imaging through electron-directed soft ionization. A special film of semiconductors has been designed for collection of fingerprints. Nanoparticles of bismuth cobalt zinc oxide were compressed on a conductive metal substrate (Al or Cu sticky tape) under 10 MPa pressure. Resultant uniform thin films provide tight and shining surfaces on which fingers are impressed. Irradiation of ultraviolet laser pulses (355 nm) on the thin film instantly generates photoelectrons that can be captured by adsorbed organic molecules and subsequently cause electron-directed ionization and fragmentation. Imaging of latent fingerprints is achieved by visualization of the spatial distribution of these molecular ions and structural information-rich fragment ions. Atomic electron emission together with finely tuned laser beam size improve spatial resolution. With the LAET technique, imaging analysis not only can identify physical shapes but also reveal endogenous metabolites present in females and males, detect contacts with prohibited substances, and resolve overlapped latent fingerprints. PMID:25647159

  13. Chemical imaging of latent fingerprints by mass spectrometry based on laser activated electron tunneling.

    PubMed

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Zhong, Hongying

    2015-03-01

    Identification of endogenous and exogenous chemicals contained in latent fingerprints is important for forensic science in order to acquire evidence of criminal identities and contacts with specific chemicals. Mass spectrometry has emerged as a powerful technique for such applications without any derivatization or fluorescent tags. Among these techniques, MALDI (Matrix Assisted Laser Desorption Ionization) provides small beam size but has interferences with MALDI matrix materials, which cause ion suppressions as well as limited spatial resolution resulting from uneven distribution of MALDI matrix crystals with different sizes. LAET (Laser Activated Electron Tunneling) described in this work offers capabilities for chemical imaging through electron-directed soft ionization. A special film of semiconductors has been designed for collection of fingerprints. Nanoparticles of bismuth cobalt zinc oxide were compressed on a conductive metal substrate (Al or Cu sticky tape) under 10 MPa pressure. Resultant uniform thin films provide tight and shining surfaces on which fingers are impressed. Irradiation of ultraviolet laser pulses (355 nm) on the thin film instantly generates photoelectrons that can be captured by adsorbed organic molecules and subsequently cause electron-directed ionization and fragmentation. Imaging of latent fingerprints is achieved by visualization of the spatial distribution of these molecular ions and structural information-rich fragment ions. Atomic electron emission together with finely tuned laser beam size improve spatial resolution. With the LAET technique, imaging analysis not only can identify physical shapes but also reveal endogenous metabolites present in females and males, detect contacts with prohibited substances, and resolve overlapped latent fingerprints.

  14. Glioblastoma stem cells: radiobiological response to ionising radiations of different qualities.

    PubMed

    Pecchia, I; Dini, V; Ricci-Vitiani, L; Biffoni, M; Balduzzi, M; Fratini, E; Belli, M; Campa, A; Esposito, G; Cirrone, G; Romano, F; Stancampiano, C; Pelacchi, F; Pallini, R; Tabocchini, M A

    2015-09-01

    Glioblastoma multiforme (GBM) is the most common and malignant primary brain tumour, with very poor prognosis. The high recurrence rate and failure of conventional treatments are expected to be related to the presence of radio-resistant cancer stem cells (CSCs) inside the tumour mass. CSCs can both self-renew and differentiate into the heterogeneous lineages of cancer cells. Recent evidence showed a higher effectiveness of C-ions and protons in inactivating CSCs, suggesting a potential advantage of Hadrontherapy compared with conventional radiotherapy for GBM treatment. To investigate the mechanisms involved in the molecular and cellular responses of CSCs to ionising radiations, two GBM stem cell (GSC) lines, named lines 1 and 83, which were derived from patients with different clinical outcomes and having different metabolic profiles (as shown by NMR spectroscopy), were irradiated with (137)Cs photons and with protons or C-ions of 62 MeV u(-1) in the dose range of 5-40 Gy. The biological effects investigated were: cell death, cell cycle progression, and DNA damage induction and repair. Preliminary results show a different response to ionising radiation between the two GSC lines for the different end points investigated. Further experiments are in progress to consolidate the data and to get more insights on the influence of radiation quality.

  15. Glycomic Analysis of Glycans Released from Glycoproteins Using Chemical Immobilization and Mass Spectrometry

    PubMed Central

    Yang, Shuang; Zhang, Hui

    2014-01-01

    Protein glycosylation is one of most common protein modifications and is involved in many biological activities. N-linked and O-linked glycosylation not only represents abundant glycan modifications, but also are structurally diverse. Mass spectrometry has emerged as a major method for glycomic analysis. However, glycan extraction from proteins and glycan modification are two critical steps in glycomic analysis of glycans using mass spectrometry. In this protocol, we describe a novel and high-throughput method for isolation and modification of glycans from glycoproteins using a chemoenzymatic approach on solid-phase. Proteins are first immobilized to a solid support and unconjugated molecules are washed away; glycans, while still linked to glycoproteins on the solid support, can be treated enzymatically or chemically on solid-phase for glycan derivatization. Glycans are then released from the solid support for analysis by mass spectrometry. The procedures outlined are robust and useful for high-throughput glycomic analysis from complex biological or clinical samples. PMID:25205566

  16. Mass Spectrometric Quantification of Histone Post-translational Modifications by a Hybrid Chemical Labeling Method

    PubMed Central

    Maile, Tobias M.; Izrael-Tomasevic, Anita; Cheung, Tommy; Guler, Gulfem D.; Tindell, Charles; Masselot, Alexandre; Liang, Jun; Zhao, Feng; Trojer, Patrick; Classon, Marie; Arnott, David

    2015-01-01

    Mass spectrometry is a powerful alternative to antibody-based methods for the analysis of histone post-translational modifications (marks). A key development in this approach was the deliberate propionylation of histones to improve sequence coverage across the lysine-rich and hydrophilic tails that bear most modifications. Several marks continue to be problematic however, particularly di- and tri-methylated lysine 4 of histone H3 which we found to be subject to substantial and selective losses during sample preparation and liquid chromatography-mass spectrometry. We developed a new method employing a “one-pot” hybrid chemical derivatization of histones, whereby an initial conversion of free lysines to their propionylated forms under mild aqueous conditions is followed by trypsin digestion and labeling of new peptide N termini with phenyl isocyanate. High resolution mass spectrometry was used to collect qualitative and quantitative data, and a novel web-based software application (Fishtones) was developed for viewing and quantifying histone marks in the resulting data sets. Recoveries of 53 methyl, acetyl, and phosphoryl marks on histone H3.1 were improved by an average of threefold overall, and over 50-fold for H3K4 di- and tri-methyl marks. The power of this workflow for epigenetic research and drug discovery was demonstrated by measuring quantitative changes in H3K4 trimethylation induced by small molecule inhibitors of lysine demethylases and siRNA knockdown of epigenetic modifiers ASH2L and WDR5. PMID:25680960

  17. Chemical ionization mass spectrometry using carbon nanotube field emission electron sources.

    PubMed

    Radauscher, Erich J; Keil, Adam D; Wells, Mitch; Amsden, Jason J; Piascik, Jeffrey R; Parker, Charles B; Stoner, Brian R; Glass, Jeffrey T

    2015-11-01

    A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities. Graphical Abstract ᅟ. PMID:26133527

  18. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    PubMed

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-01

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources. PMID:27281271

  19. Chemical Ionization Mass Spectrometry Using Carbon Nanotube Field Emission Electron Sources

    NASA Astrophysics Data System (ADS)

    Radauscher, Erich J.; Keil, Adam D.; Wells, Mitch; Amsden, Jason J.; Piascik, Jeffrey R.; Parker, Charles B.; Stoner, Brian R.; Glass, Jeffrey T.

    2015-11-01

    A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities.

  20. Autonomous bio-chemical decontaminator (ABCD) against weapons of mass destruction

    NASA Astrophysics Data System (ADS)

    Hyacinthe, Berg P.

    2006-05-01

    The proliferation of weapons of mass destruction (WMD) and the use of such elements pose an eminent asymmetric threat with disastrous consequences to the national security of any nation. In particular, the use of biochemical warfare agents against civilians and unprotected troops in international conflicts or by terrorists against civilians is considered as a very peculiar threat. Accordingly, taking a quarantine-before-inhalation approach to biochemical warfare, the author introduces the notion of autonomous biochemical decontamination against WMD. In the unfortunate event of a biochemical attack, the apparatus proposed herein is intended to automatically detect, identify, and more importantly neutralize a biochemical threat. Along with warnings concerning a cyber-WMD nexus, various sections cover discussions on human senses and computer sensors, corroborating evidence related to detection and neutralization of chemical toxins, and cyber-assisted olfaction in stand alone, peer-to-peer, and network settings. In essence, the apparatus can be used in aviation and mass transit security to initiate mass decontamination by dispersing a decontaminant aerosol or to protect the public water supply against a potential bioterrorist attack. Future effort may involve a system-on-chip (SoC) embodiment of this apparatus that allows a safer environment for the emerging phenomenon of cyber-assisted olfaction and morph cell phones into ubiquitous sensors/decontaminators. Although this paper covers mechanisms and protocols to avail a neutralizing substance, further research will need to explore the substance's various pharmacological profiles and potential side effects.

  1. In Situ Chemical Composition Measurements of Planetary Surfaces with a Laser Ablation Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Brigitte Neuland, Maike; Riedo, Andreas; Meyer, Stefan; Mezger, Klaus; Tulej, Marek; Wurz, Peter

    2013-04-01

    The knowledge of the chemical composition of moons, comets, asteroids or other planetary bodies is of particular importance for the investigation of the origin and evolution of the Solar System. For cosmochemistry, the elemental and isotopic composition of the surface material is essential information to investigate origin, differentiation and evolution processes of the body and therefore the history of our Solar System [1]. We show that the use of laser-based mass spectrometers is essential in such research because of their high sensitivity in the ppm range and their capability for quantitative elemental and isotopic analysis. A miniaturised Laser Ablation Time-of-Flight Mass Spectrometer (LMS) was developed in our group to study the elemental composition of solid samples [2]. The instrument's small size and light weight make it suitable for an application on a space mission to determine the elemental composition of a planetary surface for example [3]. Meteorites offer the excellent possibility to study extraterrestrial material in the laboratory. To demonstrate the sensitivity and functionality of the LMS instrument, a sample of the Allende meteorite has been investigated with a high spatial resolution. The LMS measurements allowed investigations of the elemental abundances in the Allende meteorite and detailed studies of the mineralogy and volatility [4]. These approaches can be of considerable interest for in situ investigation of grains and inhomogeneous materials with high sensitivity on a planetary surface. [1] Wurz, P., Whitby, J., Managadze, G., 2009, Laser Mass Spectrometry in Planetary Science, AIP Conf. Proc. CP1144, 70-75. [2] Tulej, M., Riedo, A., Iakovleva, M., Wurz, P., 2012, Int. J. Spec., On Applicability of a Miniaturized Laser Ablation Time of Flight Mass Spectrometer for Trace Element Measurements, article ID 234949. [3] Riedo, A., Bieler, A., Neuland, M., Tulej, M., Wurz, P., 2012, Performance evaluation of a miniature laser ablation time

  2. Detection of Chemical/Biological Agents and Stimulants using Quadrupole Ion Trap Mass Spectrometry

    SciTech Connect

    Harmon, S.H.; Hart, K.J.; Vass, A.A.; Wise, M.B.; Wolf, D.A.

    1999-06-14

    Detection of Chemical/Biological Agents and Simulants A new detector for chemical and biological agents is being developed for the U. S. Army under the Chemical and Biological Mass Spectrometer Block II program. The CBMS Block II is designed to optimize detection of both chemical and biological agents through the use of direct sampling inlets [I], a multi- ported sampling valve and a turbo- based vacuum system to support chemical ionization. Unit mass resolution using air as the buffer gas [2] has been obtained using this design. Software to control the instrument and to analyze the data generated from the instrument has also been newly developed. Detection of chemical agents can be accomplished. using the CBMS Block II design via one of two inlets - a l/ I 6'' stainless steel sample line -Chemical Warfare Air (CW Air) or a ground probe with enclosed capillary currently in use by the US Army - CW Ground. The Block II design is capable of both electron ionization and chemical ionization. Ethanol is being used as the Cl reagent based on a study indicating best performance for the Biological Warfare (BW) detection task (31). Data showing good signal to noise for 500 pg of methyl salicylate injected into the CW Air inlet, 50 ng of dimethylmethylphosphonate exposed to the CW Ground probe and 5 ng of methyl stearate analyzed using the pyrolyzer inlet were presented. Biological agents are sampled using a ''bio-concentrator'' unit that is designed to concentrate particles in the low micron range. Particles are collected in the bottom of a quartz pyrolyzer tube. An automated injector is being developed to deliver approximately 2 pL of a methylating reagent, tetramethylamonium- hydroxide to 'the collected particles. Pyrolysis occurs by rapid heating to ca. 55OOC. Biological agents are then characterized by their fatty acid methyl ester profiles and by other biomarkers. A library of ETOH- Cl/ pyrolysis MS data of microorganisms used for a recently published study [3] has been

  3. Dilepton production as a useful probe of quark gluon plasma with temperature dependent chemical potential quark mass

    NASA Astrophysics Data System (ADS)

    Kumar, Yogesh; Singh, S. Somorendro

    2016-07-01

    We extend the previous study of dilepton production using [S. Somorendro Singh and Y. Kumar, Can. J. Phys. 92 (2014) 31] based on a simple quasiparticle model of quark-gluon plasma (QGP). In this model, finite value of quark mass uses temperature dependent chemical potential the so-called Temperature Dependent Chemical Potential Quark Mass (TDCPQM). We calculate dilepton production in the relevant range of mass region. It is observed that the production rate is marginally enhanced from the earlier work. This is due to the effect of TDCPQM and its effect is highly significant in the production of dilepton.

  4. Chemical analysis of bleach and hydroxide-based solutions after decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX).

    PubMed

    Hopkins, F B; Gravett, M R; Self, A J; Wang, M; Chua, Hoe-Chee; Hoe-Chee, C; Lee, H S Nancy; Sim, N Lee Hoi; Jones, J T A; Timperley, C M; Riches, J R

    2014-08-01

    Detailed chemical analysis of solutions used to decontaminate chemical warfare agents can be used to support verification and forensic attribution. Decontamination solutions are amongst the most difficult matrices for chemical analysis because of their corrosive and potentially emulsion-based nature. Consequently, there are relatively few publications that report their detailed chemical analysis. This paper describes the application of modern analytical techniques to the analysis of decontamination solutions following decontamination of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). We confirm the formation of N,N-diisopropylformamide and N,N-diisopropylamine following decontamination of VX with hypochlorite-based solution, whereas they were not detected in extracts of hydroxide-based decontamination solutions by nuclear magnetic resonance (NMR) spectroscopy or gas chromatography-mass spectrometry. We report the electron ionisation and chemical ionisation mass spectroscopic details, retention indices, and NMR spectra of N,N-diisopropylformamide and N,N-diisopropylamine, as well as analytical methods suitable for their analysis and identification in solvent extracts and decontamination residues.

  5. The chemical evolution of Dwarf Galaxies with galactic winds - the role of mass and gas distribution

    NASA Astrophysics Data System (ADS)

    Hensler, Gerhard; Recchi, Simone

    2015-08-01

    Energetic feedback from Supernovae and stellar winds can drive galactic winds. Dwarf galaxies (DGs), due to their shallower potential wells, are assumed to be more vulnera-ble to these energetic processes. Metal loss through galactic winds is also commonly invoked to explain the low metal content of DGs.Our main aim in this presentation is to show that galactic mass cannot be the only pa-rameter determining the fraction of metals lost by a galaxy. In particular, the distribution of gas must play an equally important role. We perform 2-D chemo-dynamical simula-tions of galaxies characterized by different gas distributions, masses and gas fractions. The gas distribution can change the fraction of lost metals through galactic winds by up to one order of magnitude. In particular, disk-like galaxies tend to lose metals more easily than roundish ones. Consequently, also the final element abundances attained by models with the same mass but with different gas distributions can vary by up to one dex. Confirming previous studies, we also show that the fate of gas and freshly pro-duced metals strongly depends on the mass of the galaxy. Smaller galaxies (with shal-lower potential wells) more easily develop large-scale outflows; therefore, the fraction of lost metals tends to be higher.Another important issue is that the invoked mechanism to transform central cusps to cored dark-matter distributions by baryon loss due to strong galactic winds cannot work in general, must be critically tested, and should be clearly discernible by the chemical evolution of DGs.

  6. Developing Fieldable Systems for Chemical Sensing Using Field Asymmetric Ion Mobility Spectrometry and Mass Spectrometry

    SciTech Connect

    Kevin Kyle, Stephan Weeks, R. Trainham

    2008-03-01

    Currently, there is an urgent need for field-rugged and field-programmable sensor systems that provide highly selective, universal monitoring of vapors and aerosols at detectable levels from persons or areas involved with illicit chemical/biological/explosives (CBE) production. These devices must be portable, low cost, robust, and provide accurate measurements to avoid both false positive and negative results. Furthermore, the information provided by the devices must be received in a timely manner so that informed decisions can be immediately made and the appropriate actions taken. Two technologies that are unparalleled in their sensitivity, selectivity, and trace-level detection capabilities are field asymmetric ion mobility spectrometry (FAIMS) and mass spectrometry. Here, we will show progress that has been made toward developing fieldable FAIMS systems and mass spectrometers. Working in collaboration with Sionex Corporation, the microDMx detector was equipped with a continuous air sampling system to develop selective methods for the analysis of compounds of interest. A microdiaphragm pump (KNF Neuberger, Inc.) is used to pull in gas-phase analytes directly from the air for separation and detection with the FAIMS system. The FAIMS evaluation platform (SVAC) unit currently measures 9.8-inch x 4.6-inch x 3.2-inch, weighs 3.1 lb, and utilizes a {sup 63}Ni source to ionize incoming compounds. Analytes entering the unit are separated and identified by their characteristic response to the compensation voltage (V{sub c}) at a given rf field strength (V{sub rf}). This response has been observed to be unique for a wide range of substances studied. If additional verification were required or a targeted analyte present in a complex chemical matrix, a FAIMS unit equipped with a fast gas chromatography column has been evaluated. The unit combines the separation capabilities of gas chromatography with the selectivity of FAIMS. It measures 9.5-inch x 5.25-inch x 3.5-inch

  7. Triage, monitoring, and treatment of mass casualty events involving chemical, biological, radiological, or nuclear agents

    PubMed Central

    Ramesh, Aruna C.; Kumar, S.

    2010-01-01

    In a mass casualty situation due to chemical, biological, radiological, or nuclear (CBRN) event, triage is absolutely required for categorizing the casualties in accordance with medical care priorities. Dealing with a CBRN event always starts at the local level. Even before the detection and analysis of agents can be undertaken, zoning, triage, decontamination, and treatment should be initiated promptly. While applying the triage system, the available medical resources and maximal utilization of medical assets should be taken into consideration by experienced triage officers who are most familiar with the natural course of the injury presented and have detailed information on medical assets. There are several triage systems that can be applied to CBRN casualties. With no one standardized system globally or nationally available, it is important for deploying a triage and decontamination system which is easy to follow and flexible to the available medical resources, casualty number, and severity of injury. PMID:21829319

  8. Chemical cross-linking and native mass spectrometry: A fruitful combination for structural biology.

    PubMed

    Sinz, Andrea; Arlt, Christian; Chorev, Dror; Sharon, Michal

    2015-08-01

    Mass spectrometry (MS) is becoming increasingly popular in the field of structural biology for analyzing protein three-dimensional-structures and for mapping protein-protein interactions. In this review, the specific contributions of chemical crosslinking and native MS are outlined to reveal the structural features of proteins and protein assemblies. Both strategies are illustrated based on the examples of the tetrameric tumor suppressor protein p53 and multisubunit vinculin-Arp2/3 hybrid complexes. We describe the distinct advantages and limitations of each technique and highlight synergistic effects when both techniques are combined. Integrating both methods is especially useful for characterizing large protein assemblies and for capturing transient interactions. We also point out the future directions we foresee for a combination of in vivo crosslinking and native MS for structural investigation of intact protein assemblies.

  9. Demonstration of real-time monitoring of a photolithographic exposure process using chemical ionization mass spectrometry

    SciTech Connect

    Mowry, C.D.

    1998-02-01

    Silicon wafers are coated with photoresist and exposed to ultraviolet (UV) light in a laboratory to simulate typical conditions expected in an actual semiconductor manufacturing process tool. Air is drawn through the exposure chamber and analyzed using chemical ionization mass spectrometry (CI/MS). Species that evaporate or outgas from the wafer are thus detected. The purpose of such analyses is to determine the potential of CI/MS as a real-time process monitoring tool. Results demonstrate that CI/MS can remotely detect the products evolved before, during, and after wafer UV exposure; and that the quantity and type of products vary with the photoresist coated on the wafer. Such monitoring could provide semiconductor manufacturers benefits in quality control and process analysis. Tool and photoresist manufacturers could also realize benefits from this measurement technique with respect to new tool, method, or photoresist development. The benefits realized can lead to improved device yields and reduced product and development costs.

  10. Triage, monitoring, and treatment of mass casualty events involving chemical, biological, radiological, or nuclear agents.

    PubMed

    Ramesh, Aruna C; Kumar, S

    2010-07-01

    In a mass casualty situation due to chemical, biological, radiological, or nuclear (CBRN) event, triage is absolutely required for categorizing the casualties in accordance with medical care priorities. Dealing with a CBRN event always starts at the local level. Even before the detection and analysis of agents can be undertaken, zoning, triage, decontamination, and treatment should be initiated promptly. While applying the triage system, the available medical resources and maximal utilization of medical assets should be taken into consideration by experienced triage officers who are most familiar with the natural course of the injury presented and have detailed information on medical assets. There are several triage systems that can be applied to CBRN casualties. With no one standardized system globally or nationally available, it is important for deploying a triage and decontamination system which is easy to follow and flexible to the available medical resources, casualty number, and severity of injury.

  11. Verification of chemical composition of commercially available propolis extracts by gas chromatography-mass spectrometry analysis.

    PubMed

    Czyżewska, Urszula; Konończuk, Joanna; Teul, Joanna; Drągowski, Paweł; Pawlak-Morka, Renata; Surażyński, Arkadiusz; Miltyk, Wojciech

    2015-05-01

    Propolis is a resin that is collected by honeybees from various plant sources. Due to its pharmacological properties, it is used in commercial production of nutritional supplements in pharmaceutical industry. In this study, gas chromatography-mass spectrometry was applied for quality control analysis of the three commercial specimens containing aqueous-alcoholic extracts of bee propolis. More than 230 constituents were detected in analyzed products, including flavonoids, chalcones, cinnamic acids and their esters, phenylpropenoid glycerides, and phenylpropenoid sesquiterpenoids. An allergenic benzyl cinnamate ester was also identified in all tested samples. This analytical method allows to evaluate biological activity and potential allergenic components of bee glue simultaneously. Studies on chemical composition of propolis samples may provide new approach to quality and safety control analysis in production of propolis supplementary specimens.

  12. Determination of dexamethasone in urine by gas chromatography with negative chemical ionization mass spectrometry.

    PubMed

    Huetos Hidalgo, Olga; Jiménez López, Manuel; Ajenjo Carazo, Elisa; San Andrés Larrea, Manuel; Reuvers, Thea B A

    2003-05-01

    Dexamethasone, as some other synthetic corticosteroids, is licensed for therapy in veterinary practice, but its misuse as a growth promotor, often in combination with beta-agonists, is forbidden. In this report an analytical method is described for the detection and confirmation of very low concentrations of dexamethasone in urine. The influence of enzymatic hydrolysis time of samples with glucuronidase was studied. The proposed method consisted of the enzymatic hydrolysis of urine samples, which were then extracted and concentrated using solid-phase cartridges with mixed reversed-phase materials (OASIS). No further clean-up step was found to be necessary. Eluates were derivatized following a previously described method [Analyst 119 (1994) 2557]. Detection, identification and quantification of residues of this compound was carried out by gas chromatography with mass spectrometry in the negative chemical ionization mode. The proposed procedure permits the determination of dexamethasone in urine at levels as low as 0.2 ng ml(-1)

  13. Chemical cross-linking and native mass spectrometry: A fruitful combination for structural biology

    PubMed Central

    Sinz, Andrea; Arlt, Christian; Chorev, Dror; Sharon, Michal

    2015-01-01

    Mass spectrometry (MS) is becoming increasingly popular in the field of structural biology for analyzing protein three-dimensional-structures and for mapping protein–protein interactions. In this review, the specific contributions of chemical crosslinking and native MS are outlined to reveal the structural features of proteins and protein assemblies. Both strategies are illustrated based on the examples of the tetrameric tumor suppressor protein p53 and multisubunit vinculin-Arp2/3 hybrid complexes. We describe the distinct advantages and limitations of each technique and highlight synergistic effects when both techniques are combined. Integrating both methods is especially useful for characterizing large protein assemblies and for capturing transient interactions. We also point out the future directions we foresee for a combination of in vivo crosslinking and native MS for structural investigation of intact protein assemblies. PMID:25970732

  14. Water chemical ionization mass spectrometry of aldehydes, ketones esters, and carboxylic acids

    SciTech Connect

    Hawthorne, S.B.; Miller, D.J.

    1986-11-01

    Chemical ionization mass spectrometry (CI) of aliphatic and aromatic carbonyl compounds using water as the reagent gas provides intense pseudomolecular ions and class-specific fragmentation patterns that can be used to identify aliphatic aldehydes, ketones, carboxylic acids, and esters. The length of ester acyl and alkyl groups can easily be determined on the basis of loss of alcohols from the protonated parent. Water CI provides for an approximately 200:1 selectivity of carbonyl species over alkanes. No reagent ions are detected above 55 amu, allowing species as small as acetone, propanal, acetic acid, and methyl formate to be identified. When deuterate water was used as the reagent, only the carboxylic acids and ..beta..-diketones showed significant H/D exchange. The use of water CI to identify carbonyl compounds in a wastewater from the supercritical water extraction of lignite coal, in lemon oil, and in whiskey volatiles is discussed.

  15. Self-care Decontamination within a Chemical Exposure Mass-casualty Incident.

    PubMed

    Monteith, Raymond G; Pearce, Laurie D R

    2015-06-01

    Growing awareness and concern for the increasing frequency of incidents involving hazardous materials (HazMat) across a broad spectrum of contaminants from chemical, biological, radiological, and nuclear (CBRN) sources indicates a clear need to refine the capability to respond successfully to mass-casualty contamination incidents. Best results for decontamination from a chemical agent will be achieved if done within minutes following exposure, and delays in decontamination will increase the length of time a casualty is in contact with the contaminate. The findings presented in this report indicate that casualties involved in a HazMat/CBRN mass-casualty incident (MCI) in a typical community would not receive sufficient on-scene care because of operational delays that are integral to a standard HazMat/CBRN first response. This delay in response will mean that casualty care will shift away from the incident scene into already over-tasked health care facilities as casualties seek aid on their own. The self-care decontamination protocols recommended here present a viable option to ensure decontamination is completed in the field, at the incident scene, and that casualties are cared for more quickly and less traumatically than they would be otherwise. Introducing self-care decontamination procedures as a standard first response within the response community will improve the level of care significantly and provide essential, self-care decontamination to casualties. The process involves three distinct stages which should not be delayed; these are summarized by the acronym MADE: Move/Assist, Disrobe/Decontaminate, Evaluate/Evacuate.

  16. Self-care Decontamination within a Chemical Exposure Mass-casualty Incident.

    PubMed

    Monteith, Raymond G; Pearce, Laurie D R

    2015-06-01

    Growing awareness and concern for the increasing frequency of incidents involving hazardous materials (HazMat) across a broad spectrum of contaminants from chemical, biological, radiological, and nuclear (CBRN) sources indicates a clear need to refine the capability to respond successfully to mass-casualty contamination incidents. Best results for decontamination from a chemical agent will be achieved if done within minutes following exposure, and delays in decontamination will increase the length of time a casualty is in contact with the contaminate. The findings presented in this report indicate that casualties involved in a HazMat/CBRN mass-casualty incident (MCI) in a typical community would not receive sufficient on-scene care because of operational delays that are integral to a standard HazMat/CBRN first response. This delay in response will mean that casualty care will shift away from the incident scene into already over-tasked health care facilities as casualties seek aid on their own. The self-care decontamination protocols recommended here present a viable option to ensure decontamination is completed in the field, at the incident scene, and that casualties are cared for more quickly and less traumatically than they would be otherwise. Introducing self-care decontamination procedures as a standard first response within the response community will improve the level of care significantly and provide essential, self-care decontamination to casualties. The process involves three distinct stages which should not be delayed; these are summarized by the acronym MADE: Move/Assist, Disrobe/Decontaminate, Evaluate/Evacuate. PMID:25915603

  17. Chemical discrimination in turbulent gas mixtures with MOX sensors validated by gas chromatography-mass spectrometry.

    PubMed

    Fonollosa, Jordi; Rodríguez-Luján, Irene; Trincavelli, Marco; Vergara, Alexander; Huerta, Ramón

    2014-10-16

    Chemical detection systems based on chemo-resistive sensors usually include a gas chamber to control the sample air flow and to minimize turbulence. However, such a kind of experimental setup does not reproduce the gas concentration fluctuations observed in natural environments and destroys the spatio-temporal information contained in gas plumes. Aiming at reproducing more realistic environments, we utilize a wind tunnel with two independent gas sources that get naturally mixed along a turbulent flow. For the first time, chemo-resistive gas sensors are exposed to dynamic gas mixtures generated with several concentration levels at the sources. Moreover, the ground truth of gas concentrations at the sensor location was estimated by means of gas chromatography-mass spectrometry. We used a support vector machine as a tool to show that chemo-resistive transduction can be utilized to reliably identify chemical components in dynamic turbulent mixtures, as long as sufficient gas concentration coverage is used. We show that in open sampling systems, training the classifiers only on high concentrations of gases produces less effective classification and that it is important to calibrate the classification method with data at low gas concentrations to achieve optimal performance.

  18. Chemical Discrimination in Turbulent Gas Mixtures with MOX Sensors Validated by Gas Chromatography-Mass Spectrometry

    PubMed Central

    Fonollosa, Jordi; Rodríguez-Luján, Irene; Trincavelli, Marco; Vergara, Alexander; Huerta, Ramón

    2014-01-01

    Chemical detection systems based on chemo-resistive sensors usually include a gas chamber to control the sample air flow and to minimize turbulence. However, such a kind of experimental setup does not reproduce the gas concentration fluctuations observed in natural environments and destroys the spatio-temporal information contained in gas plumes. Aiming at reproducing more realistic environments, we utilize a wind tunnel with two independent gas sources that get naturally mixed along a turbulent flow. For the first time, chemo-resistive gas sensors are exposed to dynamic gas mixtures generated with several concentration levels at the sources. Moreover, the ground truth of gas concentrations at the sensor location was estimated by means of gas chromatography-mass spectrometry. We used a support vector machine as a tool to show that chemo-resistive transduction can be utilized to reliably identify chemical components in dynamic turbulent mixtures, as long as sufficient gas concentration coverage is used. We show that in open sampling systems, training the classifiers only on high concentrations of gases produces less effective classification and that it is important to calibrate the classification method with data at low gas concentrations to achieve optimal performance. PMID:25325339

  19. Desorption electrospray ionization mass spectrometry reveals surface-mediated antifungal chemical defense of a tropical seaweed

    PubMed Central

    Lane, Amy L.; Nyadong, Leonard; Galhena, Asiri S.; Shearer, Tonya L.; Stout, E. Paige; Parry, R. Mitchell; Kwasnik, Mark; Wang, May D.; Hay, Mark E.; Fernandez, Facundo M.; Kubanek, Julia

    2009-01-01

    Organism surfaces represent signaling sites for attraction of allies and defense against enemies. However, our understanding of these signals has been impeded by methodological limitations that have precluded direct fine-scale evaluation of compounds on native surfaces. Here, we asked whether natural products from the red macroalga Callophycus serratus act in surface-mediated defense against pathogenic microbes. Bromophycolides and callophycoic acids from algal extracts inhibited growth of Lindra thalassiae, a marine fungal pathogen, and represent the largest group of algal antifungal chemical defenses reported to date. Desorption electrospray ionization mass spectrometry (DESI-MS) imaging revealed that surface-associated bromophycolides were found exclusively in association with distinct surface patches at concentrations sufficient for fungal inhibition; DESI-MS also indicated the presence of bromophycolides within internal algal tissue. This is among the first examples of natural product imaging on biological surfaces, suggesting the importance of secondary metabolites in localized ecological interactions, and illustrating the potential of DESI-MS in understanding chemically-mediated biological processes. PMID:19366672

  20. Particulate matter mass and chemical component concentrations over four Chinese cities along the western Pacific coast.

    PubMed

    Xu, Hong; Bi, Xiao-Hui; Zheng, Wei-Wei; Wu, Jian-Hui; Feng, Yin-Chang

    2015-02-01

    China has witnessed rapid economic growth in the past three decades, especially in coastal areas. Particulate matter (PM) pollution is becoming increasingly serious in China's cities along the western Pacific coast with the rapid development of China's society and economy. This study analyzed PM (PM10 and PM2.5) in terms of their mass and chemical composition in four coastal Chinese cities. The goal was to study the spatial variation and characteristics of PM pollution in sites under different levels of economic development and in diverse natural environments. A distinct trend for concentrations of PM and related chemical species was observed and increased from south to north in Haikou, Ningbo, Qingdao, and Tianjin. Secondary inorganic aerosols, crustal materials, and organic matter dominated the composition of both PM10 and PM2.5. Crustal materials were the most abundant species in the northern coastal areas because these areas have less vegetation cover and lower humidity than southern coastal areas. The presence of high SO4 (2-)/nitrate (NO3 (-)) concentrations indicated that the burning of coals gives significant contributions to PM10 and PM2.5. The differences observed in the characteristics of PM pollution in these coastal cities are probably caused by different levels of industrial and urban development.

  1. Determination of household chemicals using gas chromatography and liquid chromatography with tandem mass spectrometry.

    PubMed

    Trenholm, Rebecca A; Vanderford, Brett J; Drewes, Jörg E; Snyder, Shane A

    2008-05-01

    A method has been developed for the determination of 24 household high production volume (HPV) chemicals in municipal wastewater systems using solid-phase extraction (SPE) and analyses using both gas chromatography and liquid chromatography, each with tandem mass spectrometry (GC-MS/MS and LC-MS/MS). Target compounds include pesticides, antioxidants, fragrances, plasticizers, preservatives and personal care products. Method reporting limits ranged from 0.1 to 100 ng/L in water and recoveries for most compounds were between 54 and 112%. Household HPVs were consistently detected in raw sewage entering three full-scale wastewater treatment plants. Compounds such as vanillin, DEET, benzophenone, 3-indolebutyric acid, bisphenol A, triclosan and triclocarban were detected in all wastewater influent and effluent samples, but were significantly lower in the effluent. Many of the remaining compounds were detected in the influent, but below detection in effluent samples. Menthol and phenoxyethanol had the highest observed concentrations in influent samples ranging from 1.5 to 13 microg/L for menthol, and 8.8 to 22 microg/L for phenoxyethanol. MGK-11, methylresorcinol, trifluralin, hexabromododecane, acriflavin and atrazine were not detected in any samples. The method described here detects a broad range of HPV chemicals with great sensitivity and selectivity.

  2. Odor and odorous chemical emissions from dairy and swine facilities: Part 5-Simultaneous chemical and sensory analysis with Gas Chromatography - Mass Spectrometry - Olfactometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Simultaneous chemical and sensory analyses using gas chromatography-mass spectrometry-olfactometry (GC-MS-O) for air samples collected at barn exhaust fans were used for quantification and ranking of odor impact of target odorous gases. Fifteen target odorous VOCs (odorants) were selected. Air sampl...

  3. Selectivity of negative ion chemical ionization mass spectrometry for benzo(a)pyrene

    SciTech Connect

    Hilpert, L.R.; Byrd, G.D.; Vogt, C.R.

    1984-09-01

    Gas chromatography/negative ion chemical ionization mass spectrometry (GC/NICIMS) was used as a selective and sensitive technique for the detection of benzo(a)pyrene (BaP). Under optimized conditions, the molecular anion, M/sup -/, of BaP was more than 3 orders of magnitude more abundant than that of its isomer benzo(e)pyrene (BeP) using methane as the reagent gas. Quantities of BaP as low as 1 pg can easily be detected in the selected ion monitoring mode and the response vs. concentration was linear over a range of 3 orders of magnitude. The absolute sensitivity and the selectivity for detection were found to depend on the pressure and temperature in the ion source of the mass spectrometer. NICIMS was used for the quantitative determination of BaP, indeno(1,2,3-cd)pyrene, and benzo(ghl)perylene in a sample of petroleum crude oil as part of the process of certifying the oil as a Standard Reference Material.

  4. Chemical and Isotopic Thresholds in Charring: Implications for the Interpretation of Charcoal Mass and Isotopic Data.

    PubMed

    Pyle, Lacey A; Hockaday, William C; Boutton, Thomas; Zygourakis, Kyriacos; Kinney, Timothy J; Masiello, Caroline A

    2015-12-15

    Charcoal plays a significant role in the long-term carbon cycle, and its use as a soil amendment is promoted as a C sequestration strategy (biochar). One challenge in this research area is understanding the heterogeneity of charcoal properties. Although the maximum reaction temperature is often used as a gauge of pyrolysis conditions, pyrolysis duration also changes charcoal physicochemical qualities. Here, we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in charcoal chemical properties with variation in CI. We find two types of responses to CI: either linear or threshold relationships. Mass yield decreases linearly with CI, while a threshold exists across which % C, % N, and δ(15)N exhibit large changes. This CI threshold co-occurs with an increase in charcoal aromaticity. C isotopes do not change from original biomass values, supporting the use of charcoal δ(13)C signatures to infer paleoecological conditions. Fractionation of N isotopes indicates that fire may be enriching soils in (15)N through pyrolytic N isotope fractionation. This influx of "black N" could have a significant impact on soil N isotopes, which we show theoretically using a simple mass-balance model.

  5. Chemical and Isotopic Thresholds in Charring: Implications for the Interpretation of Charcoal Mass and Isotopic Data.

    PubMed

    Pyle, Lacey A; Hockaday, William C; Boutton, Thomas; Zygourakis, Kyriacos; Kinney, Timothy J; Masiello, Caroline A

    2015-12-15

    Charcoal plays a significant role in the long-term carbon cycle, and its use as a soil amendment is promoted as a C sequestration strategy (biochar). One challenge in this research area is understanding the heterogeneity of charcoal properties. Although the maximum reaction temperature is often used as a gauge of pyrolysis conditions, pyrolysis duration also changes charcoal physicochemical qualities. Here, we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in charcoal chemical properties with variation in CI. We find two types of responses to CI: either linear or threshold relationships. Mass yield decreases linearly with CI, while a threshold exists across which % C, % N, and δ(15)N exhibit large changes. This CI threshold co-occurs with an increase in charcoal aromaticity. C isotopes do not change from original biomass values, supporting the use of charcoal δ(13)C signatures to infer paleoecological conditions. Fractionation of N isotopes indicates that fire may be enriching soils in (15)N through pyrolytic N isotope fractionation. This influx of "black N" could have a significant impact on soil N isotopes, which we show theoretically using a simple mass-balance model. PMID:26523420

  6. Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically Etched Emitters

    SciTech Connect

    Marginean, Ioan; Tang, Keqi; Smith, Richard D.; Kelly, Ryan T.

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. No unimolecular response was observed within this flow rate range during the analysis of an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic in given experimental conditions. While little to no gain in signal-to-noise was achieved at ultralow flow rates for concentration-limited analyses, experiments consuming the same amount of analyte suggest that mass-limited analyses will benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. By operating under optimal conditions, consumption of just 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. These findings have important implications for the analysis of trace biological samples.

  7. Rotation planar chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Van Berkel, Gary J; Llave, Jonathan J; De Apadoca, Marilyn F; Ford, Michael J

    2004-01-15

    The coupling of a rotation planar preparative thin-layer chromatography system on-line with mass spectrometry is demonstrated using a simple plumbing scheme and a self-aspirating heated nebulizer probe of a corona discharge atmospheric pressure chemical ionization source. The self-aspiration of the heated nebulizer delivers approximately 20 microL/min of the 3.0 mL/min eluate stream to the mass spectrometer, eliminating the need for an external pump in the system. The viability of the coupling is demonstrated with a three-dye mixture composed of fat red 7B, solvent green 3, and solvent blue 35 separated and eluted from a silica gel-coated rotor using toluene. The real-time characterization of the dyes eluting from the rotor is illustrated in positive ion full-scan mode. Other self-aspirating ion source systems including atmospheric pressure photoionization, electrospray ionization, and inductively coupled plasma ionization, for example, might be configured and used in a similar manner coupled to the chromatograph to expand the types of analytes that could be ionized, detected, and characterized effectively. PMID:14719901

  8. Rotation planar chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Van Berkel, Gary J; Llave, Jonathan J; De Apadoca, Marilyn F; Ford, Michael J

    2004-01-15

    The coupling of a rotation planar preparative thin-layer chromatography system on-line with mass spectrometry is demonstrated using a simple plumbing scheme and a self-aspirating heated nebulizer probe of a corona discharge atmospheric pressure chemical ionization source. The self-aspiration of the heated nebulizer delivers approximately 20 microL/min of the 3.0 mL/min eluate stream to the mass spectrometer, eliminating the need for an external pump in the system. The viability of the coupling is demonstrated with a three-dye mixture composed of fat red 7B, solvent green 3, and solvent blue 35 separated and eluted from a silica gel-coated rotor using toluene. The real-time characterization of the dyes eluting from the rotor is illustrated in positive ion full-scan mode. Other self-aspirating ion source systems including atmospheric pressure photoionization, electrospray ionization, and inductively coupled plasma ionization, for example, might be configured and used in a similar manner coupled to the chromatograph to expand the types of analytes that could be ionized, detected, and characterized effectively.

  9. Strategies for the chemical analysis of highly porous bone scaffolds using secondary ion mass spectrometry.

    PubMed

    Wang, Daming; Poologasundarampillai, Gowsihan; van den Bergh, Wouter; Chater, Richard J; Kasuga, Toshihiro; Jones, Julian R; McPhail, David S

    2014-02-01

    Understanding the distribution of critical elements (e.g. silicon and calcium) within silica-based bone scaffolds synthesized by different methods is central to the optimization of these materials. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to determine this information due to its very high surface sensitivity and its ability to map all the elements and compounds in the periodic table with high spatial resolution. The SIMS image data can also be combined with depth profiles to construct three-dimensional chemical maps. However, the scaffolds have interconnected pore networks, which are very challenging structures for the SIMS technique. To overcome this problem two experimental methodologies have been developed. The first method involved the use of the focused ion beam technique to obtain clear images of the regions of interest and subsequently mark them by introducing fiducial marks; the samples were then analysed using the ToF-SIMS technique to yield the chemical analyses of the regions of interest. The second method involved impregnating the pores using a suitable reagent so that a flat surface could be achieved, and this was followed by secondary ion mapping and 3D chemical imaging with ToF-SIMS. The samples used in this work were sol-gel 70S30C foam and electrospun fibres and calcium-containing silica/gelatin hybrid scaffolds. The results demonstrate the feasibility of both these experimental methodologies and indicate that these methods can provide an opportunity to compare various artificial bone scaffolds, which will be of help in improving scaffold synthesis and processing routes. The techniques are also transferable to many other types of porous material. PMID:24457328

  10. Strategies for the chemical analysis of highly porous bone scaffolds using secondary ion mass spectrometry.

    PubMed

    Wang, Daming; Poologasundarampillai, Gowsihan; van den Bergh, Wouter; Chater, Richard J; Kasuga, Toshihiro; Jones, Julian R; McPhail, David S

    2014-02-01

    Understanding the distribution of critical elements (e.g. silicon and calcium) within silica-based bone scaffolds synthesized by different methods is central to the optimization of these materials. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to determine this information due to its very high surface sensitivity and its ability to map all the elements and compounds in the periodic table with high spatial resolution. The SIMS image data can also be combined with depth profiles to construct three-dimensional chemical maps. However, the scaffolds have interconnected pore networks, which are very challenging structures for the SIMS technique. To overcome this problem two experimental methodologies have been developed. The first method involved the use of the focused ion beam technique to obtain clear images of the regions of interest and subsequently mark them by introducing fiducial marks; the samples were then analysed using the ToF-SIMS technique to yield the chemical analyses of the regions of interest. The second method involved impregnating the pores using a suitable reagent so that a flat surface could be achieved, and this was followed by secondary ion mapping and 3D chemical imaging with ToF-SIMS. The samples used in this work were sol-gel 70S30C foam and electrospun fibres and calcium-containing silica/gelatin hybrid scaffolds. The results demonstrate the feasibility of both these experimental methodologies and indicate that these methods can provide an opportunity to compare various artificial bone scaffolds, which will be of help in improving scaffold synthesis and processing routes. The techniques are also transferable to many other types of porous material.

  11. Chemical Nature Of Titan’s Organic Aerosols Constrained from Spectroscopic and Mass Spectrometric Observations

    NASA Astrophysics Data System (ADS)

    Imanaka, Hiroshi; Cruikshank, D. P.

    2012-10-01

    The Cassini-Huygens observations greately extend our knowledge about Titan’s organic aerosols. The Cassini INMS and CAPS observations clearly demonstrate the formation of large organic molecules in the ionosphere [1, 2]. The VIMS and CIRS instruments have revealed spectral features of the haze covering the mid-IR and far-IR wavelengths [3, 4, 5, 6]. This study attempts to speculate the possible chemical nature of Titan’s aerosols by comparing the currently available observations with our laboratory study. We have conducted a series of cold plasma experiment to investigate the mass spectrometric and spectroscopic properties of laboratory aerosol analogs [7, 8]. Titan tholins and C2H2 plasma polymer are generated with cold plasma irradiations of N2/CH4 and C2H2, respectively. Laser desorption mass spectrum of the C2H2 plasma polymer shows a reasonable match with the CAPS positive ion mass spectrum. Furthermore, spectroscopic features of the the C2H2 plasma polymer in mid-IR and far-IR wavelegths qualitatively show reasonable match with the VIMS and CIRS observations. These results support that the C2H2 plasma polymer is a good candidate material for Titan’s aerosol particles at the altitudes sampled by the observations. We acknowledge funding supports from the NASA Cassini Data Analysis Program, NNX10AF08G, and from the NASA Exobiology Program, NNX09AM95G, and the Cassini Project. [1] Waite et al. (2007) Science 316, 870-875. [2] Crary et al. (2009) Planet. Space Sci. 57, 1847-1856. [3] Bellucci et al. (2009) Icarus 201, 198-216. [4] Anderson and Samuelson (2011) Icarus 212, 762-778. [5] Vinatier et al. (2010) Icarus 210, 852-866. [6] Vinatier et al. (2012) Icarus 219, 5-12. [7] Imanaka et al. (2004) Icarus 168, 344-366. [8] Imanaka et al. (2012) Icarus 218, 247-261.

  12. Seasonality of new particle formation in Vienna, Austria - Influence of air mass origin and aerosol chemical composition

    NASA Astrophysics Data System (ADS)

    Wonaschütz, Anna; Demattio, Anselm; Wagner, Robert; Burkart, Julia; Zíková, Naděžda; Vodička, Petr; Ludwig, Wolfgang; Steiner, Gerhard; Schwarz, Jaroslav; Hitzenberger, Regina

    2015-10-01

    The impact of air mass origin and season on aerosol chemical composition and new particle formation and growth events (NPF events) in Vienna, Austria, is investigated using impactor samples from short-term campaigns and two long-term number size distribution datasets. The results suggest that air mass origin is most important for bulk PM concentrations, chemical composition of the coarse fraction (>1.5 μm) and the mass size distribution, and less important for chemical composition of the fine fraction (<1.5 μm). Continental air masses (crustal elements) were distinguished from air masses of marine origin (traces of sea salt). NPF events were most frequent in summer (22% of measurement days), and least frequent in winter (3% of measurement days). They were associated with above-average solar radiation and ozone concentrations, but were largely independent of PM2.5. Air mass origin was a secondary influence on NPF, largely through its association with meteorological conditions. Neither a strong dependence on the PM2.5 loading of the air masses, nor indications of a source area for NPF precursors outside the city were found.

  13. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis

    NASA Astrophysics Data System (ADS)

    Zhang, Xue-Song; Yang, Guang-Xi; Jiang, Hong; Liu, Wu-Jun; Ding, Hong-Sheng

    2013-01-01

    Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass.

  14. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis

    PubMed Central

    Zhang, Xue-Song; Yang, Guang-Xi; Jiang, Hong; Liu, Wu-Jun; Ding, Hong-Sheng

    2013-01-01

    Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass. PMID:23350028

  15. Intracellular water exchange for measuring the dry mass, water mass and changes in chemical composition of living cells.

    PubMed

    Feijó Delgado, Francisco; Cermak, Nathan; Hecht, Vivian C; Son, Sungmin; Li, Yingzhong; Knudsen, Scott M; Olcum, Selim; Higgins, John M; Chen, Jianzhu; Grover, William H; Manalis, Scott R

    2013-01-01

    We present a method for direct non-optical quantification of dry mass, dry density and water mass of single living cells in suspension. Dry mass and dry density are obtained simultaneously by measuring a cell's buoyant mass sequentially in an H2O-based fluid and a D2O-based fluid. Rapid exchange of intracellular H2O for D2O renders the cell's water content neutrally buoyant in both measurements, and thus the paired measurements yield the mass and density of the cell's dry material alone. Utilizing this same property of rapid water exchange, we also demonstrate the quantification of intracellular water mass. In a population of E. coli, we paired these measurements to estimate the percent dry weight by mass and volume. We then focused on cellular dry density - the average density of all cellular biomolecules, weighted by their relative abundances. Given that densities vary across biomolecule types (RNA, DNA, protein), we investigated whether we could detect changes in biomolecular composition in bacteria, fungi, and mammalian cells. In E. coli, and S. cerevisiae, dry density increases from stationary to exponential phase, consistent with previously known increases in the RNA/protein ratio from up-regulated ribosome production. For mammalian cells, changes in growth conditions cause substantial shifts in dry density, suggesting concurrent changes in the protein, nucleic acid and lipid content of the cell.

  16. Electron impact ionisation cross sections for atomic and molecular allotropes of phosphorous and arsenic

    NASA Astrophysics Data System (ADS)

    Bhutadia, Harshad; Chaudhari, Ashok; Vinodkumar, Minaxi

    2015-12-01

    We report electron impact total ionisation cross sections for phosphorous (P), arsenic (As), diphosphorous (P2), diarsenic (As2), tetra phosphorous (P4) and tetra arsenic (As4) from the threshold of the target to 2000 eV. We employed spherical complex optical potential to compute total inelastic cross sections (Qinel). The total ionisation cross section is extracted from the total inelastic cross section using the complex scattering potential-ionisation contribution method. The results of most of the targets studied here compare well with the measurements and the theoretical data wherever available. The correlation between the peak of ionisation cross sections with the number of target electrons and polarisability is also reported. It is observed that the maximum ionisation cross sections depend linearly on the number of target electrons and polarisability of the target. This linear correlation is used to predict the maximum ionisation cross sections for the targets (I2, HI and PF3) where no experimental data are available.

  17. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies.

    PubMed

    Schowalter, Steven J; Chen, Kuang; Rellergert, Wade G; Sullivan, Scott T; Hudson, Eric R

    2012-04-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm ∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates.

  18. Profiling the substitution pattern of xyloglucan derivatives by integrated enzymatic hydrolysis, hydrophilic-interaction liquid chromatography and mass spectrometry.

    PubMed

    Liu, Jun; Kisonen, Victor; Willför, Stefan; Xu, Chunlin; Vilaplana, Francisco

    2016-09-01

    Plant polysaccharides constitute arguably the most complex family of biomacromolecules in terms of the stereochemistry and regiochemistry of their intramolecular linkages. The chemical modification of such polysaccharides introduces an additional level of complexity for structural determinations. We have developed an integrated analytical procedure combining selective enzymatic hydrolysis, hydrophilic interaction liquid chromatography (HILIC), and mass spectrometry (MS) to describe the substitution pattern of xyloglucan (XyG) and its chemo-enzymatic derivatives (cationic, anionic, and benzyl aminated). Enzymatic hydrolysis of XyG derivatives by a xyloglucan-specific endoglucanase (XEG) generates oligosaccharides amenable for mass spectrometric identification with distinct structures, based on enzymatic substrate recognition and hydrolytic pattern. Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF-MS) and electrospray ionisation mass spectrometry (ESI-MS) offer qualitative mass profiling of the chemical derivatives. Separation and identification of the complex oligosaccharide profiles released by enzymatic hydrolysis is achieved by hyphenation of hydrophilic interaction liquid chromatography with mass spectrometry (HILIC-ESI-MS). Further fragmentation by tandem mass spectrometry (ESI-MS/MS) in positive mode enables the structural sequencing of modified XyG oligosaccharides and the identification of the substituent position without further derivatisation. This integrated approach can be used to obtain semi-quantitative information of the substitution pattern of hemicellulose derivatives, with fundamental implications for their modification mechanisms and performance. PMID:27524300

  19. The universal relation of galactic chemical evolution: the origin of the mass-metallicity relation

    SciTech Connect

    Zahid, H. Jabran; Dima, Gabriel I.; Kudritzki, Rolf-Peter; Kewley, Lisa J.; Geller, Margaret J.; Hwang, Ho Seong; Silverman, John D.; Kashino, Daichi

    2014-08-20

    We examine the mass-metallicity relation for z ≲ 1.6. The mass-metallicity relation follows a steep slope with a turnover, or 'knee', at stellar masses around 10{sup 10} M {sub ☉}. At stellar masses higher than the characteristic turnover mass, the mass-metallicity relation flattens as metallicities begin to saturate. We show that the redshift evolution of the mass-metallicity relation depends only on the evolution of the characteristic turnover mass. The relationship between metallicity and the stellar mass normalized to the characteristic turnover mass is independent of redshift. We find that the redshift-independent slope of the mass-metallicity relation is set by the slope of the relationship between gas mass and stellar mass. The turnover in the mass-metallicity relation occurs when the gas-phase oxygen abundance is high enough that the amount of oxygen locked up in low-mass stars is an appreciable fraction of the amount of oxygen produced by massive stars. The characteristic turnover mass is the stellar mass, where the stellar-to-gas mass ratio is unity. Numerical modeling suggests that the relationship between metallicity and the stellar-to-gas mass ratio is a redshift-independent, universal relationship followed by all galaxies as they evolve. The mass-metallicity relation originates from this more fundamental universal relationship between metallicity and the stellar-to-gas mass ratio. We test the validity of this universal metallicity relation in local galaxies where stellar mass, metallicity, and gas mass measurements are available. The data are consistent with a universal metallicity relation. We derive an equation for estimating the hydrogen gas mass from measurements of stellar mass and metallicity valid for z ≲ 1.6 and predict the cosmological evolution of galactic gas masses.

  20. Mass

    SciTech Connect

    Quigg, Chris

    2007-12-05

    In the classical physics we inherited from Isaac Newton, mass does not arise, it simply is. The mass of a classical object is the sum of the masses of its parts. Albert Einstein showed that the mass of a body is a measure of its energy content, inviting us to consider the origins of mass. The protons we accelerate at Fermilab are prime examples of Einsteinian matter: nearly all of their mass arises from stored energy. Missing mass led to the discovery of the noble gases, and a new form of missing mass leads us to the notion of dark matter. Starting with a brief guided tour of the meanings of mass, the colloquium will explore the multiple origins of mass. We will see how far we have come toward understanding mass, and survey the issues that guide our research today.

  1. Clustering, methodology, and mechanistic insights into acetate chemical ionization using high-resolution time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Brophy, Patrick; Farmer, Delphine K.

    2016-08-01

    We present a comprehensive characterization of cluster control and transmission through the Tofwerk atmospheric pressure interface installed on various chemical ionization time-of-flight mass spectrometers using authentic standards. This characterization of the atmospheric pressure interface allows for a detailed investigation of the acetate chemical ionization mechanisms and the impact of controlling these mechanisms on sensitivity, selectivity, and mass spectral ambiguity with the aim of non-targeted analysis. Chemical ionization with acetate reagent ions is controlled by a distribution of reagent ion-neutral clusters that vary with relative humidity and the concentration of the acetic anhydride precursor. Deprotonated carboxylic acids are primarily detected only if sufficient declustering is employed inside the atmospheric pressure interface. The configuration of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) using an acetate chemical ionization source for non-targeted analysis is discussed. Recent approaches and studies characterizing acetate chemical ionization as it applies to the HR-TOF-CIMS are evaluated in light of the work presented herein.

  2. Investigation of micrometre-sized fossils by a laser ablation mass spectrometer designed for in situ space research

    NASA Astrophysics Data System (ADS)

    Tulej, M.; Neubeck, A.; Ivarsson, M.; Neuland, M. B.; Riedo, A.; Meyer, S.; Wurz, P.

    2015-10-01

    Detection of extraterrestrial life is an ongoing goal in space exploration. The detection of signatures of life by means of chemical composition, elemental and isotopic, is one of the most important approaches. There is a need for advanced instruments and methods that can accomplish this task. We present the first investigations of chemical composition measurements of putative microfossils in natural samples using a miniature laser ablation/ionisation time-of-flight mass spectrometer (LMS). The primary aim of the study was investigation of the instrument's capabilities for element composition and isotopic abundance analysis of micro-sized samples.

  3. Using Chemical Tracers to Estimate Pesticide Mass Discharge in an Agricultural Watershed

    NASA Astrophysics Data System (ADS)

    Simmons, A. N.; Allen-King, R. M.; Van Biersel, T. P.; Keller, C. K.; Smith, J. L.

    2001-12-01

    The goal of this research is to use environmental tracers to quantify the contributions of subsurface and surface runoff to predict the mass discharge of non-point source agricultural pollutants to rivers at multiple scales of study. Easily measured chemical tracers, such as electrical conductivity (EC), are used to distinguish ground and surface water contributions to the river system. The study area is the Missouri Flat Creek watershed, a 14,400 ha semi-arid dryland agricultural setting located near Pullman, WA. Ground and surface water samples are collected at approximately two-week intervals from an ephemeral stream and a tile drain located in actively farmed and topographically constrained fields ( ~20 ha), and from seven stream-gaging stations. Surface water discharge is monitored continuously. Samples are routinely analyzed for two pesticides (the insecticide lindane or gamma-hexachlorocyclohexane (HCH) and the herbicide triallate, S-(2,3,3-trichloroallyl) diisopropylthiocarbamate), a nutrient (nitrate), and the tracers EC and silica. Lindane is applied as a seed coating on most spring and fall crops in the region. Observed lindane concentrations in the different hydrologic reservoirs ranged over approximately two orders of magnitude, from typically less than the detection limit ( ~0.005 μ g/L) in most soil pore water and groundwater samples to a weighted mean of 0.25 μ g/L in field (ephemeral stream) surface runoff. A two-component, ground and surface water, hydrograph separation was performed using tile drain and ephemeral stream tracer concentrations from field plots to represent groundwater and surface runoff end-members. The hydrograph separation was used to predict lindane discharge. Reasonable agreement between model and observed lindane discharge timing and trend supports the hypothesis that in-stream pesticide is derived from annual surface runoff. During the high flow winter months, the model predictions are two to five times greater than

  4. Nitrogen losses from dairy manure estimated through nitrogen mass balance and chemical markers

    USGS Publications Warehouse

    Hristov, Alexander N.; Zaman, S.; Vander Pol, M.; Ndegwa, P.; Campbell, L.; Silva, S.

    2009-01-01

    Ammonia is an important air and water pollutant, but the spatial variation in its concentrations presents technical difficulties in accurate determination of ammonia emissions from animal feeding operations. The objectives of this study were to investigate the relationship between ammonia volatilization and ??15N of dairy manure and the feasibility of estimating ammonia losses from a dairy facility using chemical markers. In Exp. 1, the N/P ratio in manure decreased by 30% in 14 d as cumulative ammonia losses increased exponentially. Delta 15N of manure increased throughout the course of the experiment and ??15N of emitted ammonia increased (p < 0.001) quadratically from -31??? to -15 ???. The relationship between cumulative ammonia losses and ??15N of manure was highly significant (p < 0.001; r2 = 0.76). In Exp. 2, using a mass balance approach, approximately half of the N excreted by dairy cows (Bos taurus) could not be accounted for in 24 h. Using N/P and N/K ratios in fresh and 24-h manure, an estimated 0.55 and 0.34 (respectively) of the N excreted with feces and urine could not be accounted for. This study demonstrated that chemical markers (P, K) can be successfully used to estimate ammonia losses from cattle manure. The relationship between manure ??15N and cumulative ammonia loss may also be useful for estimating ammonia losses. Although promising, the latter approach needs to be further studied and verified in various experimental conditions and in the field. Copyright ?? 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

  5. A chemical ionization mass spectrometry technique for airborne measurements of ammonia

    NASA Astrophysics Data System (ADS)

    Nowak, J. B.; Neuman, J. A.; Kozai, K.; Huey, L. G.; Tanner, D. J.; Holloway, J. S.; Ryerson, T. B.; Frost, G. J.; McKeen, S. A.; Fehsenfeld, F. C.

    2007-05-01

    A chemical ionization mass spectrometer (CIMS) utilizing protonated acetone dimer ion chemistry to measure gas-phase ammonia (NH3) from the NOAA WP-3D aircraft is described. The average sensitivity determined from in-flight standard addition calibrations ranged from 2.6 to 5 ion counts s-1 pptv-1, depending on flow conditions, for 1 MHz of reagent ion signal. The instrument time response was determined to be 5 s from the 2 e-folding signal decay time after removal of a standard addition calibration. The instrumental background varied from flight to flight ranging from 0.5 to 1.3 ppbv. The variability between successive background measurements ranged from 50 pptv to 100 pptv. Total uncertainty for the 5 s data was conservatively estimated to be ±(30% + 125 pptv). Two NH3 sources were sampled during the New England Air Quality Study-Intercontinental Transport and Chemical Transformation (NEAQS-ITCT) 2004 campaign, one urban and one agricultural. During the 25 July flight, enhancements in NH3 mixing ratios were coincident with enhancements in CO, NOx, and SO2 mixing ratios downwind of New York City. The NH3 mixing ratios in the urban outflow plume ranged from 0.4 to 1 ppbv, or enhancements of 0.2 to 0.8 ppbv above local background. During the 15 August flight, NH3 mixing ratios were enhanced 0.3 to 0.45 ppbv above local background directly downwind of an agricultural area northeast of Atlanta, Georgia. The NH3 CIMS instrument has shown the ability to measure sub-ppbv NH3 levels at high time resolution from an aircraft.

  6. Chemical reactions induced by high-velocity molecular impacts: challenges for closed-source mass spectrometry

    NASA Astrophysics Data System (ADS)

    Austin, Daniel

    2016-07-01

    Analysis of upper atmosphere composition using closed-source neutral mass spectrometers (e.g., Cassini INMS, MAVEN NGIMS) is subject to error due to chemical reactions caused by the high-velocity impacts of neutral molecules on the source surfaces. In addition to species traditionally considered "surface reactive" (e.g., O, N) it is likely that many or all impacting molecules are vibrationally excited to the point that chemical changes can occur. Dissociation, fragmentation, formation of radicals and ions, and other reactions likely obscure analysis of the native atmospheric composition, particularly of organic compounds. Existing techniques are not capable of recreating the relevant impact chemistry in the lab. We report on the development of a new capability allowing reactions of high-velocity neutrals impacting surfaces to be characterized directly. Molecules introduced into a vacuum chamber are impacted at several km/s by the surface of a high-speed rotor. These molecules subsequently impact multiple times on other surfaces within the vacuum chamber until they are thermalized, after which they are cryogenically collected and analyzed. Reaction pathways and thermodynamics for volatile compounds are then determined. We will present current results on this project, including data from low- and mid-range velocity experiments. This type of information is critical to clarify prior flight results and plan for future missions. Finally, we present a new type of inlet intended to significantly reduce fragmentation for impact velocities typical of a fly-by mission. Theoretical analysis indicates that this new inlet may reduce fragmentation by more than an order of magnitude for any encounter velocity.

  7. Chemical equilibria of rare earth oxides in glow-discharge mass spectrometry

    SciTech Connect

    Mei, Y.

    1992-01-01

    This research centers around method development and fundamental exploration of the rare earth elements (REE) in glow discharge mass spectrometry (GDMS). The capability of GDMS to analyze directly solids materials eliminates the sample dissolution and preconcentration steps required by many other methods. The simplicity of sample preparation and instrumental operation makes GDMS a promising analytical technique for the field of earth science. Initial studies were dedicated to improving the detection sensitivity of GDMS in analyzing the REE. This was accomplished by eliminating water contamination, a factor that was found to prevent the conversion of the rare earth oxidized to their atomic form in the glow discharge plasma. Methods experimented for water elimination included the uses of both a cryogenic cooling device and getter reagents. When used to determine the REE concentrations in a standard rock sample, the chemical elimination approach yielded comparable results to that obtained by other analytical methods. Further studies focused on probing the chemical reactions involving the REE and other plasma constituents in the glow discharge. It is proposed that the availability of the atomic REE in the glow discharge is strongly influenced by the oxidant and reductant contents in the plasma. Species that contain oxygen tend to shift the redox equilibria of REE toward the formation of their oxides, whereas species that compete for oxygen help reduce the oxidant content in the plasma, and shift the REE redox equilibria toward the formation of the REE atoms. Factors that govern the reaction processes of the REE equilibria were investigated by means of plasma reagent introduction and time-resolved discharge operation. Results indicate that while redox equilibria between the elemental REE and their monoxides exist on the cathode surface and in the gas phase, interactions occurring in the gas phase are probably the main paths for this equilibration in the glow discharge.

  8. Chemical analysis of diesel engine nanoparticles using a nano-DMA/thermal desorption particle beam mass spectrometer.

    PubMed

    Tobias, H J; Beving, D E; Ziemann, P J; Sakurai, H; Zuk, M; McMurry, P H; Zarling, D; Waytulonis, R; Kittelson, D B

    2001-06-01

    Diesel engines are known to emit high number concentrations of nanoparticles (diameter < 50 nm), but the physical and chemical mechanisms by which they form are not understood. Information on chemical composition is lacking because the small size, low mass concentration, and potential for contamination of samples obtained by standard techniques make nanoparticles difficult to analyze. A nano-differential mobility analyzer was used to size-select nanoparticles (mass median diameter approximately 25-60 nm) from diesel engine exhaust for subsequent chemical analysis by thermal desorption particle beam mass spectrometry. Mass spectra were used to identify and quantify nanoparticle components, and compound molecular weights and vapor pressures were estimated from calibrated desorption temperatures. Branched alkanes and alkyl-substituted cycloalkanes from unburned fuel and/or lubricating oil appear to contribute most of the diesel nanoparticle mass. The volatility of the organic fraction of the aerosol increases as the engine load decreases and as particle size increases. Sulfuric acid was also detected at estimated concentrations of a few percent of the total nanoparticle mass. The results are consistent with a mechanism of nanoparticle formation involving nucleation of sulfuric acid and water, followed by particle growth by condensation of organic species.

  9. Chemical characterization of freshly emitted particulate matter from aircraft exhaust using single particle mass spectrometry

    NASA Astrophysics Data System (ADS)

    Abegglen, Manuel; Brem, B. T.; Ellenrieder, M.; Durdina, L.; Rindlisbacher, T.; Wang, J.; Lohmann, U.; Sierau, B.

    2016-06-01

    Non-volatile aircraft engine emissions are an important anthropogenic source of soot particles in the upper troposphere and in the vicinity of airports. They influence climate and contribute to global warming. In addition, they impact air quality and thus human health and the environment. The chemical composition of non-volatile particulate matter emission from aircraft engines was investigated using single particle time-of-flight mass spectrometry. The exhaust from three different aircraft engines was sampled and analyzed. The soot particulate matter was sampled directly behind the turbine in a test cell at Zurich Airport. Single particle analyses will focus on metallic compounds. The particles analyzed herein represent a subset of the emissions composed of the largest particles with a mobility diameter >100 nm due to instrumental restrictions. A vast majority of the analyzed particles was shown to contain elemental carbon, and depending on the engine and the applied thrust the elemental carbon to total carbon ratio ranged from 83% to 99%. The detected metallic compounds were all internally mixed with the soot particles. The most abundant metals in the exhaust were Cr, Fe, Mo, Na, Ca and Al; V, Ba, Co, Cu, Ni, Pb, Mg, Mn, Si, Ti and Zr were also detected. We further investigated potential sources of the ATOFMS-detected metallic compounds using Inductively Coupled Plasma Mass Spectrometry. The potential sources considered were kerosene, engine lubrication oil and abrasion from engine wearing components. An unambiguous source apportionment was not possible because most metallic compounds were detected in several of the analyzed sources.

  10. Chemical characterization of freshly emitted particulate matter from aircraft exhaust using single particle mass spectrometry

    NASA Astrophysics Data System (ADS)

    Abegglen, Manuel; Brem, B. T.; Ellenrieder, M.; Durdina, L.; Rindlisbacher, T.; Wang, J.; Lohmann, U.; Sierau, B.

    2016-06-01

    Non-volatile aircraft engine emissions are an important anthropogenic source of soot particles in the upper troposphere and in the vicinity of airports. They influence climate and contribute to global warming. In addition, they impact air quality and thus human health and the environment. The chemical composition of non-volatile particulate matter emission from aircraft engines was investigated using single particle time-of-flight mass spectrometry. The exhaust from three different aircraft engines was sampled and analyzed. The soot particulate matter was sampled directly behind the turbine in a test cell at Zurich Airport. Single particle analyses will focus on metallic compounds. The particles analyzed herein represent a subset of the emissions composed of the largest particles with a mobility diameter >100 nm due to instrumental restrictions. A vast majority of the analyzed particles was shown to contain elemental carbon, and depending on the engine and the applied thrust the elemental carbon to total carbon ratio ranged from 83% to 99%. The detected metallic compounds were all internally mixed with the soot particles. The most abundant metals in the exhaust were Cr, Fe, Mo, Na, Ca and Al; V, Ba, Co, Cu, Ni, Pb, Mg, Mn, Si, Ti and Zr were also detected. We further investigated potential sources of the ATOFMS-detected metallic compounds using Inductively Coupled Plasma Mass Spectrometry. The potential sources considered were kerosene, engine lubrication oil and abrasion from engine wearing components. An unambiguous source apportionment was not possible because most metallic compounds were detected in several of the analyzed sources.

  11. Masses and age of the chemically peculiar double-lined binary χ Lupi

    NASA Astrophysics Data System (ADS)

    Le Bouquin, J.-B.; Beust, H.; Duvert, G.; Berger, J. P.; Ménard, F.; Zins, G.

    2013-03-01

    Aims: We aim at measuring the stellar parameters of the two chemically peculiar components of the B9.5Vp HgMn + A2 Vm double-lined spectroscopic binary HD 141556 (χ Lup), whose period is 15.25 days. Methods: We combined historical radial velocity measurements with new spatially resolved astrometric observations from PIONIER/VLTI to reconstruct the three-dimensional orbit of the binary, and thus obtained the individual masses. We fit the available photometric points together with the flux ratios provided by interferometry to constrain the individual sizes, which we compared to predictions from evolutionary models. Results: The individual masses of the components are Ma = 2.84 ± 0.12 M⊙ and Mb = 1.94 ± 0.09 M⊙. The dynamical distance is compatible with the Hipparcos parallax. We find linear stellar radii of Ra = 2.85 ± 0.15 R⊙ and Rb = 1.75 ± 0.18 R⊙. This result validates a posteriori the flux ratio used in previous detailed abundance studies. Assuming coevality, we determine a slightly sub-solar initial metallicity Z = 0.012 ± 0.003 and an age of (2.8 ± 0.3) × 108 years. Finally, our results imply that the primary rotates more slowly than its synchronous velocity, while the secondary is probably synchronous. We show that strong tidal coupling during the pre-main sequence evolution followed by a full decoupling at zero-age main sequence provides a plausible explanation for these very low rotation rates. Based on data collected with the PIONIER visitor-instrument installed at the ESO Paranal Observatory under program 088.D-0828.Appendices are available in electronic form at http://www.aanda.org

  12. A miniature laser ablation mass spectrometer for quantitative in situ chemical composition investigation of lunar surface

    NASA Astrophysics Data System (ADS)

    Brigitte Neuland, Maike; Grimaudo, Valentine; Mezger, Klaus; Moreno-García, Pavel; Riedo, Andreas; Tulej, Marek; Wurz, Peter

    2016-04-01

    The chemical composition of planetary bodies, moons, comets and asteroids is a key to understand their origin and evolution [Wurz,2009]. Measurements of the elemental and isotopic composition of rocks yield information about the formation of the planetary body, its evolution and following processes shaping the planetary surface. From the elemental composition, conclusions about modal mineralogy and petrology can be drawn. Isotope ratios are a sensitive indicator for past events on the planetary body and yield information about origin and transformation of the matter, back to events that occurred in the early solar system. Finally, measurements of radiogenic isotopes make it possible to carry out dating analyses. All these topics, particularly in situ dating analyses, quantitative elemental and highly accurate isotopic composition measurements, are top priority scientific questions for future lunar missions. An instrument for precise measurements of chemical composition will be a key element in scientific payloads of future landers or rovers on lunar surface. We present a miniature laser ablation mass spectrometer (LMS) designed for in situ research in planetary and space science and optimised for measurements of the chemical composition of rocks and soils on a planetary surface. By means of measurements of standard reference materials we demonstrate that LMS is a suitable instrument for in situ measurements of elemental and isotopic composition with high precision and accuracy. Measurements of soil standards are used to confirm known sensitivity coefficients of the instrument and to prove the power of LMS for quantitative elemental analyses [Neuland,2016]. For demonstration of the capability of LMS to measure the chemical composition of extraterrestrial material we use a sample of Allende meteorite [Neuland,2014]. Investigations of layered samples confirm the high spatial resolution in vertical direction of LMS [Grimaudo,2015], which allows in situ studying of past

  13. A pan-European study of capabilities to manage mass casualties from the release of chemical agents: the MASH project.

    PubMed

    Baker, David J; Murray, Virginia S G; Carli, Pierre A

    2013-01-01

    The European Union (EU) Mass Casualties and Health (MASH) project that ran between 2008 and 2010 was designed to study the management of mass casualties from chemical and radiological releases and associated health implications. One area of study for this project concerned arrangements within EU Member States for the management of mass casualties following a chemical release. This was undertaken via a confidential online questionnaire that was sent to selected points of contact throughout the EU. Responses were obtained from 18 states from respondents holding senior positions in chemical planning and incident response. Information gathered shows a lack of uniformity within the EU about the organization of responses to chemical releases and the provision of medical care. This article presents the overall findings of the study demonstrating differences between countries on planning and organization, decontamination, prehospital emergency medical responses, clinical diagnoses, and therapy and aftercare. Although there may be an understandable reluctance from national respondents to share information on security and other grounds, the findings, nevertheless, revealed substantial differences between current planning and operational responses within the EU states for the management of mass chemical casualties. The existing international networks for response to radiation incidents are not yet matched by equivalent networks for chemical responses yet sufficient information was available from the study to identify potential deficiencies, identify common casualty management pathways, and to make recommendations for future operations within the EU. Improvements in awareness and training and the application of modern information and communications will help to remedy this situation. Specialized advanced life support and other medical care for chemical casualties appear lacking in some countries. A program of specialized training and action are required to apply the findings

  14. Analysis of isomeric polycyclic aromatic hydrocarbons by charge-exchange chemical ionization mass spectrometry

    SciTech Connect

    Simonsick, W.J. Jr.; Hites, R.A.

    1984-12-01

    Charge-exchange chemical ionization mass spectrometry (using a 15% mixture of methane in argon) yields abundant M/sup +/, M + H/sup +/, M + C/sub 2/H/sub 5//sup +/ ions of polycyclic aromatic hydrocarbons (PAH). On the basis of the relative intensities of the M + H/sup +/ ion to the M/sup +/ ion, this technique can differentiate, in a predictable manner, isomeric structures of PAH. The operating conditions were evaluated and optimized; the most significant contributions to the variations in the (M + H)/sup +//M/sup +/ ratios are the temperature, pressure, and condition of the ion source. The optimum ion source temperature (250/sup 0/C) and pressure (0.8 torr) are easily controlled and regulated. The variable contamination of the ion source is compensated by an internal standard 1,2,3,5-tetrafluorobenzene. The analyses of Standard Reference Materials 1648 and 1649 (air particulate samples) and a carbon black extract are reported. Triphenylene and chrysene, although not chromatographically resolved, can be quantitated by using this technique. The identification of acephenanthrylene based on the measurement of ratios and calculated ionization potentials is also presented.

  15. Rapid detection of drugs in biofluids using atmospheric pressure chemi/chemical ionization mass spectrometry.

    PubMed

    Chen, Lee Chuin; Hashimoto, Yutaka; Furuya, Hiroko; Takekawa, Kenichi; Kubota, Takeo; Hiraoka, Kenzo

    2009-02-01

    We have demonstrated that, with simple pH adjustment, volatile drugs such as methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine (MDMA), ketamine, and valproic acid could be analyzed rapidly from raw biofluid samples (e.g. urine and serum) without dilution, or extraction, using atmospheric pressure ionization. The ion source was a variant type of atmospheric pressure chemical ionization (APCI) that used a dielectric barrier discharge (DBD) to generate the metastable helium gas and reagent ions. The sample solution was loaded in a disposable glass pipette, and the volatile compounds were purged by nitrogen gas to be reacted with the metastable helium gas. The electrodes of the DBD were arranged in such a way that the generated glow discharge was confined within the discharge tube and was not exposed to the analytes. A needle held at 100-500 V was placed between the ion-sampling orifice and the discharge tube to guide the analyte ions into the mass spectrometer. After pH adjustment of the biofluid sample, the amphiphilic drugs were in the form of a water-insoluble oil, which could be concentrated on the liquid surface. By gentle heating of the sample to increase the evaporation rate, rapid and sensitive detection of these drugs in raw urine and serum samples could be achieved in less than 2 min for each sample. PMID:19125420

  16. Chemical cross-linkers for protein structure studies by mass spectrometry.

    PubMed

    Paramelle, David; Miralles, Guillaume; Subra, Gilles; Martinez, Jean

    2013-02-01

    The cross-linking approach combined with MS for protein structure determination is one of the most striking examples of multidisciplinary success. Indeed, it has become clear that the bottleneck of the method was the detection and the identification of low-abundance cross-linked peptides in complex mixtures. Sample treatment or chromatography separation partially addresses these issues. However, the main problem comes from over-represented unmodified peptides, which do not yield any structural information. A real breakthrough was provided by high mass accuracy measurement, because of the outstanding technical developments in MS. This improvement greatly simplified the identification of cross-linked peptides, reducing the possible combinations matching with an observed m/z value. In addition, the huge amount of data collected has to be processed with dedicated software whose role is to propose distance constraints or ideally a structural model of the protein. In addition to instrumentation and algorithms efficiency, significant efforts have been made to design new cross-linkers matching all the requirements in terms of reactivity and selectivity but also displaying probes or reactive systems facilitating the isolation, the detection of cross-links, or the interpretation of MS data. These chemical features are reviewed and commented on in the light of the more recent strategies. PMID:23255214

  17. Laser-Induced Acoustic Desorption/Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Gao, Jinshan; Borton, David J.; Owen, Benjamin C.; Jin, Zhicheng; Hurt, Matt; Amundson, Lucas M.; Madden, Jeremy T.; Qian, Kuangnan; Kenttämaa, Hilkka I.

    2010-01-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a linear quadrupole ion trap mass spectrometer (LQIT). Model compounds representing a wide variety of different types, including basic nitrogen and oxygen compounds, aromatic and aliphatic compounds, as well as unsaturated and saturated hydrocarbons, were tested separately and as a mixture. These model compounds were successfully evaporated into the gas phase by using LIAD and then ionized by using APCI with different reagents. Four APCI reagent systems were tested: the traditionally used mixture of methanol and water, neat benzene, neat carbon disulfide, and nitrogen gas (no liquid reagent). The mixture of methanol and water produced primarily protonated molecules, as expected. However, only the most basic compounds yielded ions under these conditions. In sharp contrast, using APCI with either neat benzene or neat carbon disulfide as the reagent resulted in the ionization of all the analytes studied to predominantly yield stable molecular ions. Benzene yielded a larger fraction of protonated molecules than carbon disulfide, which is a disadvantage. A similar amount of fragmentation was observed for these reagents. When the experiment was performed without a liquid reagent(nitrogen gas was the reagent), more fragmentation was observed. Analysis of a known mixture as well as a petroleum cut was also carried out. In summary, the new experiment presented here allows the evaporation of thermally labile compounds, both polar and nonpolar, without dissociation or aggregation, and their ionization to form stable molecular ions. PMID:21472571

  18. Real-time flavor release from French fries using atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    van Loon, Wil A M; Linssen, Jozef P H; Boelrijk, Alexandra E M; Burgering, Maurits J M; Voragen, Alphons G J

    2005-08-10

    Flavor release from French fries was measured with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) using both assessors (in vivo) and a mouth model system (in vitro). Several volatiles measured with APCI were identified with MS-MS. The effect of frying time, salt addition, and an alternative process using superheated steam was determined on I(max) (maximum intensity of compounds) and on t(max) (time of maximum intensity). In vitro a "chewing" frequency of 0.60 Hz caused an increased t(max) for low molecular weight compounds compared to the other frequencies tested. Above 0.93 Hz further increase in the frequency did not affect t(max). Trends observed with in vivo experiments could be verified with in vitro experiments. I(max) correlated well with frying time. Addition of salt resulted in a decreased t(max), suggesting a salting-out effect. The alternative process caused a layer of oil on the surface, and this resulted in a higher t(max), but no effect on I(max) was found. This phenomenon may be critical for the sensory quality and would not have been observed with static volatile measurements, demonstrating the value of flavor release measurements.

  19. The influence of stopping power on the ionisation quench factor.

    PubMed

    García, G; Grau, Malonda A

    2002-01-01

    Stopping power values for high energies have been computed applying the first Born approximation and the Bethe formula. However, this approximation tends to overestimate these cross sections at low energies, reaching discrepancies on the order of 50% at energies below 1 keV for most of the molecular targets of interest. In this paper we propose a method to obtain accurate low energy stopping powers of electrons by combining total cross section measurements with a theoretical treatment of the elastic process. We determine the optimum value of the kB parameter of ionisation quenching for the stopping power obtained in this paper.

  20. NICIL: Non-Ideal magnetohydrodynamics Coefficients and Ionisation Library

    NASA Astrophysics Data System (ADS)

    Wurster, James

    2016-08-01

    NICIL (Non-Ideal magnetohydrodynamics Coefficients and Ionisation Library) calculates the ionization values and the coefficients of the non-ideal magnetohydrodynamics terms of Ohmic resistivity, the Hall effect, and ambipolar diffusion. Written as a standalone Fortran90 module that can be implemented in existing codes, NICIL is fully parameterizable, allowing the user to choose which processes to include and decide the values of the free parameters. The module includes both cosmic ray and thermal ionization; the former includes two ion species and three species of dust grains (positively charged, negatively charged and neutral), and the latter includes five elements which can be doubly ionized.

  1. Determination of BROMATE AT PARTS-PER-TRILLION LEVELS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY WITH NEGATIVE CHEMICAL IONIZATION

    EPA Science Inventory

    The ozonation of bromide-containing source waters produces bromate as a class 2B carcinogenic disinfection by-product. The present work describes the determination of bromate by gas chromatography-negative chemical ionization mass spectrometry (GC-NCIMS) following a bromate react...

  2. The effect of the mass and initial chemical form of neptunium on its molecular associations in blood and liver.

    PubMed

    Paquet, F; Ramounet, B; Métivier, H; Taylor, D M

    1996-09-01

    The present investigation was aimed at establishing the distribution of neptunium in blood and liver cells as a function of the mass and chemical form of the radionuclide injected. Four groups of rats received intravenous injections of 237Np(V), 237Np(IV), 239Np(V) or 239Np(IV). Twenty-four hours after injection of the radionuclide, subcellular structures of the liver were separated by ultracentrifugation and serum and liver cytosol were subjected to gel permeation chromatography. The intracellular distribution of neptunium in liver depends on the mass of the radionuclide injected; the relative specific activity for 237Np compared to 239Np was 2 in nuclei and 0.5-0.9 in cytosol. By contrast, the initial chemical form of the radionuclide has no significant effect on its intracellular distribution. In cytosol, neptunium was bound mainly by two proteins of molecular weight 450 and 200 kDa, respectively. The former was identified as ferritin, but the latter remains unidentified. In this compartment, no effect of mass or chemical form was seen. In blood, the bulk of the radionuclide was bound to transferrin whatever the mass and initial chemical form injected.

  3. Lightning-driven inner radiation belt energy deposition into the atmosphere: implications for ionisation-levels and neutral chemistry

    NASA Astrophysics Data System (ADS)

    Rodger, C. J.; Enell, C.-F.; Turunen, E.; Clilverd, M. A.; Thomson, N. R.; Verronen, P. T.

    2007-08-01

    Lightning-generated whistlers lead to coupling between the troposphere, the Van Allen radiation belts and the lower-ionosphere through Whistler-induced electron precipitation (WEP). Lightning produced whistlers interact with cyclotron resonant radiation belt electrons, leading to pitch-angle scattering into the bounce loss cone and precipitation into the atmosphere. Here we consider the relative significance of WEP to the lower ionosphere and atmosphere by contrasting WEP produced ionisation rate changes with those from Galactic Cosmic Radiation (GCR) and solar photoionisation. During the day, WEP is never a significant source of ionisation in the lower ionosphere for any location or altitude. At nighttime, GCR is more significant than WEP at altitudes <68 km for all locations, above which WEP starts to dominate in North America and Central Europe. Between 75 and 80 km altitude WEP becomes more significant than GCR for the majority of spatial locations at which WEP deposits energy. The size of the regions in which WEP is the most important nighttime ionisation source peaks at ~80 km, depending on the relative contributions of WEP and nighttime solar Lyman-α. We also used the Sodankylä Ion Chemistry (SIC) model to consider the atmospheric consequences of WEP, focusing on a case-study period. Previous studies have also shown that energetic particle precipitation can lead to large-scale changes in the chemical makeup of the neutral atmosphere by enhancing minor chemical species that play a key role in the ozone balance of the middle atmosphere. However, SIC modelling indicates that the neutral atmospheric changes driven by WEP are insignificant due to the short timescale of the WEP bursts. Overall we find that WEP is a significant energy input into some parts of the lower ionosphere, depending on the latitude/longitude and altitude, but does not play a significant role in the neutral chemistry of the mesosphere.

  4. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

  5. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs. PMID:24678766

  6. Chemical Composition of Intermediate-mass Star Members of the M6 (NGC 6405) Open Cluster

    NASA Astrophysics Data System (ADS)

    Kılıçoğlu, T.; Monier, R.; Richer, J.; Fossati, L.; Albayrak, B.

    2016-03-01

    We present here the first abundance analysis of 44 late B-, A-, and F-type members of the young open cluster M6 (NGC 6405, age about 75 Myr). Low- and medium-resolution spectra, covering the 4500-5840 Å wavelength range, were obtained using the FLAMES/GIRAFFE spectrograph attached to the ESO Very Large Telescopes. We determined the atmospheric parameters using calibrations of the Geneva photometry and by adjusting the Hβ profiles to synthetic ones. The abundances of up to 20 chemical elements, from helium to mercury, were derived for 19 late B, 16 A, and 9 F stars by iteratively adjusting synthetic spectra to the observations. We also derived a mean cluster metallicity of [Fe/H] = 0.07 ± 0.03 dex from the iron abundances of the F-type stars. We find that for most chemical elements, the normal late B- and A-type stars exhibit larger star-to-star abundance variations than the F-type stars probably because of the faster rotation of the B and A stars. The abundances of C, O, Mg, Si, and Sc appear to be anticorrelated with that of Fe, while the opposite holds for the abundances of Ca, Ti, Cr, Mn, Ni, Y, and Ba as expected if radiative diffusion is efficient in the envelopes of these stars. In the course of this analysis, we discovered five new peculiar stars: one mild Am, one Am, and one Fm star (HD 318091, CD-32 13109, GSC 07380-01211, CP1), one HgMn star (HD 318126, CP3), and one He-weak P-rich (HD 318101, CP4) star. We also discovered a new spectroscopic binary, most likely a SB2. We performed a detailed modeling of HD 318101, the new He-weak P-rich CP star, using the Montréal stellar evolution code XEVOL which self-consistently treats all particle transport processes. Although the overall abundance pattern of this star is properly reproduced, we find that detailed abundances (in particular the high P excess) resisted modeling attempts even when a range of turbulence profiles and mass-loss rates were considered. Solutions are proposed which are still under

  7. Gaseous composition measured by a chemical ionization mass spectrometer in fresh and aged ship plumes

    NASA Astrophysics Data System (ADS)

    Faxon, Cameron; Psichoudaki, Magda; Kuuluvainen, Heino; Hallquist, Åsa; Thomson, Erik; Pettersson, Jan; Hallquist, Mattias

    2015-04-01

    The port of Gothenburg is the largest port of the Nordic countries with numerous ships calling the port daily. The ship exhausts contain numerous pollutants including gases such as SO2 and NOx as well as particulate matter and soot. The exhaust also contains numerous organic compounds, a large fraction of which are unidentified. These organics are oxidized in the atmosphere producing more oxygenated and potentially less volatile compounds that may contribute to the secondary organic aerosol (SOA). This work focuses on the characterization of fresh gaseous species present in the exhaust plumes of the passing ships and also on their photochemical aging. Between 26 September and 12 November 2014 measurements were conducted at a sampling site located on a small peninsula at the entrance of Gothenburg's port. The campaign was divided in two periods. During the first period, the fresh plumes of the passing ships were measured through a main inlet. During the second period, the sample passed through the same inlet and was then introduced into a Potential Aerosol Mass (PAM) reactor. The PAM reactor uses UV lamps and high concentrations of oxidants (OH radicals and O3) to oxidize the organic species present in the plumes. The oxidation that takes place within the reactor can be equivalent to up to one week of atmospheric oxidation. Preliminary tests showed that the oxidation employed in the current camping corresponded to 3.4 days in the atmosphere. A Time-of-Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) was employed to monitor the concentration of different organic species present in the fresh and aged plumes. Water (positive) and iodide (negative) ionization methods were employed were water was primarily used for fresh plumes (large fraction of non-polar compounds) while iodide was used for the aged plumes (primarily oxidised products). The H2O, O3 and SO2 concentrations inside the PAM chamber were monitored, and an organic tracer for OH exposure determination

  8. Control and Automation of Fluid Flow, Mass Transfer and Chemical Reactions in Microscale Segmented Flow

    NASA Astrophysics Data System (ADS)

    Abolhasani, Milad

    Flowing trains of uniformly sized bubbles/droplets (i.e., segmented flows) and the associated mass transfer enhancement over their single-phase counterparts have been studied extensively during the past fifty years. Although the scaling behaviour of segmented flow formation is increasingly well understood, the predictive adjustment of the desired flow characteristics that influence the mixing and residence times, remains a challenge. Currently, a time consuming, slow and often inconsistent manual manipulation of experimental conditions is required to address this task. In my thesis, I have overcome the above-mentioned challenges and developed an experimental strategy that for the first time provided predictive control over segmented flows in a hands-off manner. A computer-controlled platform that consisted of a real-time image processing module within an integral controller, a silicon-based microreactor and automated fluid delivery technique was designed, implemented and validated. In a first part of my thesis I utilized this approach for the automated screening of physical mass transfer and solubility characteristics of carbon dioxide (CO2) in a physical solvent at a well-defined temperature and pressure and a throughput of 12 conditions per hour. Second, by applying the segmented flow approach to a recently discovered CO2 chemical absorbent, frustrated Lewis pairs (FLPs), I determined the thermodynamic characteristics of the CO2-FLP reaction. Finally, the segmented flow approach was employed for characterization and investigation of CO2-governed liquid-liquid phase separation process. The second part of my thesis utilized the segmented flow platform for the preparation and shape control of high quality colloidal nanomaterials (e.g., CdSe/CdS) via the automated control of residence times up to approximately 5 minutes. By introducing a novel oscillatory segmented flow concept, I was able to further extend the residence time limitation to 24 hours. A case study of a

  9. Exploring Potential Chemical Transformation by Chemical Profiling Approach for Rapidly Evaluating Chemical Consistency between Sun-Dried and Sulfur-Fumigated Radix Paeoniae Alba Using Ultraperformance Liquid Chromatography Coupled with Time-of-Flight Mass Spectrometry

    PubMed Central

    Zhang, Jida; Cai, Hao; Cao, Gang; Liu, Xiao; Wen, Chengping; Fan, Yongsheng

    2013-01-01

    Ultraperformance liquid chromatography coupled with time-of-flight mass spectrometry (UPLC-QTOF/MS) based on a chemical profiling method was applied to rapidly evaluate the chemical consistency between sun-dried and sulfur-fumigated Radix Paeoniae Alba. By virtue of the high resolution, high speed of UPLC, and the accurate mass measurement of TOFMS coupled with reliable MarkerLynx software, five newly assigned monoterpene glycoside sulfonates were found and identified in sulfur-fumigated Radix Paeoniae Alba samples. This method could be applied for rapid quality evaluation of different kinds of sulfur-fumigated Radix Paeoniae Alba among commercial samples. PMID:24381637

  10. Atmospheric Amines and Ammonia Measured with a Chemical Ionization Mass Spectrometer (CIMS)

    SciTech Connect

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, Alex B.; Madronich, Sasha; Sierra-Hernandez, M. R.; Lawler, M.; Smith, James N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, Eric S.; Porcelli, L.; Brune, W. H.; Goldstein, Allen H.; Lee, S.-H

    2014-11-19

    We report ambient measurements of amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a Southeastern U.S. forest in Alabama and a moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1-C6) at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast U.S. At the moderately polluted Kent site, higher concentrations of amines (C1-C6, from pptv to tens of pptv) and ammonia (up to 6 ppbv) were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.

  11. Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Harris, Glenn A.

    Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in

  12. Passive Sampling and High Resolution Mass Spectrometry for Chemical Profiling of French Coastal Areas with a Focus on Marine Biotoxins.

    PubMed

    Zendong, Zita; Bertrand, Samuel; Herrenknecht, Christine; Abadie, Eric; Jauzein, Cécile; Lemée, Rodolphe; Gouriou, Jérémie; Amzil, Zouher; Hess, Philipp

    2016-08-16

    Passive samplers (solid phase adsorption toxin tracking: SPATT) are able to accumulate biotoxins produced by microalgae directly from seawater, thus providing useful information for monitoring of the marine environment. SPATTs containing 0.3, 3, and 10 g of resin were deployed at four different coastal areas in France and analyzed using liquid chromatography coupled to high resolution mass spectrometry. Quantitative targeted screening provided insights into toxin profiles and showed that toxin concentrations and profiles in SPATTs were dependent on the amount of resin used. Between the three amounts of resin tested, SPATTs containing 3 g of resin appeared to be the best compromise, which is consistent with the use of 3 g of resin in SPATTs by previous studies. MassHunter and Mass Profiler Professional softwares were used for data reprocessing and statistical analyses. A differential profiling approach was developed to investigate and compare the overall chemical diversity of dissolved substances in different coastal water bodies. Principal component analysis (PCA) allowed for spatial differentiation between areas. Similarly, SPATTs retrieved from the same location at early, medium, and late deployment periods were also differentiated by PCA, reflecting seasonal variations in chemical profiles and in the microalgal community. This study used an untargeted metabolomic approach for spatial and temporal differentiation of marine environmental chemical profiles using SPATTs, and we propose this approach as a step forward in the discovery of chemical markers of short- or long-term changes in the microbial community structure. PMID:27463836

  13. A study of ionisation of free and clustered molecules under the action of femtosecond laser radiation

    SciTech Connect

    Apatin, V M; Kompanets, V O; Lokhman, V N; Ogurok, N-D D; Poydashev, D G; Ryabov, E A; Chekalin, S V

    2014-05-30

    We have investigated the processes of excitation and ionisation of monomers and clusters of CF{sub 3}I, IF{sub 2}CCOF and Fe(CO){sub 5} molecules under the action of femtosecond laser radiation at the wavelengths of 266, 400 and 800 nm. It is concluded that the nature of the excitation of free molecules and clustered molecules by femtosecond pulses is different. The simulation of the ionisation yield of the objects under study has shown that the multiphoton ionisation is the key mechanism in the case of free molecules, while the field ionisation may play a significant role for clusters, in particular, in the case of ionisation at the wavelength of λ = 800 nm. (interaction of radiation with matter)

  14. Spatial localisation of curcumin and rapid screening of the chemical compositions of turmeric rhizomes (Curcuma longa Linn.) using Direct Analysis in Real Time-Mass Spectrometry (DART-MS).

    PubMed

    Rahman, A F M Motiur; Angawi, Rihab F; Kadi, Adnan A

    2015-04-15

    Curcumin is a potent antioxidant agent having versatile biological activities is present in turmeric rhizomes (Curcuma longa Linn.). Powder of turmeric rhizomes is consumes as curry spicy worldwide, especially in Asia. In this study, we demonstrate that, bioactive curcumin and its analog demethoxycurcumin are chiefly concentrated in the pith rather than the other parts of the turmeric rhizomes and it was discovered using modern atmospheric ionisation source 'Direct Analysis in Real Time' (DART) connected with an Ion Trap Mass Spectrometry. In addition, all the major components present in turmeric rhizomes were detected in positive and/or in negative ion mode using DART. PMID:25466050

  15. Spatial localisation of curcumin and rapid screening of the chemical compositions of turmeric rhizomes (Curcuma longa Linn.) using Direct Analysis in Real Time-Mass Spectrometry (DART-MS).

    PubMed

    Rahman, A F M Motiur; Angawi, Rihab F; Kadi, Adnan A

    2015-04-15

    Curcumin is a potent antioxidant agent having versatile biological activities is present in turmeric rhizomes (Curcuma longa Linn.). Powder of turmeric rhizomes is consumes as curry spicy worldwide, especially in Asia. In this study, we demonstrate that, bioactive curcumin and its analog demethoxycurcumin are chiefly concentrated in the pith rather than the other parts of the turmeric rhizomes and it was discovered using modern atmospheric ionisation source 'Direct Analysis in Real Time' (DART) connected with an Ion Trap Mass Spectrometry. In addition, all the major components present in turmeric rhizomes were detected in positive and/or in negative ion mode using DART.

  16. First Order Chemical Reaction Effects on Exponentially Accelerated Vertical Plate with Variable Mass Diffusion in the Presence of Thermal Radiation

    NASA Astrophysics Data System (ADS)

    Muthucumaraswamy, R.; Lakshmi, C. S.

    2015-05-01

    Effects of transfer of mass and free convection on the flow field of an incompressible viscous fluid past an exponentially accelerated vertical plate with variable surface temperature and mass diffusion are studied. Results for velocity, concentration, temperature are obtained by solving governing equations using the Laplace transform technique. It is observed that the velocity increases with decreasing values of the chemical reaction parameter or radiation parameter. But the trend is just reversed with respect to the time parameter. The skin friction is also studied.

  17. Analytical pyrolysis mass spectrometry: new vistas opened by temperature-resolved in-source PYMS

    NASA Astrophysics Data System (ADS)

    Boon, Jaap J.

    1992-09-01

    Analytical pyrolysis mass spectrometry (PYMS) is introduced and its applications to the analysis of synthetic polymers, biopolymers, biomacromolecular systems and geomacromolecules are critically reviewed. Analytical pyrolysis inside the ionisation chamber of a mass spectrometer, i.e. in-source PYMS, gives a complete inventory of the pyrolysis products evolved from a solid sample. The temperature-resolved nature of the experiment gives a good insight into the temperature dependence of the volatilisation and pyrolytic dissociation processes. Chemical ionisation techniques appear to be especially suitable for the analysis of oligomeric fragments released in early stages of the pyrolysis of polymer systems. Large oligomeric fragments were observed for linear polymers such as cellulose (pentadecamer), polyhydroxyoctanoic acid (tridecamer) and polyhydroxybutyric acid (heneicosamer). New in-source PYMS data are presented on artists' paints, the plant polysaccharides cellulose and xyloglucan, several microbial polyhydroxyalkanoates, wood and enzyme-digested wood, biodegraded roots and a fossil cuticle of Miocene age. On-line and off-line pyrolysis chromatography mass spectrometric approaches are also discussed. New data presented on high temperature gas chromatography--mass spectrometry of deuterio-reduced permethylated pyrolysates of cellulose lead to a better understanding of polysaccharide dissociation mechanisms. Pyrolysis as an on-line sample pretreatment method for organic macromolecules in combination with MS techniques is a very challenging field of mass spectrometry. Pyrolytic dissociation and desorption is not at all a chaotic process but proceeds according to very specific mechanisms.

  18. The influence of Oort clouds on the mass and chemical balance of the interstellar medium

    SciTech Connect

    Stern, S.A.; Shull, J.M. )

    1990-08-01

    The contribution of stellar encounters and interstellar erosion to comet cloud mass injection to the ISM is calculated. It is shown that evaporative mass loss from passing stars and SNe results in an average Galactic mass injection rate of up to 10 to the -5th solar mass/yr if such clouds are frequent around solar-type stars. Cometary erosion by interstellar grains produces an injection rate of 10 to the -5th to 10 to the -4th solar mass/yr. An injection rate of 2 x 10 to the -5th solar mass/yr is calculated. Each of these rates could be increased by a factor of about 15 if the comet clouds contain a significant amount of smaller debris. It is concluded that the total mass injection rate of material to the ISM by comet clouds is small compared to other ISM mass injection sources. Comet cloud mass loss to the ISM could be responsible for a sizeable fraction of the metal and dust abundances of the ISM if Oort clouds are common. 50 refs.

  19. The influence of Oort clouds on the mass and chemical balance of the interstellar medium

    NASA Technical Reports Server (NTRS)

    Stern, S. Alan; Shull, J. Michael

    1990-01-01

    The contribution of stellar encounters and interstellar erosion to comet cloud mass injection to the ISM is calculated. It is shown that evaporative mass loss from passing stars and SNe results in an average Galactic mass injection rate of up to 10 to the -5th solar mass/yr if such clouds are frequent around solar-type stars. Cometary erosion by interstellar grains produces an injection rate of 10 to the -5th to 10 to the -4th solar mass/yr. An injection rate of 2 x 10 to the -5th solar mass/yr is calculated. Each of these rates could be increased by a factor of about 15 if the comet clouds contain a significant amount of smaller debris. It is concluded that the total mass injection rate of material to the ISM by comet clouds is small compared to other ISM mass injection sources. Comet cloud mass loss to the ISM could be responsible for a sizeable fraction of the metal and dust abundances of the ISM if Oort clouds are common.

  20. Data requirements for protein identification using chemically-assisted fragmentation and tandem mass spectrometry.

    PubMed

    Juhlin, Kenton D; Swift, Dionne D; Lacey, Martin P; Correa, Paul E; Keough, Thomas W

    2005-01-01

    Many laboratories identify proteins by searching tandem mass spectrometry data against genomic or protein sequence databases. These database searches typically use the measured peptide masses or the derived peptide sequence and, in this paper, we focus on the latter. We study the minimum peptide sequence data requirements for definitive protein identification from protein sequence databases. Accurate mass measurements are not needed for definitive protein identification, even when a limited amount of sequence data is available for searching. This information has implications for the mass spectrometry performance (and cost), data base search strategies and proteomics research.

  1. Direct chemical profiling of olive (Olea europaea) fruit epicuticular waxes by direct electrospray-ultrahigh resolution mass spectrometry.

    PubMed

    Vichi, Stefania; Cortés-Francisco, Nuria; Romero, Agustí; Caixach, Josep

    2015-03-01

    In the present paper, an electrospray ionization (ESI)-Orbitrap method is proposed for the direct chemical profiling of epicuticular wax (EW) from Olea europaea fruit. It constitutes a rapid and efficient tool suitable for a wide-ranging screening of a large number of samples. In a few minutes, the method provides a comprehensive characterization of total EW extracts, based on the molecular formula of their components. Accurate mass measurements are obtained by ultrahigh resolution mass spectrometry, and compositional restrictions are set on the basis of the information available from previous studies of olive EW. By alternating positive and negative ESI modes within the same analysis, complementary results are obtained and a wide range of chemical species is covered. This provides a detailed compositional overview that otherwise would only be available by applying multiple analytical techniques.

  2. Assessing the regional impact of Indonesian biomass burning emissions based on organic molecular tracers and chemical mass balance modeling

    NASA Astrophysics Data System (ADS)

    Engling, G.; He, J.; Betha, R.; Balasubramanian, R.

    2014-01-01

    Biomass burning activities commonly occur in Southeast Asia (SEA), and are particularly intense in Indonesia during dry seasons. The effect of biomass smoke emissions on air quality in the city state of Singapore was investigated during a haze episode in October 2006. Substantially increased levels of airborne particulate matter (PM) and associated chemical species were observed during the haze period. Specifically, the enhancement in the concentration of molecular tracers for biomass combustion such as levoglucosan by as much as two orders of magnitude and diagnostic ratios of individual organic compounds indicated that biomass burning emissions caused a regional smoke haze episode due to their long-range transport by prevailing winds. With the aid of air mass back trajectories and chemical mass balance modeling, large-scale forest and peat fires in Sumatra and Kalimantan were identified as the sources of the smoke aerosol, exerting a significant impact on air quality in downwind areas, such as Singapore.

  3. Assessing the regional impact of indonesian biomass burning emissions based on organic molecular tracers and chemical mass balance modeling

    NASA Astrophysics Data System (ADS)

    Engling, G.; He, J.; Betha, R.; Balasubramanian, R.

    2014-08-01

    Biomass burning activities commonly occur in Southeast Asia (SEA), and are particularly intense in Indonesia during the dry seasons. The effect of biomass smoke emissions on air quality in the city state of Singapore was investigated during a haze episode in October 2006. Substantially increased levels of airborne particulate matter (PM) and associated chemical species were observed during the haze period. Specifically, the enhancement in the concentration of molecular tracers for biomass combustion such as levoglucosan by as much as two orders of magnitude and the diagnostic ratios of individual organic compounds indicated that biomass burning emissions caused a regional smoke haze episode due to their long-range transport by prevailing winds. With the aid of air mass backward trajectories and chemical mass balance modeling, large-scale forest and peat fires in Sumatra and Kalimantan were identified as the sources of the smoke aerosol, exerting a significant impact on air quality in downwind areas, such as Singapore.

  4. Differentiation of regioisomeric aromatic ketocarboxylic acids by positive mode atmospheric pressure chemical ionization collision-activated dissociation tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer.

    PubMed

    Amundson, Lucas M; Owen, Benjamin C; Gallardo, Vanessa A; Habicht, Steven C; Fu, Mingkun; Shea, Ryan C; Mossman, Allen B; Kenttämaa, Hilkka I

    2011-04-01

    Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS(n)) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at different collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.

  5. Protection of the environment from ionising radiation: ethical issues.

    PubMed

    Oughton, Deborah

    2003-01-01

    The paper identifies some of the main ethical issues concerning the protection of the environment from radiation and suggests ways in which ethics can aid in developing a system of protection. After a presentation of background on ethical theory and environmental ethics, three main issues related to environmental protection are discussed: First, the question of valuing the environment and implications for the definition of harm and monetary valuation of environmental goods; second, difficulties with scientific uncertainty and applications of the precautionary principle; and third, issues concerned with the distribution of risk and its relevance for participation in decision-making. In summary, the paper argues that there are strong ethical grounds to provide for the protection of the environment and that, all other things being equal, there is no reason to treat ionising radiation differently to other environmental stressors.

  6. Hazards of ionising radiation: 100 years of observations on man.

    PubMed Central

    Doll, R.

    1995-01-01

    In November 1895, when Conrad Röntgen serendipitously discovered X-rays, epidemiology was effectively limited to the study of infectious disease. What little epidemiological work was done in other fields was done as part of clinical medicine or under the heading of geographical pathology. The risks from exposure to X-rays and subsequently from other types of ionising radiation were consequently discovered by qualitative association or animal experiment. They did not begin to be quantified in humans until half a century later, when epidemiology emerged as a scientific discipline capable of quantifying risks of non-infectious disease and the scientific world was alerted to the need for assessing the effects of the radiation to which large populations might be exposed by the use of nuclear energy in peace and war. PMID:8519643

  7. Protection of the environment from ionising radiation: ethical issues.

    PubMed

    Oughton, Deborah

    2003-01-01

    The paper identifies some of the main ethical issues concerning the protection of the environment from radiation and suggests ways in which ethics can aid in developing a system of protection. After a presentation of background on ethical theory and environmental ethics, three main issues related to environmental protection are discussed: First, the question of valuing the environment and implications for the definition of harm and monetary valuation of environmental goods; second, difficulties with scientific uncertainty and applications of the precautionary principle; and third, issues concerned with the distribution of risk and its relevance for participation in decision-making. In summary, the paper argues that there are strong ethical grounds to provide for the protection of the environment and that, all other things being equal, there is no reason to treat ionising radiation differently to other environmental stressors. PMID:12590067

  8. Regioisomeric analysis of triacylglycerols using silver-ion liquid chromatography-atmospheric pressure chemical ionization mass spectrometry: comparison of five different mass analyzers.

    PubMed

    Holčapek, Michal; Dvořáková, Hana; Lísa, Miroslav; Girón, Ana Jimenéz; Sandra, Pat; Cvačka, Josef

    2010-12-24

    Silver-ion high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization mass spectrometry (APCI-MS) is used for the regioisomeric analysis of triacylglycerols (TGs). Standard mixtures of TG regioisomers are prepared by the randomization reaction from 8 mono-acid TG standards (tripalmitin, tristearin, triarachidin, triolein, trielaidin, trilinolein, trilinolenin and tri-gamma-linolenin). In total, 32 different regioisomeric doublets and 11 triplets are synthesized, separated by silver-ion HPLC using three serial coupled chromatographic columns giving a total length of 75cm. The retention of TGs increases strongly with the double bond (DB) number and slightly for regioisomers having more DBs in sn-1/3 positions. DB positional isomers (linolenic vs. γ-linolenic acids) are also separated and their reverse retention order in two different mobile phases is demonstrated. APCI mass spectra of all separated regioisomers are measured on five different mass spectrometers: single quadrupole LC/MSD (Agilent Technologies), triple quadrupole API 3000 (AB SCIEX), ion trap Esquire 3000 (Bruker Daltonics), quadrupole time-of-flight micrOTOF-Q (Bruker Daltonics) and LTQ Orbitrap XL (Thermo Fisher Scientific). The effect of different types of mass analyzer on the ratio of [M+H-R(i)COOH](+) fragment ions in APCI mass spectra is lower compared to the effect of the number of DBs, their position on the acyl chain and the regiospecific distribution of acyl chains on the glycerol skeleton. Presented data on [M+H-R(i)COOH](+) ratios measured on five different mass analyzers can be used for the direct regioisomeric determination in natural and biological samples.

  9. Pattern of aerosol mass loading and chemical composition over the atmospheric environment of an urban coastal station

    NASA Astrophysics Data System (ADS)

    Bindu, G.; Nair, Prabha R.; Aryasree, S.; Hegde, Prashant; Jacob, Salu

    2016-02-01

    Aerosol sampling was carried out at four locations in and around Cochin (9°58‧ N, 76°17‧ E), an urban area, located on the southwest coast of India. The gravimetric estimates of aerosol mass loading showed wide range from 78 μg m-3 to >450 μg m-3, occasionally reaching values >500 μg m-3, associated with regional source characteristics. Most of the values were above the air quality standard. Both boundary layer and synoptic scale airflow pattern play role in the temporal features in aerosol mass loading and chemical composition. Chemical analysis of the aerosol samples were done for anionic species viz; F-, Cl-, Br-, NO2-,   NO3-,   PO43-,   SO42- and metallic/cationic species viz; Na, Ca, K, Mg, NH4+, Fe, Al, Cu, Mg, Pb, etc using Ion Chromatography, Atomic Absorption Spectroscopy (AAS) and Inductively Coupled Plasma- Atomic Emission Spectroscopy (ICP-AES). At all the locations, extremely high mass concentration of SO42- was observed with the mean value of 13±6.4 μg m-3 indicating the strong anthropogenic influence. Statistical analysis of the chemical composition data was carried out and the principal factors presented. Seasonal variation of these chemical species along with their percentage contributions and regional variations were also examined. Increase in level of Na in aerosol samples indicated the influence of monsoonal activity. Most of the species showed mass concentrations well above those measured over another coastal site Thiruvananthapuram (8°29‧ N, 76°57‧ E) situated ~220 km south of Cochin revealing the highly localized aerosol features.

  10. Resolving Ionisation and Metallicity on Parsec Scales Across Primordial Analogues with HST-WFC3

    NASA Astrophysics Data System (ADS)

    James, B. L.; Auger, M.; Calzetti, D.; Kewley, L.; Aloisi, A.; Pettini, M.; Trussler, J.

    2016-06-01

    Nearby Blue Compact Dwarf (BCD) galaxies are excellent laboratories for conducting detailed spatially resolved spectroscopic analyses of star-formation (SF), feedback, and chemical evolution in relatively pristine, low-metallicity environments analogous to those thought to exist in the early Universe. In this talk I will show a new, extensive dataset of narrow-band HST-WFC3 imaging where I essentially use HST as a high-spatial-resolution IFU to map six major emission lines in unprecedented detail, including HeII emission from WR stars. In this pioneering study, I spatially resolve diagnostic line ratios on sub-pc scales in two BCDs and deduce which ionisation mechanisms (e.g. shocks and/or photoionisation) are at work and assess their role in shaping the global galaxy properties. Moreover, I will present the first 'metallicity image' of a star-forming galaxy, revealing inhomogeneities on scales as small as <50~pc. This work not only demonstrates the benefits of high-resolution spatially-resolved observations in assessing the effects of feedback mechanisms and accurate chemical abundances, but also the limitations of emission line diagnostic tools which can break down on scales smaller than a H II region. Both aspects are especially relevant as we enter the era of extremely large telescopes, when observing structure on ˜~10~pc scales will no longer be limited to the local universe.

  11. High-resolution chemical depth profiling of solid material using a miniature laser ablation/ionization mass spectrometer.

    PubMed

    Grimaudo, Valentine; Moreno-García, Pavel; Riedo, Andreas; Neuland, Maike B; Tulej, Marek; Broekmann, Peter; Wurz, Peter

    2015-02-17

    High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.

  12. An isotopic analysis of ionising radiation as a source of sulphuric acid

    NASA Astrophysics Data System (ADS)

    Enghoff, M. B.; Bork, N.; Hattori, S.; Meusinger, C.; Nakagawa, M.; Pedersen, J. O. P.; Danielache, S.; Ueno, Y.; Johnson, M. S.; Yoshida, N.; Svensmark, H.

    2012-06-01

    Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find an enrichment factor (δ34S) of 8.7 ± 0.4‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

  13. An isotope view on ionising radiation as a source of sulphuric acid

    NASA Astrophysics Data System (ADS)

    Enghoff, M. B.; Bork, N.; Hattori, S.; Meusinger, C.; Nakagawa, M.; Pedersen, J. O. P.; Danielache, S.; Ueno, Y.; Johnson, M. S.; Yoshida, N.; Svensmark, H.

    2012-02-01

    Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find a δ34S value of 8.7 ± 0.4‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

  14. An isotopic view of ionising radiation as a source of sulphuric acid

    NASA Astrophysics Data System (ADS)

    Enghoff, M. B.; Bork, N.; Hattori, S.; Meusinger, C.; Nakagawa, M.; Pedersen, J. O. P.; Danielache, S. O.; Ueno, Y.; Johnson, M. S.; Yoshida, N.; Svensmark, H.

    2012-04-01

    Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism remains undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find a d34S value of 8.7 ± 0.4 ‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

  15. Chemical residues in Dolphins from the US Atlantic coast including atlantic bottlenose obtained during the 1987/88 mass mortality

    SciTech Connect

    Kuehl, D.W.; Haebler, R.; Potter, C.

    1991-01-01

    Bottlenose dolphins (Tursiops truncatus) collected during the 1987/88 mass mortality event along the Atlantic coast of the United States have been analyzed for anthropogenic chemical contaminants. Average contaminant concentrations in adult males were higher than the average concentrations measured in adult females. Females could be divided into two groups by contaminant concentrations, one with low concentrations, and another with concentrations 4.4 times (PCBs) to 8.9 times (p,p'-DDE) greater. Contaminant concentrations in bottlenose were generally greater than the concentrations measured in either common (Delphinus delphis) or white-sided (Lagernorhynchus acutus) dolphins from the western North Atlantic Ocean. A subset of animals screened for unusual chemical contaminants showed that numerous polybrominated chemicals were present, including polybrominated biphenyls and diphenyl ethers not previously found in marine mammals from U.S. coastal waters.

  16. The advancement of chemical cross-linking and mass spectrometry for structural proteomics: from single proteins to protein interaction networks.

    PubMed

    Sinz, Andrea

    2014-12-01

    During the last 15 years, chemical cross-linking combined with mass spectrometry (MS) and computational modeling has advanced from investigating 3D-structures of isolated proteins to deciphering protein interaction networks. In this article, the author discusses the advent, the development and the current status of the chemical cross-linking/MS strategy in the context of recent technological developments. A direct way to probe in vivo protein-protein interactions is by site-specific incorporation of genetically encoded photo-reactive amino acids or by non-directed incorporation of photo-reactive amino acids. As the chemical cross-linking/MS approach allows the capture of transient and weak interactions, it has the potential to become a routine technique for unraveling protein interaction networks in their natural cellular environment.

  17. Chemical attraction of Dermacentor variabilis ticks parasitic to Peromyscus leucopus based on host body mass and sex.

    PubMed

    Dallas, Tad; Foré, Stephanie

    2013-10-01

    Macroparasites are commonly aggregated on a small subset of a host population. Previous explanations for this aggregation relate to differences in immunocompetence or the degree to which hosts encounter parasites. We propose active tick host choice through chemical attraction as a potential mechanism leading to aggregated tick burdens. We test this hypothesis using a Y-maze olfactometer, comparing chemical attraction responses of larval and nymphal Dermacentor variabilis ticks parasitic to the white-footed mouse, Peromyscus leucopus, as a function of host sex and host body mass. We hypothesized that larger hosts and male hosts would be most attractive to searching ticks, as these hosts commonly have higher tick burdens in the field. Chemical attraction trials were run in the presence and absence of a known tick attractant, host-produced carbon dioxide (CO2). Male hosts and larger hosts were preferred by nymphal D. variabilis in the presence and absence of CO2, whereas larvae had no detectable host preference. The current study suggests that host-produced chemical cues may promote aggregated tick burdens among hosts of a single species based on host body mass and sex. PMID:23543274

  18. Chemical attraction of Dermacentor variabilis ticks parasitic to Peromyscus leucopus based on host body mass and sex.

    PubMed

    Dallas, Tad; Foré, Stephanie

    2013-10-01

    Macroparasites are commonly aggregated on a small subset of a host population. Previous explanations for this aggregation relate to differences in immunocompetence or the degree to which hosts encounter parasites. We propose active tick host choice through chemical attraction as a potential mechanism leading to aggregated tick burdens. We test this hypothesis using a Y-maze olfactometer, comparing chemical attraction responses of larval and nymphal Dermacentor variabilis ticks parasitic to the white-footed mouse, Peromyscus leucopus, as a function of host sex and host body mass. We hypothesized that larger hosts and male hosts would be most attractive to searching ticks, as these hosts commonly have higher tick burdens in the field. Chemical attraction trials were run in the presence and absence of a known tick attractant, host-produced carbon dioxide (CO2). Male hosts and larger hosts were preferred by nymphal D. variabilis in the presence and absence of CO2, whereas larvae had no detectable host preference. The current study suggests that host-produced chemical cues may promote aggregated tick burdens among hosts of a single species based on host body mass and sex.

  19. APOGEE Chemical Tagging Constraint on the Maximum Star Cluster Mass in the Alpha-enhanced Galactic Disk

    NASA Astrophysics Data System (ADS)

    Ting, Yuan-Sen; Conroy, Charlie; Rix, Hans-Walter

    2016-01-01

    Stars born from the same molecular cloud should be nearly homogeneous in their element abundances. The concept of chemical tagging is to identify members of disrupted clusters by their clustering in element abundance space. Chemical tagging requires large samples of stars with precise abundances for many individual elements. With uncertainties of {σ }[X/{{Fe}]} and {σ }[{Fe/{{H}}]}≃ 0.05 for 10 elements measured for \\gt {10}4 stars, the APOGEE DR12 spectra may be the first well-suited data set to put this idea into practice. We find that even APOGEE data offer only ∼500 independent volume elements in the 10-dimensional abundance space, when we focus on the α-enhanced Galactic disk. We develop and apply a new algorithm to search for chemically homogeneous sets of stars against a dominant background. By injecting star clusters into the APOGEE data set, we show that chemically homogeneous clusters with masses ≳ 3× {10}7 {M}ȯ would be easily detectable and yet no such signal is seen in the data. By generalizing this approach, we put a first abundance-based constraint on the cluster mass function for the old disk stars in the Milky Way.

  20. Ionisation Equilibrium for the Non-Maxwellian Electron n-Distributions in Solar Flares: Updated Calculations

    NASA Astrophysics Data System (ADS)

    Dzifčáková, Elena; Dudík, Jaroslav

    2015-12-01

    We use the latest available atomic data to calculate the ionisation and recombination rates for the non-Maxwellian n-distributions, which were shown previously to provide a good fit to the enhanced intensities of dielectronic satellite lines during solar flares. The ionisation and recombination coefficients are subsequently used to derive the ionisation equilibrium. To do so, we consider odd values of n ranging from 1 to 19, i.e., from Maxwellian to strongly non-Maxwellian cases. These calculations involve all elements with proton number up to 30, i.e., H to Zn. The n-distributions modify both the ionisation and the recombination rates. The ionisation rates decrease more steeply at lower pseudo-temperatures, while the radiative recombination rate is reduced due to a lower number of low-energy electrons. The peaks of the dielectronic recombination rates become narrower. These changes are reflected in the ionisation equilibrium. Ion abundance peaks become narrower and can also be shifted, mostly towards higher temperatures. The He-like ions are an important exception, as they are formed in a larger temperature range than that for the Maxwellian distribution. The ions Si xiii - xiv used previously for the diagnostics of the n-distributions are affected only weakly, confirming the determination of n. The ionisation equilibria are available as the electronic supplementary material in a format compatible with the CHIANTI database.

  1. Electron-impact excited term ionisation along the Boron isonuclear sequence

    NASA Astrophysics Data System (ADS)

    Ballance, C. P.; Lee, T.; Ludlow, J. A.; Loch, S. D.; Pindzola, M. S.

    2010-03-01

    Non-perturbative theoretical methods over the last decade have mainly focused on electron-impact ionization of the ground and first metastable states for light fusion related species [1]. However, collisional-radiative models predict that effective ionisation rates, which include the ionisation from excited levels of an atom, can be an order of magnitude greater greater than those which include the groundstate alone. For example, this stepwise ionisation has been experimentally confirmed by measurements taken at the DIII-D facility as part of a Li transport study, where excited state ionisation was found to be essential in describing Li transport [2]. We shall present in our poster an overview of excited state ionisation along the boron ionisation sequence. Using boron as a test case, we focus on the most appropriate use of computationally non-perturbative methods and simpler non-pertubative/semi-empirical methods to account for excited ionisation along other iso-nuclear sequences.[4pt] [1] Griffin D C and Pindzola M S, Adv. Atm. Mol. Opt. Phys. 54, 203 (2006)[0pt] [2] Allain J P, Whyte D G and Brooks J N, Nucl. Fusion 44 655 (2004)

  2. Differentiation of human kidney stones induced by melamine and uric acid using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Jia, Bin; Ouyang, Yongzhong; Sodhi, Rana N S; Hu, Bin; Zhang, Tingting; Li, Jianqiang; Chen, Huanwen

    2011-03-01

    Clinically obtained human kidney stones of different pathogenesis were dissolved in acetic acid/methanol solutions and then rapidly analyzed by surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without any desalination treatment. The mass spectral fingerprints of six groups of kidney stone samples were rapidly recorded in the mass range of m/z 50-400. A set of ten melamine-induced kidney stone samples and nine uric acid derived kidney stone samples were successfully differentiated from other groups by principal component analysis of SDAPCI-MS fingerprints upon positive-ion detection mode. In contrast, the mass spectra recorded using negative-ion detection mode did not give enough information to differentiate those stone samples. The results showed that in addition to the melamine, the chemical compounds enwrapped in the melamine-induced kidney stone samples differed from other kidney stone samples, providing useful hints for studying on the formation mechanisms of melamine-induced kidney stones. This study also provides useful information on establishing a MS-based platform for rapid analysis of the melamine-induced human kidney stones at molecular levels.

  3. Anabolic implant effects on visceral organ mass, chemical body composition, and estimated energetic efficiency in cloned (genetically identical) beef steers.

    PubMed

    Hutcheson, J P; Johnson, D E; Gerken, C L; Morgan, J B; Tatum, J D

    1997-10-01

    Six sets of four genetically identical Brangus steers (n = 24; X BW 409 kg) were used to determine the effect of different anabolic implants on visceral organ mass, chemical body composition, estimated tissue deposition, and energetic efficiency. Steers within a clone set were randomly assigned to one of the following implant treatments: C, no implant; E, estrogenic; A, androgenic, or AE, androgenic + estrogenic. Steers were slaughtered 112 d after implanting; visceral organs were weighed and final body composition determined by mechanical grinding and chemical analysis of the empty body. Mass of the empty gastrointestinal tract (GIT) was reduced approximately 9% (P < .10) in steers implanted with estrogen alone or in combination with an androgen. Liver mass was increased (P < .10) from 6 to 14% by implants. Steers implanted with the AE combination had greater (P < .10) daily protein accretion (163.4 g/d) than either E (128.8 g/d) or A (137.1 g/d), and, because the combination improved gain above C (101.1 g/d), this demonstrates the additive effects of a combination implant on protein deposition. Anabolic implants did not alter (P > .10) the efficiency of ME utilization. In general, estrogenic implants decreased GIT, androgenic implants increased liver, and all implants increased hide mass. Steers implanted with an AE combination had additive effects on protein deposition compared with either implant alone. The NEg requirements for body gain are estimated to be reduced 19% by estrogenic or combination implants. PMID:9331863

  4. Optimized electron-optical system of a static mass-spectrometer for simultaneous isotopic and chemical analysis

    NASA Astrophysics Data System (ADS)

    Gall', L. N.; Masyukevich, S. V.; Sachenko, V. D.; Gall', N. R.

    2016-01-01

    A new approach to control the linear dimensions of analytical electrophysical systems is suggested. This approach uses the lens properties of electron-optical elements with a curvilinear axis. It is shown that such an approach can be effectively applied, in particular, to synthesize ion-optical systems (IOSs) for static magnetic mass spectrometers and can be implemented owing to off-axis fundamental points, the "poles" of an electron-optical system, introduced earlier by one of the authors. The capabilities of the new approach are demonstrated with the synthesis of the IOS of a static mass spectrometer dedicated for isotopic and chemical analysis with an increased resolution. A new IOS not only provides desired high ion-optical parameters at decreased dimensions of the mass spectrometer as a whole but also makes it possible to loosen requirements for the manufacturing accuracy of IOS main elements.

  5. Biological and chemical weapons of mass destruction: updated clinical therapeutic countermeasures since 2003.

    PubMed

    Pettineo, Christopher; Aitchison, Robert; Leikin, Scott M; Vogel, Stephen N; Leikin, Jerrold B

    2009-01-01

    The objective of this article is to provide updated treatment options for bioterrorism agents. This updated synopsis includes recent clinical cases and treatment recommendations that have arisen in the last 5 years. The decontamination, treatment, and disposition of these biologic and chemical agents are presented alphabetically by agent type: biologic, chemical, and radiologic/nuclear. The information provided outlines only new treatment options since 2003.

  6. Detection of nerve agents using proton transfer reaction mass spectrometry with ammonia as reagent gas.

    PubMed

    Ringer, Joachim M

    2013-01-01

    The chemical warfare agents (CWA) Sarin, Soman, Cyclosarin and Tabun were characterised by proton transfer mass spectrometry (PTRMS). It was found that PTRMS is a suitable technique to detect nerve agents highly sensitively, highly selectively and in near real-time. Methods were found to suppress molecule fragmentation which is significant under PTRMS hollow cathode ionisation conditions. In this context, the drift voltage (as one of the most important system parameters) was varied and ammonia was introduced as an additional chemical reagent gas. Auxiliary chemicals such as ammonia affect ionisation processes and are quite common in context with detectors for CWAs based on ion mobility spectrometry (IMS). With both, variation of drift voltage and ammonia as the reagent gas, fragmentation can be suppressed effectively. Suppression of fragmentation is crucial particularly concerning the implementation of an algorithm for automated agent identification in field applications. On the other hand, appearance of particular fragments might deliver additional information. Degradation and rearrangement products of nerve agents are not distinctive for the particular agent but for the chemical class they belong to. It was found that switching between ammonia doped and ordinary water ionisation chemistry can easily be performed within a few seconds. Making use of this effect it is possible to switch between fragment and molecular ion peak spectra. Thus, targeted fragmentation can be used to confirm identification based only on single peak detection. PTRMS turned out to be a promising technique for future CWA detectors. In terms of sensitivity, response time and selectivity (or confidence of identification, respectively) PTRMS performs as a bridging technique between IMS and GC-MS.

  7. Detection of nerve agents using proton transfer reaction mass spectrometry with ammonia as reagent gas.

    PubMed

    Ringer, Joachim M

    2013-01-01

    The chemical warfare agents (CWA) Sarin, Soman, Cyclosarin and Tabun were characterised by proton transfer mass spectrometry (PTRMS). It was found that PTRMS is a suitable technique to detect nerve agents highly sensitively, highly selectively and in near real-time. Methods were found to suppress molecule fragmentation which is significant under PTRMS hollow cathode ionisation conditions. In this context, the drift voltage (as one of the most important system parameters) was varied and ammonia was introduced as an additional chemical reagent gas. Auxiliary chemicals such as ammonia affect ionisation processes and are quite common in context with detectors for CWAs based on ion mobility spectrometry (IMS). With both, variation of drift voltage and ammonia as the reagent gas, fragmentation can be suppressed effectively. Suppression of fragmentation is crucial particularly concerning the implementation of an algorithm for automated agent identification in field applications. On the other hand, appearance of particular fragments might deliver additional information. Degradation and rearrangement products of nerve agents are not distinctive for the particular agent but for the chemical class they belong to. It was found that switching between ammonia doped and ordinary water ionisation chemistry can easily be performed within a few seconds. Making use of this effect it is possible to switch between fragment and molecular ion peak spectra. Thus, targeted fragmentation can be used to confirm identification based only on single peak detection. PTRMS turned out to be a promising technique for future CWA detectors. In terms of sensitivity, response time and selectivity (or confidence of identification, respectively) PTRMS performs as a bridging technique between IMS and GC-MS. PMID:24308198

  8. Chemical Composition of Latent Fingerprints by Gas Chromatography-Mass Spectrometry

    ERIC Educational Resources Information Center

    Hartzell-Baguley, Brittany; Hipp, Rachael E.; Morgan, Neal R.; Morgan, Stephen L.

    2007-01-01

    An experiment in which gas chromatography-mass spectrometry (GC-MS) is used for latent fingerprint extraction and analysis on glass beads or glass slides is conducted. The results determine that the fingerprint residues are gender dependent.

  9. The near field/far field model with constant application of chemical mass and exponentially decreasing emission of the mass applied.

    PubMed

    Nicas, Mark

    2016-07-01

    The near field/far field (NF/FF) model is a contaminant dispersion construct that permits making airborne contaminant exposure estimates for an individual located close to an emission source. In the present analysis, chemical emission involves a constant mass rate of chemical application to surfaces, denoted I (mg/min), and an exponentially decreasing rate of emission of the chemical from the surfaces with rate constant α (min(-1)). The time-dependent emission rate function is: G(t), mg/min = I - I exp(- αt), where time t is in minutes. The exact time-dependent equations for the contaminant concentration in the NF and the FF are presented. These equations are used to revise a previous analysis of a study in which a penetrant liquid containing benzene was applied to parts on a work table in a test room. The previous analysis assumed that the benzene was applied as a bolus at the start of a 15-min use period, whereas the present analysis assumes the same total benzene mass was applied at a uniform rate over the 15-min use period, but with the same evaporation rate constant α. The new G(t) function leads to a lower 15-min time weighted average NF benzene concentration that better matches the experimental data. It is also shown that the exact equation for the NF concentration is well approximated by combining two well-mixed single-zone equations. The approximation method is mathematically simpler and obviates the need to derive the exact NF equation. PMID:26861562

  10. The Chemical Exhaust Hazards of Dichlorosilane Deposits Determined with FT-ICR Mass Spectrometry

    SciTech Connect

    JAREK, RUSSELL L.; THORNBERG, STEVEN M.

    1999-10-01

    Flammable deposits have been analyzed from the exhaust systems of tools employing dichlorosilane (DCS) as a processing gas. Exact mass determinations with a high-resolution Fourier-transform ion-cyclotron resonance (FT-ICR) mass spectrometer allowed the identification of various polysiloxane species present in such an exhaust flow. Ion-molecule reactions indicate the preferred reaction pathway of siloxane formation is through HCl loss, leading to the highly reactive polysiloxane that was detected in the flammable deposits.

  11. Chemical modification of proteins to improve the accuracy of their relative molecular mass determination by electrophoresis.

    PubMed

    Dolnik, Vladislav; Gurske, William A

    2011-10-01

    We studied the electrophoretic behavior of basic proteins (cytochrome c and histone III) and developed a carbamylation method that normalizes their electrophoretic size separation and improves the accuracy of their relative molecular mass determined electrophoretically. In capillary zone electrophoresis with cationic hitchhiking, native cytochrome c does not sufficiently bind cationic surfactants due to electrostatic repulsion between the basic protein and cationic surfactant. Carbamylation suppresses the strong positive charge of the basic proteins and results in more accurate relative molecular masses.

  12. Plant seed species identification from chemical fingerprints: a high-throughput application of direct analysis in real time mass spectrometry.

    PubMed

    Lesiak, Ashton D; Cody, Robert B; Dane, A John; Musah, Rabi A

    2015-09-01

    Plant species identification based on the morphological features of plant parts is a well-established science in botany. However, species identification from seeds has largely been unexplored, despite the fact that the seeds contain all of the genetic information that distinguishes one plant from another. Using seeds of genus Datura plants, we show here that the mass spectrum-derived chemical fingerprints for seeds of the same species are similar. On the other hand, seeds from different species within the same genus display distinct chemical signatures, even though they may contain similar characteristic biomarkers. The intraspecies chemical signature similarities on the one hand, and interspecies fingerprint differences on the other, can be processed by multivariate statistical analysis methods to enable rapid species-level identification and differentiation. The chemical fingerprints can be acquired rapidly and in a high-throughput manner by direct analysis in real time mass spectrometry (DART-MS) analysis of the seeds in their native form, without use of a solvent extract. Importantly, knowledge of the identity of the detected molecules is not required for species level identification. However, confirmation of the presence within the seeds of various characteristic tropane and other alkaloids, including atropine, scopolamine, scopoline, tropine, tropinone, and tyramine, was accomplished by comparison of the in-source collision-induced dissociation (CID) fragmentation patterns of authentic standards, to the fragmentation patterns observed in the seeds when analyzed under similar in-source CID conditions. The advantages, applications, and implications of the chemometric processing of DART-MS derived seed chemical signatures for species level identification and differentiation are discussed.

  13. Resonant laser ablation ion trap mass spectrometry -- Recent applications for chemical analysis

    SciTech Connect

    Gill, C.G.; Garrett, A.W.; Hemberger, P.H.; Nogar, N.S.

    1995-12-31

    Resonant Laser Ablation (RLA) is a useful ionization process for selectively producing gas phase ions from a solid sample. Recent use of RLA for mass spectrometry by this group and by others has produced a wealth of knowledge and useful analytical techniques. The method relies upon the focusing of modest intensity laser pulses ({le} 10{sup 7} W {center_dot} Cm{sup {minus}2}) upon a sample surface. A small quantity of material is vaporized, and atoms of desired analyte are subsequently ionized by (n + m) photon processes in the gas phase (where n = number of photons to a resonant transition and m = number of photons to exceed the ionization limit). The authors have been using (2 + 1) resonant ionization schemes for this work. Quadrupole ion trap mass spectrometry is realizing a very prominent role in current mass spectrometric research. Ion traps are versatile, powerful and extremely sensitive mass spectrometers, capable of a variety of ionization modes, MS{sup n} type experiments, high mass ranges and high resolution, all for a fraction of the cost of other instrumentation with similar capabilities. Quadrupole ion traps are ideally suited to pulsed ionization sources such as laser ionization methods, since their normal operational method (Mass Selective Instability) relies upon the storage of ions from a finite ionization period followed by ejection and detection of these ions based upon their mass to charge ratios. The paper describes selective ionization for trace atomic analysis, selective reagent ion source for ion chemistry investigations, and the analysis of ``difficult`` environmental contaminants, i.e., TBP.

  14. Spatial and Temporal Variation in Fine Particulate Matter Mass and Chemical Composition: The Middle East Consortium for Aerosol Research Study

    PubMed Central

    Abdeen, Ziad; Heo, Jongbae; Wu, Bo; Shpund, Jacob; Vanger, Arye; Sharf, Geula; Moise, Tamar; Brenner, Shmuel; Nassar, Khaled; Saleh, Rami; Al-Mahasneh, Qusai M.; Sarnat, Jeremy A.; Schauer, James J.

    2014-01-01

    Ambient fine particulate matter (PM2.5) samples were collected from January to December 2007 to investigate the sources and chemical speciation in Palestine, Jordan, and Israel. The 24-h PM2.5 samples were collected on 6-day intervals at eleven urban and rural sites simultaneously. Major chemical components including metals, ions, and organic and elemental carbon were analyzed. The mass concentrations of PM2.5 across the 11 sites varied from 20.6 to 40.3 μg/m3, with an average of 28.7 μg/m3. Seasonal variation of PM2.5 concentrations was substantial, with higher average concentrations (37.3 μg/m3) in the summer (April–June) months compared to winter (October–December) months (26.0 μg/m3) due mainly to high contributions of sulfate and crustal components. PM2.5 concentrations in the spring were greatly impacted by regional dust storms. Carbonaceous mass was the most abundant component, contributing 40% to the total PM2.5 mass averaged across the eleven sites. Crustal components averaged 19.1% of the PM2.5 mass and sulfate, ammonium, and nitrate accounted for 16.2%, 6.4%, and 3.7%, respectively, of the total PM2.5 mass. The results of this study demonstrate the need to better protect the health and welfare of the residents on both sides of the Jordan River in the Middle East. PMID:25045751

  15. Chemical constituents of essential oils from the leaves and stem barks of four Vietnamese species of Fissistigma (Annonaceae).

    PubMed

    Thang, Tran D; Luu, Hoang V; Dung, Vo C; Tuan, Nguyen N; Hung, Nguyen H; Dai, Do N; Ogunwande, Isiaka A

    2014-01-01

    Chemical profiles of essential oils from four Fissistigma species: Fissistigma bracteolatum Chatt., Fissistigma villosissimum Merr., Fissistigma latifolium (Dunal) Merr. and Fissistigma glaucescens (Hance) Merr. were analysed by gas chromatography-flame ionisation detector and gas chromatography-mass spectrometry. Fissistigma essential oils consist mainly of sesquiterpenes (48.7-83.8%), monoterpenes (3.2-30.9%) and fatty acids (0.5-33.4%). Data on the essential oil composition of F. villosissimum, F. latifolium and F. glaucescens are reported for the first time.

  16. Mass Conservation in a Chemical Transport Model and its Effect on CO2 and SF6 Simulations

    NASA Technical Reports Server (NTRS)

    Zhu, Z.; Weaver, C.; Kawa, S. R.; Douglass, A. R.; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    Chemical transport models (CTMs) must conserve mass to be useful for applications involving assessment of the effect of various pollutants on the troposphere and stratosphere. Furthermore, calculations of the evolution of constituents such as SF6 are used to evaluate overall model transport, and interpretation of such simulations is clouded if mass conservation is not assured. For realistic simulations or predictions, it is crucial that constituents are not produced or lost by transport or other processes in the CTMs. Analysis of CO2 and SF6 experiments using a CTM shows that problems with mass conservation can seriously degrade the simulations. Failure to conserve mass results from inconsistency of the surface pressure tendency and the divergence of horizontal mass flux when the model is forced by assimilated meteorological data. We have developed an effective method to eliminate the inconsistency by modifying the divergent part of the wind field. The changes in the wind fields are quite small but the impact on mass conservation is large. Parameterizations of physical processes such as convection or turbulent transport can also affect mass conservation. The lack of conservation is small but accumulates when integrations are lengthy such as required for SF6. This lack of conservation is found using winds from either a GCM or from an assimilation system. A simple adjustment removes much of the inaccuracy in the convective parameterization. A CO2 simulation using assimilated winds from the most recent version of the Goddard Earth Observing System Data Assimilation System will be used to illustrate the impact of these transport improvements.

  17. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ.

  18. Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry.

    PubMed

    Pozzi, Romina; Bocchini, Paola; Pinelli, Francesca; Galletti, Guido C

    2011-04-01

    A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen.

  19. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ. PMID:27098411

  20. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

  1. The chemical evolution of a travertine-depositing stream: geochemical processes and mass transfer reactions

    USGS Publications Warehouse

    Lorah, M.M.; Herman, J.S.

    1988-01-01

    Focuses on quantiatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virgina. The processes of CO2 outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall. -from Authors

  2. DNAPL mass transfer and permeability reduction during in situ chemical oxidation with permanganate

    NASA Astrophysics Data System (ADS)

    Li, X. David; Schwartz, Franklin W.

    2004-03-01

    This study utilized a series of laboratory experiments to examine the DNAPL mass removal rate and permeability reduction during ISCO using permanganate (MnO4-). Results show that MnO4- oxidation is effective in removing residual DNAPL from a porous medium. The DNAPL mass removal rate correlated positively with both the hydraulic stress and the oxidant load. A power relationship model of DNAPL mass removal under ISCO was proposed. Results also show that oxidation by-products CO2(g) and Mn oxide can cause pore plugging and flow by-passing. The reduction in hydraulic conductivity due to the Mn oxide precipitates was quantified. Hydraulic conductivity reduction as high as 80% was observed for oxidizing a small quantity of TCE.

  3. Rapid Semi-Quantitative Surface Mapping of Airborne-Dispersed Chemicals Using Mass Spectrometry

    EPA Science Inventory

    Chemicals can be dispersed accidentally, deliberately, or by weather-related events. Rapid mapping of contaminant distributions is necessary to assess exposure risks and to plan remediation, when needed. Ten pulverized aspirin or NoDozTM tablets containing caffeine wer...

  4. Current issues involving screening and identification of chemical contaminants in foods by mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although quantitative analytical methods must be empirically validated prior to their actual use in a variety of applications, including regulatory monitoring of chemical adulterants in foods, validation of qualitative method performance for the analytes and matrices of interest is frequently ignore...

  5. Characterization of Nitrogen-Containing Species in Coal and Petroleum-Derived Products by Ammonia Chemical Ionization-High Resolution Mass Spectrometry

    SciTech Connect

    Veloski, Garret A.; Lynn, Ronald J.; Sprecher, Richard F.

    1997-01-01

    A coal-derived light distillate and a petroleum-derived residuum have been studied by high resolution mass spectrometry using both low-pressure ammonia chemical ionization and low-voltage electron impact ionization. A mass calibration mixture for use with ammonia chemical ionization has been developed. Selective ionization of the basic nitrogen-containing compounds by ammonia chemical ionization and compound type characterization of the resulting quasi-molecular species has been demonstrated. Several homologous series of nitrogen-containing compounds were identified in a basic extract by electron impact ionization and compared with quasimolecular analogs identified by ammonia chemical ionization.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  7. Evaluation of chemical labeling methods for identifying functional arginine residues of proteins by mass spectrometry.

    PubMed

    Wanigasekara, Maheshika S K; Chowdhury, Saiful M

    2016-09-01

    Arginine residues undergo several kinds of post-translational modifications (PTMs). These PTMs are associated with several inflammatory diseases, such as rheumatoid arthritis, atherosclerosis, and diabetes. Mass spectrometric studies of arginine modified proteins and peptides are very important, not only to identify the reactive arginine residues but also to understand the tandem mass spectrometry behavior of these peptides for assigning the sequences unambiguously. Herein, we utilize tandem mass spectrometry to report the performance of two widely used arginine labeling reagents, 1,2-cyclohexanedione (CHD) and phenylglyoxal (PG) with several arginine containing peptides and proteins. Time course labeling studies were performed to demonstrate the selectivity of the reagents in proteins or protein digests. Structural studies on the proteins were also explored to better understand the reaction sites and position of arginine residues. We found CHD showed better labeling efficiencies compared to phenylglyoxal. Reactive arginine profiling on a purified albumin protein clearly pointed out the cellular glycation modification site for this protein with high confidence. We believe these detailed mass-spectrometric studies will provide significant input to profile reactive arginine residues in large-scale studies; therefore, targeted proteomics can be performed to the short listed reactive sites for cellular arginine modifications. PMID:27543028

  8. Growth alteration and leaf biochemical responses in Phaseolus vulgaris exposed to different doses of ionising radiation.

    PubMed

    Arena, C; De Micco, V; De Maio, A

    2014-01-01

    Ionising radiation may have different effects on plant metabolism, growth and reproduction, depending on radiation dose, plant species, developmental stage and physiological traits. In this study, exposure of dwarf bean plants to different doses of X-rays (0.3, 10, 50, 100 Gy) was investigated with a multidisciplinary approach consisting of morphological, ecophysiological and biochemical analysis. Both mature and young leaves still growing during the X-rays exposure were compared with non-irradiated control leaves. In particular, leaf expansion, leaf anatomy and functional traits, as well as photosynthetic pigment content and Rubisco expression were analysed. Moreover, the activity of poly(ADP-ribose) polymerase (PARP) was also measured as an indicator of radiation-induced DNA damage. Our data showed that leaf growth is affected by high levels of radiation and demonstrate that mature leaves are more radio-resistant than young leaves, which experience severe dose-dependent changes in leaf functional traits. In particular, young leaves exhibited a reduction of area and an increase in specific mass and dry matter content, as well as a decline in Rubisco activity. Moreover, they showed elevated PARP activity and an increase in phenolic compounds in wall cells if compared with mature leaves. Both of these strategies have been interpreted as a way to help developing leaves withstand irradiation.

  9. Unsteady Heat and Mass Transfer of Chemically Reacting Micropolar Fluid in a Porous Channel with Hall and Ion Slip Currents

    PubMed Central

    2014-01-01

    This paper presents an incompressible two-dimensional heat and mass transfer of an electrically conducting micropolar fluid flow in a porous medium between two parallel plates with chemical reaction, Hall and ion slip effects. Let there be periodic injection or suction at the lower and upper plates and the nonuniform temperature and concentration at the plates are varying periodically with time. The flow field equations are reduced to nonlinear ordinary differential equations using similarity transformations and then solved numerically by quasilinearization technique. The profiles of velocity components, microrotation, temperature distribution and concentration are studied for different values of fluid and geometric parameters such as Hartmann number, Hall and ion slip parameters, inverse Darcy parameter, Prandtl number, Schmidt number, and chemical reaction rate and shown in the form of graphs. PMID:27419211

  10. QCD equation of state at nonzero chemical potential: continuum results with physical quark masses at order μ 2

    NASA Astrophysics Data System (ADS)

    Borsányi, Sz.; Endrődi, G.; Fodor, Z.; Katz, S. D.; Krieg, S.; Ratti, C.; Szabó, K. K.

    2012-08-01

    We determine the equation of state of QCD for nonzero chemical potentials via a Taylor expansion of the pressure. The results are obtained for N f = 2 + 1 flavors of quarks with physical masses, on various lattice spacings. We present results for the pressure, interaction measure, energy density, entropy density, and the speed of sound for small chemical potentials. At low temperatures we compare our results with the Hadron Resonance Gas model. We also express our observables along trajectories of constant entropy over particle number. A simple parameterization is given (the Matlab/Octave script parameterization.m, submitted to the arXiv along with the paper), which can be used to reconstruct the observables as functions of T and μ, or as functions of T and S/N.

  11. In situ measurements of atmospheric nitrous acid by chemical ionization mass spectrometry using chloride ion transfer reactions.

    PubMed

    Hirokawa, Jun; Kato, Takehiro; Mafuné, Fumitaka

    2009-10-15

    Recently, chemical ionization mass spectrometry (CIMS) has been widely applied to the in situ measurements of atmospheric trace species. In this article, we propose a new chemical ionization scheme using a chloride ion transfer reaction from SO(2)Cl(-) as the reagent ion and discuss the applicability of this technique to the detection of nitrous acid (HONO) in the atmosphere. From laboratory investigations, the detection sensitivity was found to depend on the flow rate of SO(2) introduced into the ion source region and the pressure inside the chemical ionization region, which suggests that the chemical ionization reaction is reversible. The detection sensitivity was well described in terms of the forward and backward rates. The present limit of detection is estimated to be 60 parts per trillion by volume (pptv) for an integration time of 1 min. Improvement of the CIMS instrument would enable the measurements of the daytime level of HONO, which might be less than 50 pptv. In addition, the possibility of the interference is discussed from thermodynamic considerations based on ab initio calculations, and the effects of the sampling artifacts are experimentally quantified.

  12. Real-Time Chemical Analysis of E-Cigarette Aerosols By Means Of Secondary Electrospray Ionization Mass Spectrometry.

    PubMed

    García-Gómez, Diego; Gaisl, Thomas; Barrios-Collado, César; Vidal-de-Miguel, Guillermo; Kohler, Malcolm; Zenobi, Renato

    2016-02-12

    Chemical analysis of aerosols collected from electronic cigarettes (ECs) has shown that these devices produce vapors that contain harmful and potentially harmful compounds. Conventional analytical methods used for the analysis of electronic cigarettes do not reflect the actual composition of the aerosols generated because they usually neglect the changes in the chemical composition that occur during the aerosol generation process and after collection. The aim of this work was to develop and apply a method for the real-time analysis of electronic cigarette aerosols, based on the secondary electrospray ionization technique coupled to high-resolution mass spectrometry, by mimicking the "vaping" process. Electronic cigarette aerosols were successfully analyzed and quantitative differences were found between the liquids and aerosols. Thanks to the high sensitivity shown by this method, more than 250 chemical substances were detected in the aerosols, some of them showing a high correlation with the operating power of the electronic cigarettes. The method also allows proper quantification of several chemical components such as alkaloids and flavor compounds.

  13. Chemical Composition of Micrometer-Sized Filaments in an Aragonite Host by a Miniature Laser Ablation/Ionization Mass Spectrometer.

    PubMed

    Tulej, Marek; Neubeck, Anna; Ivarsson, Magnus; Riedo, Andreas; Neuland, Maike B; Meyer, Stefan; Wurz, Peter

    2015-08-01

    Detection of extraterrestrial life is an ongoing goal in space exploration, and there is a need for advanced instruments and methods for the detection of signatures of life based on chemical and isotopic composition. Here, we present the first investigation of chemical composition of putative microfossils in natural samples using a miniature laser ablation/ionization time-of-flight mass spectrometer (LMS). The studies were conducted with high lateral (∼15 μm) and vertical (∼20-200 nm) resolution. The primary aim of the study was to investigate the instrument performance on micrometer-sized samples both in terms of isotope abundance and element composition. The following objectives had to be achieved: (1) Consider the detection and calculation of single stable isotope ratios in natural rock samples with techniques compatible with their employment of space instrumentation for biomarker detection in future planetary missions. (2) Achieve a highly accurate chemical compositional map of rock samples with embedded structures at the micrometer scale in which the rock matrix is easily distinguished from the micrometer structures. Our results indicate that chemical mapping of strongly heterogeneous rock samples can be obtained with a high accuracy, whereas the requirements for isotope ratios need to be improved to reach sufficiently large signal-to-noise ratio (SNR).

  14. Chemical Composition of Micrometer-Sized Filaments in an Aragonite Host by a Miniature Laser Ablation/Ionization Mass Spectrometer.

    PubMed

    Tulej, Marek; Neubeck, Anna; Ivarsson, Magnus; Riedo, Andreas; Neuland, Maike B; Meyer, Stefan; Wurz, Peter

    2015-08-01

    Detection of extraterrestrial life is an ongoing goal in space exploration, and there is a need for advanced instruments and methods for the detection of signatures of life based on chemical and isotopic composition. Here, we present the first investigation of chemical composition of putative microfossils in natural samples using a miniature laser ablation/ionization time-of-flight mass spectrometer (LMS). The studies were conducted with high lateral (∼15 μm) and vertical (∼20-200 nm) resolution. The primary aim of the study was to investigate the instrument performance on micrometer-sized samples both in terms of isotope abundance and element composition. The following objectives had to be achieved: (1) Consider the detection and calculation of single stable isotope ratios in natural rock samples with techniques compatible with their employment of space instrumentation for biomarker detection in future planetary missions. (2) Achieve a highly accurate chemical compositional map of rock samples with embedded structures at the micrometer scale in which the rock matrix is easily distinguished from the micrometer structures. Our results indicate that chemical mapping of strongly heterogeneous rock samples can be obtained with a high accuracy, whereas the requirements for isotope ratios need to be improved to reach sufficiently large signal-to-noise ratio (SNR). PMID:26247475

  15. In situ measurements of atmospheric nitrous acid by chemical ionization mass spectrometry using chloride ion transfer reactions.

    PubMed

    Hirokawa, Jun; Kato, Takehiro; Mafuné, Fumitaka

    2009-10-15

    Recently, chemical ionization mass spectrometry (CIMS) has been widely applied to the in situ measurements of atmospheric trace species. In this article, we propose a new chemical ionization scheme using a chloride ion transfer reaction from SO(2)Cl(-) as the reagent ion and discuss the applicability of this technique to the detection of nitrous acid (HONO) in the atmosphere. From laboratory investigations, the detection sensitivity was found to depend on the flow rate of SO(2) introduced into the ion source region and the pressure inside the chemical ionization region, which suggests that the chemical ionization reaction is reversible. The detection sensitivity was well described in terms of the forward and backward rates. The present limit of detection is estimated to be 60 parts per trillion by volume (pptv) for an integration time of 1 min. Improvement of the CIMS instrument would enable the measurements of the daytime level of HONO, which might be less than 50 pptv. In addition, the possibility of the interference is discussed from thermodynamic considerations based on ab initio calculations, and the effects of the sampling artifacts are experimentally quantified. PMID:19746928

  16. Combined Chemical and Topographic Imaging at Atmospheric Pressure via Microprobe Laser Desorption/Ionization Mass Spectrometry-Atomic Force Microscopy

    SciTech Connect

    Bradshaw, James A; Ovchinnikova, Olga S; Meyer, Kent A; Goeringer, Doug

    2009-01-01

    The operational characteristics and imaging performance are described for a new instrument comprising an atomic force microscope (AFM) coupled with a pulsed laser and a linear ion trap mass spectrometer. The AFM operating mode is used to produce topographic surface images having nanometer-scale spatial and height resolution. Spatially resolved mass spectra of ions, produced from the same surface via microprobe-mode laser desorption/ionization at atmospheric pressure, are then used to create a 100 x 100 m chemical image. The effective spatial resolution of the image (~2 m) was constrained by the limit of detection (estimated to be 109 1010 ions) rather than by the diameter of the focused laser spot or the step size of the AFM sample stage. Thus, it is expected that improvements in imaging performance can be realized by implementation of post-ionization methods.

  17. Quantitative determination of terbutaline and orciprenaline in human plasma by gas chromatography/negative ion chemical ionization/mass spectrometry.

    PubMed

    Leis, H J; Gleispach, H; Nitsche, V; Malle, E

    1990-06-01

    A method for the determination of unconjugated terbutaline and orciprenaline in human plasma is described. The assay is based on stable isotope dilution gas chromatography/negative ion chemical ionization/mass spectrometry. An inexpensive and rapid method for preparation of stable isotope labelled analogues as well as their use in quantitative gas chromatography/mass spectrometry is shown. A highly efficient sample work-up procedure with product recoveries of more than 95% is presented. The method developed permits quantitative measurement of terbutaline and orciprenaline in human plasma down to 100 pg ml-1, using 1 ml of sample. Plasma levels of terbutaline after oral administration of 5 mg of terbutaline sulphate were estimated. PMID:2357489

  18. Chemical composition and mass size distribution of PM1.0 at an elevated site in central east China

    NASA Astrophysics Data System (ADS)

    Zhang, Y. M.; Zhang, X. Y.; Sun, J. Y.; Hu, G. Y.; Shen, X. J.; Wang, Y. Q.; Wang, T. T.; Wang, D. Z.; Zhao, Y.

    2014-06-01

    Size-resolved aerosol chemical compositions were measured continuously for one and half years with an aerosol mass spectrometer (AMS) to characterize the mass and size distributions (MSDs) of each component in bulk, fresh and aged submicron particles (approximately PM1.0) at Mountain Tai, an elevated site in Central East China (CEC) from June 2010 to January 2012. The majority of the regionally-dispersed aerosols were found to be contributed from short distance mixed aerosol, mostly from its south with organics and sulfate as the major components. The annual mean mass concentrations of organics, sulfate, nitrate, ammonium and chloride were 11.2, 9.2, 7.2, 5.8 and 0.95 μg m-3, respectively, which are much lower for organics and sulfate, and slightly lower for nitrate, ammonium and chloride than those at the nearby surface rural sites. High organics were observed for all four seasons, and the relatively fresh organic aerosol (OA) containing high proportion of less-photo chemically OA, were found from long-range transported aerosol from northwest. Semi-volatile and low-volatile oxidized OAs together contributed approximately 49%, 55% in spring and 72% and 51% in winter of total OA, showing at least 50% of OA can be attributable to SOA. Seasonally, the chemical components at the elevated site showed a "winter high and autumn low" pattern, with organics, sulfate and ammonium peaking in summer. Though no obvious differences of MSDs were seen for various chemical components in the planetary boundary layer (PBL) and free troposphere (FT), the concentrations were a factor of 5-7 higher in PBL than in FT. The averaged MSDs of particles between 30-1000 nm for organics, sulfate, nitrate, and ammonium are approximately log-normal with similar mass median diameters (MMDs) of 539, 585, 542, and 545 nm, respectively, which were slightly larger than those in ground sites within North China Plain (NCP). Obvious differences in MMDs were found between fresh and aged aerosols for

  19. Coping with mass destruction: United States power projection in the nuclear and chemical third world. Monograph report

    SciTech Connect

    Cheek, G.H.

    1993-05-14

    This monograph explores the proliferation of weapons of mass destruction in the Third World, their operational impact on power projection forces, and the viability of deterrence in the future. It concludes that the proliferation of weapons of mass destruction may have grave consequences for the power projection forces in the future; simple assumptions of non-use, reliance on our nuclear deterrent or protective measures may give us a false sense of security. Proper analysis of operational vulnerabilities will be essential for future power projection. Proliferation of operational delivery systems and weapons of mass destruction continues despite treaties and the best intentions of world leaders. Weapons of mass destruction are becoming more common throughout the world and chemical and biological weapons continue to become more and more lethal. These trends are creating a multipolar world, which history has shown to be the most unstable. This unstable world will be the environment for future power projection. Deterrence in this environment is without precedent other than the Cold War paradigm. It is questionable whether deterrence will transfer outside this paradigm as Third World nations do not have the experience, balance of power, infrastructure or political stability needed to make the concept viable. Possession of weapons of mass destruction may even allow these nations to deter entry of US power projection forces into certain regions as deterrence is a two way concept. While deterrence is still an essential part of US National Strategy to prevent war, reliance on it to prevent use of weapons of mass destruction in the midst of a conflict may prove to be a false hope.

  20. Dosimetry of ionising radiation in modern radiation oncology

    NASA Astrophysics Data System (ADS)

    Kron, Tomas; Lehmann, Joerg; Greer, Peter B.

    2016-07-01

    Dosimetry of ionising radiation is a well-established and mature branch of physical sciences with many applications in medicine and biology. In particular radiotherapy relies on dosimetry for optimisation of cancer treatment and avoidance of severe toxicity for patients. Several novel developments in radiotherapy have introduced new challenges for dosimetry with small and dynamically changing radiation fields being central to many of these applications such as stereotactic ablative body radiotherapy and intensity modulated radiation therapy. There is also an increasing awareness of low doses given to structures not in the target region and the associated risk of secondary cancer induction. Here accurate dosimetry is important not only for treatment optimisation but also for the generation of data that can inform radiation protection approaches in the future. The article introduces some of the challenges and highlights the interdependence of dosimetric calculations and measurements. Dosimetric concepts are explored in the context of six application fields: reference dosimetry, small fields, low dose out of field, in vivo dosimetry, brachytherapy and auditing of radiotherapy practice. Recent developments of dosimeters that can be used for these purposes are discussed using spatial resolution and number of dimensions for measurement as sorting criteria. While dosimetry is ever evolving to address the needs of advancing applications of radiation in medicine two fundamental issues remain: the accuracy of the measurement from a scientific perspective and the importance to link the measurement to a clinically relevant question. This review aims to provide an update on both of these.

  1. Dosimetry of ionising radiation in modern radiation oncology.

    PubMed

    Kron, Tomas; Lehmann, Joerg; Greer, Peter B

    2016-07-21

    Dosimetry of ionising radiation is a well-established and mature branch of physical sciences with many applications in medicine and biology. In particular radiotherapy relies on dosimetry for optimisation of cancer treatment and avoidance of severe toxicity for patients. Several novel developments in radiotherapy have introduced new challenges for dosimetry with small and dynamically changing radiation fields being central to many of these applications such as stereotactic ablative body radiotherapy and intensity modulated radiation therapy. There is also an increasing awareness of low doses given to structures not in the target region and the associated risk of secondary cancer induction. Here accurate dosimetry is important not only for treatment optimisation but also for the generation of data that can inform radiation protection approaches in the future. The article introduces some of the challenges and highlights the interdependence of dosimetric calculations and measurements. Dosimetric concepts are explored in the context of six application fields: reference dosimetry, small fields, low dose out of field, in vivo dosimetry, brachytherapy and auditing of radiotherapy practice. Recent developments of dosimeters that can be used for these purposes are discussed using spatial resolution and number of dimensions for measurement as sorting criteria. While dosimetry is ever evolving to address the needs of advancing applications of radiation in medicine two fundamental issues remain: the accuracy of the measurement from a scientific perspective and the importance to link the measurement to a clinically relevant question. This review aims to provide an update on both of these. PMID:27351409

  2. Post-Blast Analysis of Hexamethylene Triperoxide Diamine using Liquid Chromatography-Atmospheric Pressure Chemical Ionization-Mass Spectrometry.

    PubMed

    Marsh, Christine M; Mothershead, Robert F; Miller, Mark L

    2015-09-01

    A qualitative method using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC/APCI-MS) has been developed and validated for the identification of trace hexamethylene triperoxide diamine (HMTD) using three structurally-specific ions. Residues are extracted with deionized water (DI) and identified using a gradient mobile phase program and positive ion full scan mode on a Thermo Finnigan LCQ Ion Trap Mass Spectrometer. This method was validated according to several performance characteristics for the qualitative identification of an analyte using the characteristic ions, demonstrating the method's reliability for use on forensic applications. The method's limit of detection (LOD) can identify HMTD in an extract from a cotton matrix to which 20 μg of HMTD has been applied (equivalent to 10 ppm in extract). Previous scientific publications using LC/MS have not demonstrated post-blast HMTD residue analyses and suffer from a lack of chromatographic retention, sufficient number of mass spectral ions with validation, or require more complex/expensive instrumental methods (accurate mass or MS/MS). Post-blast analyses were successfully conducted with two syringe detonations that verified the efficacy of the method on the analysis of debris and residues following detonation. PMID:26385711

  3. Desorption electrospray ionization-mass spectrometric analysis of low vapor pressure chemical particulates collected from a surface.

    PubMed

    Ewing, K J; Gibson, D; Sanghera, J; Miklos, F

    2015-01-01

    The collection of a low vapor pressure chemical simulant triethyl phosphate sorbed onto silica gel (TEP/SG) from a surface with subsequent analysis of the TEP/SG particulates using desorption electrospray ionization-mass spectrometry (DESI-MS) is described. Collection of TEP/SG particulates on a surface was accomplished using a sticky screen sampler composed of a stainless steel screen coated with partially polymerized polydimethylsiloxane (PDMS). DESI-MS analysis of TEP/SG particulates containing different percentages of TEP sorbed onto silica gel enabled the generation of response curves for the TEP ions m/z 155 and m/z 127. Using the response curves the calculation of the mass of TEP in a 25 wt% sample of TEP/SG was calculated, results show that the calculated mass of TEP was 14% different from the actual mass of TEP in the sample using the m/z 127 TEP ion response curve. Detection limits for the TEP vapor and TEP/SG particulates were calculated to be 4 μg and 6 particles, respectively.

  4. Gas Chromatography Coupled to Atmospheric Pressure Chemical Ionization FT-ICR Mass Spectrometry for Improvement of Data Reliability.

    PubMed

    Schwemer, Theo; Rüger, Christopher P; Sklorz, Martin; Zimmermann, Ralf

    2015-12-15

    Atmospheric pressure chemical ionization (APCI) offers the advantage of molecular ion information with low fragmentation. Hyphenating APCI to gas chromatography (GC) and ultrahigh resolution mass spectrometry (FT-ICR MS) enables an improved characterization of complex mixtures. Data amounts acquired by this system are very huge, and existing peak picking algorithms are usually extremely time-consuming, if both gas chromatographic and ultrahigh resolution mass spectrometric data are concerned. Therefore, automatic routines are developed that are capable of handling these data sets and further allow the identification and removal of known ionization artifacts (e.g., water- and oxygen-adducts, demethylation, dehydrogenation, and decarboxylation). Furthermore, the data quality is enhanced by the prediction of an estimated retention index, which is calculated simply from exact mass data combined with a double bond equivalent correction. This retention index is used to identify mismatched elemental compositions. The approach was successfully tested for analysis of semivolatile components in heavy fuel oil and diesel fuel as well as primary combustion particles emitted by a ship diesel research engine. As a result, 10-28% of the detected compounds, mainly low abundant species, classically assigned by using only the mass spectrometric information, were identified as not valid and removed. Although GC separation is limited by the slow acquisition rate of the FT-ICR MS (<1 Hz), a database driven retention time comparison, as commonly used for low resolution GC/MS, can be applied for revealing isomeric information.

  5. Mass densification and defect restoration in chemical vapor deposition silicon dioxide film using Ar plasma excited by microwave

    SciTech Connect

    Kawase, Kazumasa Motoya, Tsukasa; Uehara, Yasushi; Teramoto, Akinobu; Suwa, Tomoyuki; Ohmi, Tadahiro

    2014-09-01

    Silicon dioxide (SiO{sub 2}) films formed by chemical vapor deposition (CVD) have been treated with Ar plasma excited by microwave. The changes of the mass densities, carrier trap densities, and thicknesses of the CVD-SiO{sub 2} films with the Ar plasma treatments were investigated. The mass density depth profiles were estimated with X-Ray Reflectivity (XRR) analysis using synchrotron radiation. The densities of carrier trap centers due to defects of Si-O bond network were estimated with X-ray Photoelectron Spectroscopy (XPS) time-dependent measurement. The changes of the thicknesses due to the oxidation of Si substrates were estimated with the XRR and XPS. The mass densities of the CVD-SiO{sub 2} films are increased by the Ar plasma treatments. The carrier trap densities of the films are decreased by the treatments. The thicknesses of the films are not changed by the treatments. It has been clarified that the mass densification and defect restoration in the CVD-SiO{sub 2} films are caused by the Ar plasma treatments without the oxidation of the Si substrates.

  6. Gas Chromatography Coupled to Atmospheric Pressure Chemical Ionization FT-ICR Mass Spectrometry for Improvement of Data Reliability.

    PubMed

    Schwemer, Theo; Rüger, Christopher P; Sklorz, Martin; Zimmermann, Ralf

    2015-12-15

    Atmospheric pressure chemical ionization (APCI) offers the advantage of molecular ion information with low fragmentation. Hyphenating APCI to gas chromatography (GC) and ultrahigh resolution mass spectrometry (FT-ICR MS) enables an improved characterization of complex mixtures. Data amounts acquired by this system are very huge, and existing peak picking algorithms are usually extremely time-consuming, if both gas chromatographic and ultrahigh resolution mass spectrometric data are concerned. Therefore, automatic routines are developed that are capable of handling these data sets and further allow the identification and removal of known ionization artifacts (e.g., water- and oxygen-adducts, demethylation, dehydrogenation, and decarboxylation). Furthermore, the data quality is enhanced by the prediction of an estimated retention index, which is calculated simply from exact mass data combined with a double bond equivalent correction. This retention index is used to identify mismatched elemental compositions. The approach was successfully tested for analysis of semivolatile components in heavy fuel oil and diesel fuel as well as primary combustion particles emitted by a ship diesel research engine. As a result, 10-28% of the detected compounds, mainly low abundant species, classically assigned by using only the mass spectrometric information, were identified as not valid and removed. Although GC separation is limited by the slow acquisition rate of the FT-ICR MS (<1 Hz), a database driven retention time comparison, as commonly used for low resolution GC/MS, can be applied for revealing isomeric information. PMID:26560682

  7. Plasma flame for mass purification of contaminated air with chemical and biological warfare agents

    SciTech Connect

    Uhm, Han S.; Shin, Dong H.; Hong, Yong C.

    2006-09-18

    An elimination of airborne simulated chemical and biological warfare agents was carried out by making use of a plasma flame made of atmospheric plasma and a fuel-burning flame, which can purify the interior air of a large volume in isolated spaces such as buildings, public transportation systems, and military vehicles. The plasma flame generator consists of a microwave plasma torch connected in series to a fuel injector and a reaction chamber. For example, a reaction chamber, with the dimensions of a 22 cm diameter and 30 cm length, purifies an airflow rate of 5000 lpm contaminated with toluene (the simulated chemical agent) and soot from a diesel engine (the simulated aerosol for biological agents). Large volumes of purification by the plasma flame will free mankind from the threat of airborne warfare agents. The plasma flame may also effectively purify air that is contaminated with volatile organic compounds, in addition to eliminating soot from diesel engines as an environmental application.

  8. Chemical composition and mass size distribution of PM1 at an elevated site in central east China

    NASA Astrophysics Data System (ADS)

    Zhang, Y. M.; Zhang, X. Y.; Sun, J. Y.; Hu, G. Y.; Shen, X. J.; Wang, Y. Q.; Wang, T. T.; Wang, D. Z.; Zhao, Y.

    2014-11-01

    Size-resolved aerosol chemical compositions were measured continuously for 1.5 years from June 2010 to January 2012 with an aerosol mass spectrometer (AMS) to characterize the mass and size distributions (MSDs) of major chemical components in submicron particles (approximately PM1) at Mountain Tai (Mt. Tai), an elevated site in central east China. The annual mean mass concentrations of organic, sulfate, nitrate, ammonium, and chloride were 11.2, 9.2, 7.2, 5.8, and 0.95 μg m-3, respectively, which are much higher than those at most mountain sites in the USA and Europe, but lower than those at the nearby surface rural sites in China. A clear seasonality was observed for all major components throughout the study, with low concentration in fall and high in summer, and is believed to be caused by seasonal variations in planetary boundary layer (PBL) height, near surface pollutant concentrations and regional transport processes. Air masses were classified into categories impacted by PBL, lower free troposphere (LFT), new particle formation (NPF), in-cloud processes, and polluted aerosols. Organics dominated the PM1 mass during the NPF episodes, while sulfate contributed most to PM1 in cloud events. The average MSDs of particles between 30 and 1000 nm during the entire study for organics, sulfate, nitrate, and ammonium were approximately log-normal with mass median diameters (MMDs) of 539, 585, 542, and 545 nm, respectively. These values are slightly larger than those observed at ground sites within the North China Plain (NCP), likely due to the relative aged and well-mixed aerosol masses at Mt. Tai. There were no obvious differences in MMDs during the PBL, LFT, in-cloud and polluted episodes, but smaller MMDs, especially for organics, were observed during the NPF events. During the PBL, NPF, and polluted episodes, organics accounted for major proportions at smaller modes, and reached 70% at 100-200 nm particles in the polluted events. In cloud episodes, inorganics

  9. 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.

  10. Control of Chemical Effects in the Separation Process of a Differential Mobility / Mass Spectrometer System

    PubMed Central

    Schneider, Bradley B.; Coy, Stephen L.; Krylov, Evgeny V.; Nazarov, Erkinjon G.

    2013-01-01

    Differential mobility spectrometry (DMS) separates ions on the basis of the difference in their migration rates under high versus low electric fields. Several models describing the physical nature of this field mobility dependence have been proposed but emerging as a dominant effect is the clusterization model sometimes referred to as the dynamic cluster-decluster model. DMS resolution and peak capacity is strongly influenced by the addition of modifiers which results in the formation and dissociation of clusters. This process increases selectivity due to the unique chemical interactions that occur between an ion and neutral gas phase molecules. It is thus imperative to bring the parameters influencing the chemical interactions under control and find ways to exploit them in order to improve the analytical utility of the device. In this paper we describe three important areas that need consideration in order to stabilize and capitalize on the chemical processes that dominate a DMS separation. The first involves means of controlling the dynamic equilibrium of the clustering reactions with high concentrations of specific reagents. The second area involves a means to deal with the unwanted heterogeneous cluster ion populations emitted from the electrospray ionization process that degrade resolution and sensitivity. The third involves fine control of parameters that affect the fundamental collision processes, temperature and pressure. PMID:20065515

  11. Control of chemical effects in the separation process of a differential mobility mass spectrometer system.

    PubMed

    Schneider, Bradley B; Covey, Thomas R; Coy, Stephen L; Krylov, Evgeny V; Nazarov, Erkinjon G

    2010-01-01

    Differential mobility spectrometry (DMS) separates ions on the basis of the difference in their migration rates under high versus low electric fields. Several models describing the physical nature of this field mobility dependence have been proposed but emerging as a dominant effect is the clusterization model sometimes referred to as the dynamic cluster-decluster model. DMS resolution and peak capacity is strongly influenced by the addition of modifiers which results in the formation and dissociation of clusters. This process increases selectivity due to the unique chemical interactions that occur between an ion and neutral gas-phase molecules. It is thus imperative to bring the parameters influencing the chemical interactions under control and find ways to exploit them in order to improve the analytical utility of the device. In this paper, we describe three important areas that need consideration in order to stabilize and capitalize on the chemical processes that dominate a DMS separation. The first involves means of controlling the dynamic equilibrium of the clustering reactions with high concentrations of specific reagents. The second area involves a means to deal with the unwanted heterogeneous cluster ion populations emitted from the electrospray ionization process that degrade resolution and sensitivity. The third involves fine control of parameters that affect the fundamental collision processes, temperature and pressure.

  12. Quantitative assessment of chemical artefacts produced by propionylation of histones prior to mass spectrometry analysis.

    PubMed

    Soldi, Monica; Cuomo, Alessandro; Bonaldi, Tiziana

    2016-07-01

    Histone PTMs play a crucial role in regulating chromatin structure and function, with impact on gene expression. MS is nowadays widely applied to study histone PTMs systematically. Because histones are rich in arginine and lysine, classical shot-gun approaches based on trypsin digestion are typically not employed for histone modifications mapping. Instead, different protocols of chemical derivatization of lysines in combination with trypsin have been implemented to obtain "Arg-C like" digestion products that are more suitable for LC-MS/MS analysis. Although widespread, these strategies have been recently described to cause various side reactions that result in chemical modifications prone to be misinterpreted as native histone marks. These artefacts can also interfere with the quantification process, causing errors in histone PTMs profiling. The work of Paternoster V. et al. is a quantitative assessment of methyl-esterification and other side reactions occurring on histones after chemical derivatization of lysines with propionic anhydride [Proteomics 2016, 16, 2059-2063]. The authors estimate the effect of different solvents, incubation times, and pH on the extent of these side reactions. The results collected indicate that the replacement of methanol with isopropanol or ACN not only blocks methyl-esterification, but also significantly reduces other undesired unspecific reactions. Carefully titrating the pH after propionic anhydride addition is another way to keep methyl-esterification under control. Overall, the authors describe a set of experimental conditions that allow reducing the generation of various artefacts during histone propionylation. PMID:27373704

  13. Chemical and mineralogical analyses of planetary rocks using a laser ablation mass spectrometer for in situ space research

    NASA Astrophysics Data System (ADS)

    Brigitte Neuland, Maike; Mezger, Klaus; Riedo, Andreas; Tulej, Marek; Wurz, Peter

    2015-04-01

    The context chemical analysis is of considerable importance in space research. High resolution in situ studies of planetary materials can yield important information on surface heterogeneity, basic grain mineralogy and chemical composition of surface and subsurface. In turn, these data are the basis for our understanding of the physical and chemical processes which led to the formation and alteration of planetary material [1] [2]. A highly heterogeneous sample of Allende meteorite, representative for extraterrestrial material, is investigated by LMS, a miniature laser ablation mass spectrometer designed for space research [3]. In the current setup a fs-laser ablation ion source is applied, allowing chemical analysis with lateral resolution of about 10-15 μm and sub-micrometre depth resolution [4]. The reflectron TOF mass analyser is used to measure elemental and isotopic composition of the sampled surface. The LMS instrument supports mass resolution 400 and dynamic range of 108 [5]. In the current studies with the fs-ablation ion source significant improvements in the detection efficiency of several metals e.g., Ni, Co, and non-metals e.g., Si, P, S and O, was achieved comparing to our previous setup [6]. Also the values of sensitivity coefficients for these elements are determined to be close to one, which resulted in the substantial improvements of the quantitative element analysis of the sample. Since the ablation crater depth is expected to be about 1 nm/laser shot also the possible changes of the main element or isotope distribution in depth can be analysed to assess their influence on the mineralogical analysis [7]. Several areas on an Allende sample were investigated and the chemical composition across the surface was determined from the mass spectrometric analysis. Also accurate isotope analysis could be conducted for most of main elements with sufficiently high signal to noise ratio. Correlation of elements was conducted and yielded mineralogical maps

  14. Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

    PubMed

    Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

    2009-12-01

    A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites. PMID:19886654

  15. Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

    PubMed

    Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

    2009-12-01

    A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.

  16. Mass transfer constraints on the chemical evolution of an active hydrothermal system, Valles caldera, New Mexico

    USGS Publications Warehouse

    White, A.F.; Chuma, N.J.; Goff, F.

    1992-01-01

    Partial equilibrium conditions occur between fluids and secondary minerals in the Valles hydrothermal system, contained principally in the Tertiary rhyolitic Bandelier Tuff. The mass transfer processes are governed by reactive phase compositions, surface areas, water-rock ratios, reaction rates, and fluid residence times. Experimental dissolution of the vitric phase of the tuff was congruent with respect to Cl in the solid and produced reaction rates which obeyed a general Arrhenius release rate between 250 and 300??C. The 18O differences between reacted and unreacted rock and fluids, and mass balances calculations involving Cl in the glass phase, produced comparable water-rock ratios of unity, confirming the importance of irreversible reaction of the vitric tuff. A fluid residence time of approximately 2 ?? 103 years, determined from fluid reservoir volume and discharge rates, is less than 0.2% of the total age of the hydrothermal system and denotes a geochemically and isotopically open system. Mass transfer calculations generally replicated observed reservoir pH, Pco2, and PO2 conditions, cation concentrations, and the secondary mineral assemblage between 250 and 300??C. The only extraneous component required to maintain observed calcite saturation and high Pco2 pressures was carbon presumably derived from underlying Paleozoic limestones. Phase rule constraints indicate that Cl was the only incompatible aqueous component not controlled by mineral equilibrium. Concentrations of Cl in the reservoir directly reflect mass transport rates as evidenced by correlations between anomalously high Cl concentrations in the fluids and tuff in the Valles caldera relative to other hydrothermal systems in rhyolitic rocks. ?? 1992.

  17. Portable gas chromatograph mass spectrometer for on-site chemical analyses

    DOEpatents

    Haas, Jeffrey S.; Bushman, John F.; Howard, Douglas E.; Wong, James L.; Eckels, Joel D.

    2002-01-01

    A portable, lightweight (approximately 25 kg) gas chromatograph mass spectrometer, including the entire vacuum system, can perform qualitative and quantitative analyses of all sample types in the field. The GC/MS has a conveniently configured layout of components for ease of serviceability and maintenance. The GC/MS system can be transported under operating or near-operating conditions (i.e., under vacuum and at elevated temperature) to reduce the downtime before samples can be analyzed on-site.

  18. A High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    PubMed Central

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijfhout, Falko P.

    2015-01-01

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. A range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. Here, we illustrate how the method can be used to: (1) distinguish between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required. PMID:26156000

  19. High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    SciTech Connect

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijhout, Falko P.

    2015-07-09

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. Moreover, a range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. In this paper, we illustrate how the method can be used to: (1) distinguish between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.

  20. High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    DOE PAGESBeta

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijhout, Falko P.

    2015-07-09

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. Moreover, a range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. In this paper, we illustrate how the method can be used to: (1) distinguishmore » between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.« less

  1. A High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures.

    PubMed

    Musah, Rabi A; Espinoza, Edgard O; Cody, Robert B; Lesiak, Ashton D; Christensen, Earl D; Moore, Hannah E; Maleknia, Simin; Drijfhout, Falko P

    2015-07-09

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. A range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. Here, we illustrate how the method can be used to: (1) distinguish between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.

  2. Chemical characterization of high-molar-mass fractions in a Norway spruce knotwood ethanol extract.

    PubMed

    Smeds, Annika I; Eklund, Patrik C; Willför, Stefan M

    2016-10-01

    The low-molar-mass (LMM) fraction, only, i.e., the GC-eluting compounds, which are mainly lignans, has been characterized in Norway spruce knotwood hydrophilic extracts previously. Of this fraction, many lignans and sesquilignans and all GC peaks supposedly representing dilignans remain unidentified. In this work, dilignans and the GC non-eluting compounds (the high-molar mass fractions, HMM) were characterized in a 7-hydroxymatairesinol-reduced knotwood ethanol extract of Norway spruce by using several fractionation and analytical techniques. A methyl tert-butyl ether (MTBE) insoluble fraction of the extract contained mainly HMM material, of which the main part was shown to consist of lignan oligomers. The oligolignans (with a molar mass up to approximately 3700 Da) seemed to be linked by 55' bonds, some of them containing one or two guaiacylglycerol ether units linked to the lignan by βO4 or β5 bonds. Several oligolignans were identified or tentatively identified. The MTBE soluble fraction, which accounted for the major part (81%) of the extract, contained mainly LMM material (lignans, sesqui- and dilignans). The part of the HMM material in the MTBE soluble fraction that was easily isolable (2%) seemed to contain polymers of fatty acids and alcohols, resin acids, and sterols. PMID:27256310

  3. A High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    NASA Astrophysics Data System (ADS)

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijfhout, Falko P.

    2015-07-01

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. A range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. Here, we illustrate how the method can be used to: (1) distinguish between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.

  4. Mass Casualty Decontamination in a Chemical or Radiological/ Nuclear Incident: Further Guiding Principles

    PubMed Central

    Carter, Holly; Amlôt, Richard; Williams, Richard; Rubin, G. James; Drury, John

    2016-01-01

    This short report presents a response to an article written by Cibulsky et al. (2016). The paper by Cibulsky et al. presents a useful and timely overview of the evidence surrounding the technical and operational aspects of mass casualty decontamination. It identifies three priority targets for future research, the third of which is how casualties' needs can be met in ways that best support compliance with and effectiveness of casualty decontamination. While further investigation into behavioural, communication and privacy issues during mass decontamination is warranted, there is now a substantial body of research in this area which is not considered in detail in the succinct summary provided by Cibulsky et al. (2016). In this short report, we summarise the available evidence around likely public behaviour during mass decontamination, effective communication strategies, and potential issues resulting from a lack of privacy. Our intention is to help further focus the research needs in this area and highlight topics on which more research is needed. PMID:27790381

  5. Mass-independent isotopic fractionation of tin in a chemical exchange reaction

    NASA Astrophysics Data System (ADS)

    Fujii, T.; Moynier, F.

    2008-12-01

    Tin isotopes were fractionated by the liquid-liquid extraction technique with a crown ether, dicyclohexano-18- crown-6 (DC18C6). Tin dichloride was dissolved in HCl to create solutions, 0.1 mol dm-3 (M) Sn(II) in various [HCl]. The organic phase was 0.1 M DC18C6 in 1,2-dichloroethane. A 5 cm3 aqueous solution and a 5 cm3 organic solution were mixed in a glass vial with a stirrer bar, and the glass vial was sealed. The two phases were stirred by a magnetic stirrer, and after the equilibrium, the two phases were separated by centrifugation. An aliquot of the upper aqueous solution was taken for analysis. These procedures were carried out at room temperature. The Sn concentration in the equilibrated aqueous phase was analyzed by ICP-AES. In order to avoid any matrix effect, possible trace of organic materials from DC18C6 was separated from the Sn on a micro-column anion-exchange resin in HBr/HNO3. An aliquot of the aqueous phase was once dried by heating and then dissolved into a HBr solution. Sn was strongly adsorbed while organic materials went through. Finally Sn was collected in a HNO3 solution. A solution containing 300 ppb of Sn in 0.05 M HNO3 was prepared for isotopic analysis. Isotopic ratios of Sn in all samples were analyzed with the MC-ICP-MS Nu plasma 500 HR at ENS Lyon coupled with a desolvating nebulizer Nu DSN-100 (with a typical precision of <100 ppm). The instrumental mass bias was controlled by bracketing each of the samples with standards. Because 120Sn is the most abundant isotopes, the isotope ratios have been measured as mSn/120Sn (m : 116, 117, 118, 119, 122, and 124). 114Sn and 115Sn were not analyzed due to their low abundances. Possible interferences with Cd on the masses 116, with Te on the mass 120, 122 and 124 were verified to be under the detection of the ICP-MS. Odd atomic mass isotopes (117Sn and 119Sn) showed deficits of enrichment comparing to the even atomic mass isotopes (116Sn, 118Sn, 122Sn, and 124Sn). This odd-even staggering

  6. Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins.

    PubMed

    van Bavel, Bert; Geng, Dawei; Cherta, Laura; Nácher-Mestre, Jaime; Portolés, Tania; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; Dunstan, Jody; Jones, Rhys; Kotz, Alexander; Winterhalter, Helmut; Malisch, Rainer; Traag, Wim; Hagberg, Jessika; Ericson Jogsten, Ingrid; Beltran, Joaquim; Hernández, Félix

    2015-09-01

    The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is

  7. Topographical and Chemical Imaging of a Phase Separated Polymer Using a Combined Atomic Force Microscopy/Infrared Spectroscopy/Mass Spectrometry Platform.

    PubMed

    Tai, Tamin; Karácsony, Orsolya; Bocharova, Vera; Van Berkel, Gary J; Kertesz, Vilmos

    2016-03-01

    In this paper, the use of a hybrid atomic force microscopy/infrared spectroscopy/mass spectrometry imaging platform was demonstrated for the acquisition and correlation of nanoscale sample surface topography and chemical images based on infrared spectroscopy and mass spectrometry. The infrared chemical imaging component of the system utilized photothermal expansion of the sample at the tip of the atomic force microscopy probe recorded at infrared wave numbers specific to the different surface constituents. The mass spectrometry-based chemical imaging component of the system utilized nanothermal analysis probes for thermolytic surface sampling followed by atmospheric pressure chemical ionization of the gas phase species produced with subsequent mass analysis. The basic instrumental setup, operation, and image correlation procedures are discussed, and the multimodal imaging capability and utility are demonstrated using a phase separated poly(2-vinylpyridine)/poly(methyl methacrylate) polymer thin film. The topography and both the infrared and mass spectral chemical images showed that the valley regions of the thin film surface were comprised primarily of poly(2-vinylpyridine) and hill or plateau regions were primarily poly(methyl methacrylate). The spatial resolution of the mass spectral chemical images was estimated to be 1.6 μm based on the ability to distinguish surface features in those images that were also observed in the topography and infrared images of the same surface.

  8. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.

    2011-04-28

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm{sup 2}V{sup -1}s{sup -1} across the temperature range from 60 to 140 C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.

  9. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization.

    PubMed

    Ewing, Robert G; Waltman, Melanie J; Atkinson, David A

    2011-06-15

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm(2)V(-1)s(-1) across the temperature range from 60 to 140 °C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 °C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer. PMID:21524145

  10. Approach toward minimizing chemical interference in FAB mass spectra: the development and application of thermally - assisted FAB

    SciTech Connect

    Ackermann, B.L.

    1987-01-01

    Interferences with fast atom bombardment (FAB) mass spectrometry can be classified into two major categories. The first includes impurities which remain after analyte isolation/purification, and is especially problematic in samples of biological origin. The second type of chemical interference originates from the matrix used for FAB. An example of the first type, also known as sample-related interference, is presented in the context of the analysis of the urinary metabolites of the analgesic acetaminophen by means of the off-line combination of reverse phase HPLC and FAB. Recommendations are made for efficient use of these two methods with specific regard to minimizing chemical interferences. In addition, a method for calculating analyte signal to background (S/B) values is introduced as a means of evaluating the quality of the FAB mass spectrum. A method known as thermally-assisted FAB (TA-FAB) is introduced as a means of minimizing matrix-related background. Success to date has been achieved using aqueous saccharide solutions as TA-FAB matrices. Several important improvements to FAB result from thermal control of the matrix including a selection against matrix background, and the possibility of valid background subtraction. The development of TA-FAB is described in the context of applications of the technique to the analysis of several representative nonvolatile biomolecules including a series of cyclic tetrapeptide mycotoxins. In the final section, the hypothesis of ternary perculation (TP) is submitted to account for behavior observed during TA-FAB.

  11. Aging of secondary organic aerosol from small aromatic VOCs. Changes in chemical composition, mass yield, volatility and hygroscopicity

    DOE PAGESBeta

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2014-12-12

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form and transform SOA from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx. The effects of chemical aging on organic aerosol (OA) composition, mass yield, volatility and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state OSC) and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OSmore » C ranged from -0.29 to 0.45 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  12. Chemical composition and mass closure of ambient coarse particles at traffic and urban-background sites in Thessaloniki, Greece.

    PubMed

    Grigoratos, Theodoros; Samara, Constantini; Voutsa, Dimitra; Manoli, Evangelia; Kouras, Athanasios

    2014-06-01

    Concentrations and chemical composition of the coarse particle fraction (PMc) were investigated at two urban sites in the city of Thessaloniki, Greece, through concurrent sampling of PM10 and PM2.5 during the warm and the cold months of the year. PMc levels at the urban-traffic site (UT) were among the highest found in literature worldwide exhibiting higher values in the cold period. PMc levels at the urban-background site (UB) were significantly lower exhibiting a reverse seasonal trend. Concentration levels of minerals and most trace metals were also higher at the UT site suggesting a stronger impact from traffic-related sources (road dust resuspension, brake and tire abrasion, road wear). According to the chemical mass closure obtained, minerals (oxides of Si, Al, Ca, Mg, Fe, Ti, and K) dominated the PMc profile, regardless of the site and the period, with organic matter and secondary inorganic aerosols (mainly nitrate) also contributing considerably to the PMc mass, particularly in the warm period. The influence of wind speed to dilution and/or resuspension of coarse particles was investigated. The source of origin of coarse particles was also investigated using surface wind data and atmospheric back-trajectory modeling. Finally, the contribution of resuspension to PMc levels was estimated for air quality management perspectives.

  13. Convection and mass-transport in laser-induced chemical vapor deposition

    NASA Technical Reports Server (NTRS)

    Patnaik, S.; Brown, R. A.

    1988-01-01

    Gas flow and energy and species transport in laser-induced chemical vapor deposition (LICVD) of amorphous silicon films by silane pyrolysis are analyzed by finite element analysis of a two-dimensional model for the process. Spatial nonuniformity of the deposited film is shown to result from diffusion controlled transport of products between the beam and substrate. Deposition profiles are affected by buoyancy-driven convection only at increased gas pressures. Horizontal orientation of the reactor with respect to gravity is optimal because the stagnation-like flow, that results adjacent to the substrate, enhances mixing, and smoothes the film profile.

  14. Metabolomics relative quantitation with mass spectrometry using chemical derivatization and isotope labeling

    DOE PAGESBeta

    O'Maille, Grace; Go, Eden P.; Hoang, Linh; Want, Elizabeth J.; Smith, Colin; O'Maille, Paul; NordstrÖm, Anders; Morita, Hirotoshi; Qin, Chuan; Uritboonthai, Wilasinee; et al

    2008-01-01

    Comprehensive detection and quantitation of metabolites from a biological source constitute the major challenges of current metabolomics research. Two chemical derivatization methodologies, butylation and amination, were applied to human serum for ionization enhancement of a broad spectrum of metabolite classes, including steroids and amino acids. LC-ESI-MS analysis of the derivatized serum samples provided a significant signal elevation across the total ion chromatogram to over a 100-fold increase in ionization efficiency. It was also demonstrated that derivatization combined with isotopically labeled reagents facilitated the relative quantitation of derivatized metabolites from individual as well as pooled samples.

  15. Chemical recoveries of technetium-99 for various procedures using inductively coupled plasma-mass spectrometry

    SciTech Connect

    Ihsanullah; East, B.W.

    1993-12-31

    The procedure for the determination of {sup 99}Tc inductively coupled plasma-mass spectrometry (ICP-MS) was based on the modification of a variety of available separation techniques. Standard Ru and Rh solutions were used for checking decontaminations and instrument response respectively. Technetium-99 and {sup 95m}Tc tracers were applied as yield monitors using ICP-MS and gamma-ray spectrometry respectively. Percent recoveries are reported for a variety of radiochemical separation procedures for water (58-83%), seaweed (10-76%), and for soil matrices (19-79%).

  16. Chemical and Trajectory Analysis of an Air Mass Plume from Asia

    NASA Astrophysics Data System (ADS)

    Guo, J. J.; Marrero, J. E.; Blake, D. R.

    2014-12-01

    Tracking the source of pollution events is important in understanding the transport of pollution plumes and impact on areas far from the source. Previous studies have shown that the rising contribution of Asian air pollution to the US has increased the number of days that pollution events exceed National Ambient Air Quality Standards (NAAQS). Whole air samples collected over the Edwards Air Force Base during a June 2014 NASA Student Airborne Research Program (SARP) flight exhibited enhancements in the concentrations of several compounds between 23-32 thousand feet. Chemical tracer analysis of these high altitude samples reveal that the air does not correspond to California emitted air. Chemical signatures in the plume, including high levels of OCS, chloroform, and methyl chloride, and low levels of methyl bromide, indicate that the plume was most heavily influence by coal combustion with contributions from biomass burning events from Asia. Low concentrations of ethene at the high altitude despite enhanced concentrations of ethane and ethyne suggest that this plume was aged. Further analysis of the plume using meteorological wind trajectories reveal that the plume had originated in China approximately 4-5 days prior. This is faster than results from previous studies that had found a Spring transport time of approximately 6 days.

  17. Chemical cross-linking/mass spectrometry targeting acidic residues in proteins and protein complexes.

    PubMed

    Leitner, Alexander; Joachimiak, Lukasz A; Unverdorben, Pia; Walzthoeni, Thomas; Frydman, Judith; Förster, Friedrich; Aebersold, Ruedi

    2014-07-01

    The study of proteins and protein complexes using chemical cross-linking followed by the MS identification of the cross-linked peptides has found increasingly widespread use in recent years. Thus far, such analyses have used almost exclusively homobifunctional, amine-reactive cross-linking reagents. Here we report the development and application of an orthogonal cross-linking chemistry specific for carboxyl groups. Chemical cross-linking of acidic residues is achieved using homobifunctional dihydrazides as cross-linking reagents and a coupling chemistry at neutral pH that is compatible with the structural integrity of most protein complexes. In addition to cross-links formed through insertion of the dihydrazides with different spacer lengths, zero-length cross-link products are also obtained, thereby providing additional structural information. We demonstrate the application of the reaction and the MS identification of the resulting cross-linked peptides for the chaperonin TRiC/CCT and the 26S proteasome. The results indicate that the targeting of acidic residues for cross-linking provides distance restraints that are complementary and orthogonal to those obtained from lysine cross-linking, thereby expanding the yield of structural information that can be obtained from cross-linking studies and used in hybrid modeling approaches. PMID:24938783

  18. Chemical cross-linking/mass spectrometry targeting acidic residues in proteins and protein complexes

    PubMed Central

    Leitner, Alexander; Joachimiak, Lukasz A.; Unverdorben, Pia; Walzthoeni, Thomas; Frydman, Judith; Förster, Friedrich; Aebersold, Ruedi

    2014-01-01

    The study of proteins and protein complexes using chemical cross-linking followed by the MS identification of the cross-linked peptides has found increasingly widespread use in recent years. Thus far, such analyses have used almost exclusively homobifunctional, amine-reactive cross-linking reagents. Here we report the development and application of an orthogonal cross-linking chemistry specific for carboxyl groups. Chemical cross-linking of acidic residues is achieved using homobifunctional dihydrazides as cross-linking reagents and a coupling chemistry at neutral pH that is compatible with the structural integrity of most protein complexes. In addition to cross-links formed through insertion of the dihydrazides with different spacer lengths, zero-length cross-link products are also obtained, thereby providing additional structural information. We demonstrate the application of the reaction and the MS identification of the resulting cross-linked peptides for the chaperonin TRiC/CCT and the 26S proteasome. The results indicate that the targeting of acidic residues for cross-linking provides distance restraints that are complementary and orthogonal to those obtained from lysine cross-linking, thereby expanding the yield of structural information that can be obtained from cross-linking studies and used in hybrid modeling approaches. PMID:24938783

  19. Chemical or biological terrorist attacks: an analysis of the preparedness of hospitals for managing victims affected by chemical or biological weapons of mass destruction.

    PubMed

    Bennett, Russell L

    2006-03-01

    The possibility of a terrorist attack employing the use of chemical or biological weapons of mass destruction (WMD) on American soil is no longer an empty threat, it has become a reality. A WMD is defined as any weapon with the capacity to inflict death and destruction on such a massive scale that its very presence in the hands of hostile forces is a grievous threat. Events of the past few years including the bombing of the World Trade Center in 1993, the Murrah Federal Building in Oklahoma City in 1995 and the use of planes as guided missiles directed into the Pentagon and New York's Twin Towers in 2001 (9/11) and the tragic incidents involving twentythree people who were infected and five who died as a result of contact with anthrax-laced mail in the Fall of 2001, have well established that the United States can be attacked by both domestic and international terrorists without warning or provocation. In light of these actions, hospitals have been working vigorously to ensure that they would be "ready" in the event of another terrorist attack to provide appropriate medical care to victims. However, according to a recent United States General Accounting Office (GAO) nationwide survey, our nation's hospitals still are not prepared to manage mass causalities resulting from chemical or biological WMD. Therefore, there is a clear need for information about current hospital preparedness in order to provide a foundation for systematic planning and broader discussions about relative cost, probable effectiveness, environmental impact and overall societal priorities. Hence, the aim of this research was to examine the current preparedness of hospitals in the State of Mississippi to manage victims of terrorist attacks involving chemical or biological WMD. All acute care hospitals in the State were selected for inclusion in this study. Both quantitative and qualitative methods were utilized for data collection and analysis. Six hypotheses were tested. Using a questionnaire

  20. Chemical or Biological Terrorist Attacks: An Analysis of the Preparedness of Hospitals for Managing Victims Affected by Chemical or Biological Weapons of Mass Destruction

    PubMed Central

    Bennett, Russell L.

    2006-01-01

    The possibility of a terrorist attack employing the use of chemical or biological weapons of mass destruction (WMD) on American soil is no longer an empty threat, it has become a reality. A WMD is defined as any weapon with the capacity to inflict death and destruction on such a massive scale that its very presence in the hands of hostile forces is a grievous threat. Events of the past few years including the bombing of the World Trade Center in 1993, the Murrah Federal Building in Oklahoma City in 1995 and the use of planes as guided missiles directed into the Pentagon and New York’s Twin Towers in 2001 (9/11) and the tragic incidents involving twenty-three people who were infected and five who died as a result of contact with anthrax-laced mail in the Fall of 2001, have well established that the United States can be attacked by both domestic and international terrorists without warning or provocation. In light of these actions, hospitals have been working vigorously to ensure that they would be “ready” in the event of another terrorist attack to provide appropriate medical care to victims. However, according to a recent United States General Accounting Office (GAO) nationwide survey, our nation’s hospitals still are not prepared to manage mass causalities resulting from chemical or biological WMD. Therefore, there is a clear need for information about current hospital preparedness in order to provide a foundation for systematic planning and broader discussions about relative cost, probable effectiveness, environmental impact and overall societal priorities. Hence, the aim of this research was to examine the current preparedness of hospitals in the State of Mississippi to manage victims of terrorist attacks involving chemical or biological WMD. All acute care hospitals in the State were selected for inclusion in this study. Both quantitative and qualitative methods were utilized for data collection and analysis. Six hypotheses were tested. Using a

  1. Chemical derivatization for electrospray ionization mass spectrometry. 1. Alkyl halides, alcohols, phenols, thiols, and amines

    SciTech Connect

    Quirke, J.M.E.; Adams, C.L.; Van Berkel, G.J. )

    1994-04-15

    Derivatization strategies and specific derivatization reactions for conversion of simple alkyl halides, alcohols, phenols, thiols, and amines to ionic or solution-ionizable derivatives, that is [open quotes]electrospray active[close quotes] (ES-active) forms of the analyte, are presented. Use of these reactions allows detection of analytes among those listed that are not normally amenable to analysis by electrospray ionization mass spectrometry (ES-MS). In addition, these reactions provide for analysis specificity and flexibility through functional group specific derivatization and through the formation of derivatives that can be detected in positive ion or in negative ion mode. For a few of the functional groups, amphoteric derivatives are formed that can be analyzed in either positive or negative ion modes. General synthetic strategies for transformation of members of these five compound classes to ES-active species are presented along with illustrative examples of suitable derivatives. Selected derivatives were prepared using model compounds and the ES mass spectra obtained for these derivatives are discussed. The analytical utility of derivatization for ES-MS analysis is illustrated in three experiments: (1) specific detection of the major secondary alcohol in oil of peppermint, (2) selective detection of phenols within a synthetic mixture of phenols, and (3) identification of the medicinal amines within a commercially available cold medication as primary, secondary or tertiary. 65 refs., 3 figs., 3 tabs.

  2. Calculation of eddy viscosity in a compressible turbulent boundary layer with mass injection and chemical reaction

    NASA Technical Reports Server (NTRS)

    Omori, S.; Gross, K. W.

    1973-01-01

    The turbulent kinetic energy equation is coupled with boundary layer equations to solve the characteristics of compressible turbulent boundary layers with mass injection and combustion. The Reynolds stress is related to the turbulent kinetic energy using the Prandtl-Wieghardt formulation. When a lean mixture of hydrogen and nitrogen is injected through a porous plate into the subsonic turbulent boundary layer of air flow and ignited by external means, the turbulent kinetic energy increases twice as much as that of noncombusting flow with the same mass injection rate of nitrogen. The magnitudes of eddy viscosity between combusting and noncombusting flows with injection, however, are almost the same due to temperature effects, while the distributions are different. The velocity profiles are significantly affected by combustion. If pure hydrogen as a transpiration coolant is injected into a rocket nozzle boundary layer flow of combustion products, the temperature drops significantly across the boundary layer due to the high heat capacity of hydrogen. At a certain distance from the wall hydrogen reacts with the combustion products, liberating an extensive amount of heat.

  3. Atmospheric pressure mass spectrometry: a new analytical chemical characterization method for dissolved organic matter in rainwater.

    PubMed

    Seitzinger, Sybil P; Styles, Renée M; Lauck, Ron; Mazurek, Monica A

    2003-01-01

    The complex mixture of organic compounds in the atmosphere influences climate, air quality, and ecosystem processes. Atmospheric pressure electrospray ionization mass spectrometry (APESI-MS) was evaluated as a potential tool for direct measurement of the total suite of individual dissolved organic matter (DOM) compounds in rainwater. The APESI-MS response was linear to all DOM compounds of atmospheric significance examined as standard solutions. Urban precipitation samples from New Brunswick, NJ (USA) were analyzed by APESI-MS over the mass-to-charge (m/z) range 50-3,000. Over 95% of the m/z ions detected were in the low m/z range (50-500). Over 300 unique m/z ions were detected across the 11 rainwater samples indicating the complexity of the mixture of DOM in rainwater. Forty percent of the organic bases (positive mode detection) and 22% of the organic acids (negative mode) occurred in at least 6 of the 11 rainwater samples. Ions corresponding to the m/z of carboxylic acids standards (nonanedioic acid; 1,4-butanedicarboxylic acid; pentanedioic acid; hydroxybutanedioic acid; and butanedioic acid) and to reduced N standards (allylurea; caffeine; imidazole; and N-2-propenylurea) occurred in at least one of the 11 rainwater samples. Total dissolved organic carbon (DOC) estimated from the APESI-MS analysis and measured by standard DOC methods were not statistically different.

  4. Topographical and Chemical Imaging of a Phase Separated Polymer Using a Combined Atomic Force Microscopy/Infrared Spectroscopy/Mass Spectrometry Platform

    DOE PAGESBeta

    Tai, Tamin; Karácsony, Orsolya; Bocharova, Vera; Van Berkel, Gary J.; Kertesz, Vilmos

    2016-02-18

    This article describes how the use of a hybrid atomic force microscopy/infrared spectroscopy/mass spectrometry imaging platform was demonstrated for the acquisition and correlation of nanoscale sample surface topography and chemical images based on infrared spectroscopy and mass spectrometry.

  5. Excitation and Ionisation dynamics in high-frequency plasmas

    NASA Astrophysics Data System (ADS)

    O'Connell, D.

    2008-07-01

    Non-thermal low temperature plasmas are widely used for technological applications. Increased demands on plasma technology have resulted in the development of various discharge concepts based on different power coupling mechanisms. Despite this, power dissipation mechanisms in these discharges are not yet fully understood. Of particular interest are low pressure radio-frequency (rf) discharges. The limited understanding of these discharges is predominantly due to the complexity of the underlying mechanisms and difficult diagnostic access to important parameters. Optical measurements are a powerful diagnostic tool offering high spatial and temporal resolution. Optical emission spectroscopy (OES) provides non-intrusive access, to the physics of the plasma, with comparatively simple experimental requirements. Improved advances in technology and modern diagnostics now allow deeper insight into fundamental mechanisms. In low pressure rf discharges insight into the electron dynamics within the rf cycle can yield vital information. This requires high temporal resolution on a nano-second time scale. The optical emission from rf discharges exhibits temporal variations within the rf cycle. These variations are particularly strong, in for example capacitively coupled plasmas (CCPs), but also easily observable in inductively coupled plasmas (ICPs), and can be exploited for insight into power dissipation. Interesting kinetic and non-linear coupling effects are revealed in capacitive systems. The electron dynamics exhibits a complex spatio-temporal structure. Excitation and ionisation, and, therefore, plasma sustainment is dominated through directed energetic electrons created through the dynamics of the plasma boundary sheath. In the relatively simple case of an asymmetric capacitively coupled rf plasma the complexity of the power dissipation is exposed and various mode transitions can be clearly observed and investigated. At higher pressure secondary electrons dominate the

  6. Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry.

    PubMed

    Pozzi, Romina; Bocchini, Paola; Pinelli, Francesca; Galletti, Guido C

    2011-04-01

    A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen. PMID:21377686

  7. Chemical characterization of bio-oils using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

    PubMed

    Tessarolo, Nathalia S; dos Santos, Luciana R M; Silva, Raphael S F; Azevedo, Débora A

    2013-03-01

    The liquid product obtained via the biomass flash pyrolysis is commonly called bio-oil or pyrolysis oil. Bio-oils can be used as sources for chemicals or as fuels, primarily in mixtures or emulsions with fossil fuels. A detailed chemical characterization of bio-oil is necessary to determine its potential uses. Such characterization demands a powerful analytical technique such as comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). Limited chemical information can be obtained from conventional gas chromatography coupled mass spectrometry (GC-MS) because of the large number of compounds and coelutions. Thus, GC×GC-TOFMS was used for the individual identification of bio-oil components from two samples prepared via the flash pyrolysis of empty palm fruit bunch and pine wood chips. To the best of our knowledge, few papers have reported comprehensive two-dimensional gas chromatography (GC×GC) for bio-oil analysis. Many classes of compounds such as phenols, benzenediols, cyclopentenones, furanones, indanones and alkylpyridines were identified. Several coelutions present in the GC-MS were resolved using GC×GC-TOFMS. Many peaks were detected for the samples by GC-MS (~166 and 129), but 631 and 857 were detected by GC×GC-TOFMS, respectively. The GC×GC-TOFMS analyses indicated that the major classes of components (analytes>0.5% relative area) in the two bio-oil samples are ketones, cyclopentenones, furanones, furans, phenols, benzenediols, methoxy- and dimethoxy-phenols and sugars. In addition, esters, aldehydes and pyridines were found for sample obtained from empty palm fruit bunch, while alcohols and cyclopentanediones were found in sample prepared from pine wood chips indicating different composition profiles due to the biomass sources. The elucidation of the composition of empty fruit bunch and pine wood chips bio-oils indicates that these oils are suitable for the production of value-added chemicals. The

  8. [Development of a chemical ionization time-of-flight mass spectrometer for continuous measurements of atmospheric hydroxyl radical].

    PubMed

    Dou, Jian; Hua, Lei; Hou, Ke-Yong; Jiang, Lei; Xie, Yuan-Yuan; Zhao, Wu-Duo; Chen, Ping; Wang, Wei-Guo; Di, Tian; Li, Hai-Yang

    2014-05-01

    A home-made chemical ionization time-of-flight mass spectrometer (TOFMS) has been developed for continuous measurements of atmospheric hydroxyl radical. Based on the atmospheric pressure chemical ionization technique, an ionization source with orthogonal dual tube structure was adopted in the instrument, which minimized the interference between the reagent gas ionization and the titration reaction. A 63Ni radioactive source was fixed inside one of the orthogonal tubes to generate reactant ion of NO(-)(3) from HNO3 vapor. Hydroxyl radical was first titrated by excess SO2 to form equivalent concentrations of H2SO4 in the other orthogonal tube, and then reacted with NO(-)(3) ions in the chemical ionization chamber, leading to HSO(-)(4) formation. The concentration of atmospheric hydroxyl radical can be directly calculated by measuring the intensities of the HSOj product ions and the NO(-)(3) reactant ions. The analytical capability of the instrument was demonstrated by measuring hydroxyl radical in laboratory air, and the concentration of the hydroxyl radical in the investigated air was calculated to be 1.6 x 106 molecules*cm ', based on 5 seconds integration. The results have shown that the instrument is competent for in situ continuous measurements of atmospheric trace radical.

  9. Mass casualties and health care following the release of toxic chemicals or radioactive material--contribution of modern biotechnology.

    PubMed

    Göransson Nyberg, Ann; Stricklin, Daniela; Sellström, Åke

    2011-12-01

    Catastrophic chemical or radiological events can cause thousands of casualties. Such disasters require triage procedures to identify the development of health consequences requiring medical intervention. Our objective is to analyze recent advancements in biotechnology for triage in mass emergency situations. In addition to identifying persons "at risk" of developing health problems, these technologies can aid in securing the unaffected or "worried well". We also highlight the need for public/private partnerships to engage in some of the underpinning sciences, such as patho-physiological mechanisms of chemical and radiological hazards, and for the necessary investment in the development of rapid assessment tools through identification of biochemical, molecular, and genetic biomarkers to predict health effects. For chemical agents, biomarkers of neurotoxicity, lung damage, and clinical and epidemiological databases are needed to assess acute and chronic effects of exposures. For radiological exposures, development of rapid, sensitive biomarkers using advanced biotechnologies are needed to sort exposed persons at risk of life-threatening effects from persons with long-term risk or no risk. The final implementation of rapid and portable diagnostics tools suitable for emergency care providers to guide triage and medical countermeasures use will need public support, since commercial incentives are lacking.

  10. Secondary ionization of chemical warfare agent simulants: atmospheric pressure ion mobility time-of-flight mass spectrometry.

    PubMed

    Steiner, Wes E; Clowers, Brian H; Haigh, Paul E; Hill, Herbert H

    2003-11-15

    For the first time, the use of a traditional ionization source for ion mobility spectrometry (radioactive nickel ((63)Ni) beta emission ionization) and three alternative ionization sources (electrospray ionization (ESI), secondary electrospray ionization (SESI), and electrical discharge (corona) ionization (CI)) were employed with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulants from both aqueous- and gas-phase samples. For liquid-phase samples, ESI was used as the sample introduction and ionization method. For the secondary ionization (SESI, CI, and traditional (63)Ni ionization) of vapor-phase samples, two modes of sample volatilization (heated capillary and thermal desorption chamber) were investigated. Simulant reference materials, which closely mimic the characteristic chemical structures of CWA as defined and described by Schedule 1, 2, or 3 of the Chemical Warfare Convention treaty verification, were used in this study. A mixture of four G/V-type nerve simulants (dimethyl methylphosphonate, pinacolyl methylphosphonate, diethyl phosphoramidate, and 2-(butylamino)ethanethiol) and one S-type vesicant simulant (2-chloroethyl ethyl sulfide) were found in each case (sample ionization and introduction methods) to be clearly resolved using the IM(tof)MS method. In many cases, reduced mobility constants (K(o)) were determined for the first time. Ion mobility drift times, flight times, relative signal intensities, and fragmentation product signatures for each of the CWA simulants are reported for each of the methods investigated. PMID:14615983

  11. Mass Casualties and Health Care Following the Release of Toxic Chemicals or Radioactive Material—Contribution of Modern Biotechnology

    PubMed Central

    Göransson Nyberg, Ann; Stricklin, Daniela; Sellström, Åke

    2011-01-01

    Catastrophic chemical or radiological events can cause thousands of casualties. Such disasters require triage procedures to identify the development of health consequences requiring medical intervention. Our objective is to analyze recent advancements in biotechnology for triage in mass emergency situations. In addition to identifying persons “at risk” of developing health problems, these technologies can aid in securing the unaffected or “worried well”. We also highlight the need for public/private partnerships to engage in some of the underpinning sciences, such as patho-physiological mechanisms of chemical and radiological hazards, and for the necessary investment in the development of rapid assessment tools through identification of biochemical, molecular, and genetic biomarkers to predict health effects. For chemical agents, biomarkers of neurotoxicity, lung damage, and clinical and epidemiological databases are needed to assess acute and chronic effects of exposures. For radiological exposures, development of rapid, sensitive biomarkers using advanced biotechnologies are needed to sort exposed persons at risk of life-threatening effects from persons with long-term risk or no risk. The final implementation of rapid and portable diagnostics tools suitable for emergency care providers to guide triage and medical countermeasures use will need public support, since commercial incentives are lacking. PMID:22408587

  12. Mass casualties and health care following the release of toxic chemicals or radioactive material--contribution of modern biotechnology.

    PubMed

    Göransson Nyberg, Ann; Stricklin, Daniela; Sellström, Åke

    2011-12-01

    Catastrophic chemical or radiological events can cause thousands of casualties. Such disasters require triage procedures to identify the development of health consequences requiring medical intervention. Our objective is to analyze recent advancements in biotechnology for triage in mass emergency situations. In addition to identifying persons "at risk" of developing health problems, these technologies can aid in securing the unaffected or "worried well". We also highlight the need for public/private partnerships to engage in some of the underpinning sciences, such as patho-physiological mechanisms of chemical and radiological hazards, and for the necessary investment in the development of rapid assessment tools through identification of biochemical, molecular, and genetic biomarkers to predict health effects. For chemical agents, biomarkers of neurotoxicity, lung damage, and clinical and epidemiological databases are needed to assess acute and chronic effects of exposures. For radiological exposures, development of rapid, sensitive biomarkers using advanced biotechnologies are needed to sort exposed persons at risk of life-threatening effects from persons with long-term risk or no risk. The final implementation of rapid and portable diagnostics tools suitable for emergency care providers to guide triage and medical countermeasures use will need public support, since commercial incentives are lacking. PMID:22408587

  13. Models of low-mass helium white dwarfs including gravitational settling, thermal and chemical diffusion, and rotational mixing

    NASA Astrophysics Data System (ADS)

    Istrate, A. G.; Marchant, P.; Tauris, T. M.; Langer, N.; Stancliffe, R. J.; Grassitelli, L.

    2016-10-01

    A large number of extremely low-mass helium white dwarfs (ELM WDs) have been discovered in recent years. The majority of them are found in close binary systems suggesting they are formed either through a common-envelope phase or via stable mass transfer in a low-mass X-ray binary (LMXB) or a cataclysmic variable (CV) system. Here, we investigate the formation of these objects through the LMXB channel with emphasis on the proto-WD evolution in environments with different metallicities. We study for the first time the combined effects of rotational mixing and element diffusion (e.g. gravitational settling, thermal and chemical diffusion) on the evolution of proto-WDs and on the cooling properties of the resulting WDs. We present state-of-the-art binary stellar evolution models computed with MESA for metallicities of Z = 0.02, 0.01, 0.001 and 0.0002, producing WDs with masses between 0.16-0.45 M⊙. Our results confirm that element diffusion plays a significant role in the evolution of proto-WDs that experience hydrogen shell flashes. The occurrence of these flashes produces a clear dichotomy in the cooling timescales of ELM WDs, which has important consequences e.g. for the age determination of binary millisecond pulsars. In addition, we confirm that the threshold mass at which this dichotomy occurs depends on metallicity. Rotational mixing is found to counteract the effect of gravitational settling in the surface layers of young, bloated ELM proto-WDs and therefore plays a key role in determining their surface chemical abundances, i.e. the observed presence of metals in their atmospheres. We predict that these proto-WDs have helium-rich envelopes through a significant part of their lifetime. This is of great importance as helium is a crucial ingredient in the driving of the κ-mechanism suggested for the newly observed ELM proto-WD pulsators. However, we find that the number of hydrogen shell flashes and, as a result, the hydrogen envelope mass at the beginning of

  14. Invasive oral cancer stem cells display resistance to ionising radiation.

    PubMed

    Gemenetzidis, Emilios; Gammon, Luke; Biddle, Adrian; Emich, Helena; Mackenzie, Ian C

    2015-12-22

    There is a significant amount of evidence to suggest that human tumors are driven and maintained by a sub-population of cells, known as cancer stem cells (CSC). In the case of head and neck cancer, such cells have been characterised by high expression levels of CD44 cell surface glycoprotein, while we have previously shown the presence of two diverse oral CSC populations in vitro, with different capacities for cell migration and proliferation. Here, we examined the response of oral CSC populations to ionising radiation (IR), a front-line measure for the treatment of head and neck tumors. We show that oral CSC initially display resistance to IR-induced growth arrest as well as relative apoptotic resistance. We propose that this is a result of preferential activation of the DNA damagerepair pathway in oral CSC with increased activation of ATM and BRCA1, elevated levels of DNA repair proteins RAD52, XLF, and a significantly faster rate of DNA double-strand-breaks clearance 24 hours following IR. By visually identifying CSC sub-populations undergoing EMT, we show that EMT-CSC represent the majority of invasive cells, and are more radio-resistant than any other population in re-constructed 3D tissues. We provide evidence that IR is not sufficient to eliminate CSC in vitro, and that sensitization of CD44hi/ESAlow cells to IR, followed by secondary EMT blockade, could be critical in order to reduce primary tumor recurrence, but more importantly to be able to eradicate cells capable of invasion and distant metastasis.

  15. Comparison of Aerosol Mass Spectrometer and Aerosol Chemical Speciation Monitor Measurements of Secondary Organic Aerosol Formation in Smog Chamber Studies

    NASA Astrophysics Data System (ADS)

    Croteau, P. L.; Hunter, J. F.; Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Canagaratna, M.; Jayne, J.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Thermal vaporization-electron impact ionization (TV-EI) mass spectrometry is a powerful tool for understanding the chemistry of secondary organic aerosol (SOA) formation and atmospheric aging. The Aerodyne Aerosol Mass Spectrometer (AMS) and recently developed Aerosol Chemical Speciation Monitor (ACSM) are two instruments that utilize the same TV-EI technique. The ACSM trades the particle sizing capability, sensitivity, speed, and resolution of the AMS for simplicity, affordability, and ease of operation - enabling stand-alone continuous sampling for extended periods of time. Here we present results of an intercomparison between a high-resolution AMS and an ACSM. Three well-studied SOA formation chamber experiments were conducted: isoprene photooxidation under high NOx conditions, m-xylene photooxidation under high NOx conditions, and α-pinene ozonolysis under low NOx conditions. Comparisons between time-series and mass spectra from these experiments, along with positive matrix factorization analysis results demonstrate that the ACSM, while it does not provide the same level of detail as an AMS, is a suitable tool for exploring the chemistry of SOA formation in chamber studies.

  16. Chemical cross-linking and mass spectrometry to determine the subunit interaction network in a recombinant human SAGA HAT subcomplex.

    PubMed

    Nguyen-Huynh, Nha-Thi; Sharov, Grigory; Potel, Clément; Fichter, Pélagie; Trowitzsch, Simon; Berger, Imre; Lamour, Valérie; Schultz, Patrick; Potier, Noëlle; Leize-Wagner, Emmanuelle

    2015-08-01

    Understanding the way how proteins interact with each other to form transient or stable protein complexes is a key aspect in structural biology. In this study, we combined chemical cross-linking with mass spectrometry to determine the binding stoichiometry and map the protein-protein interaction network of a human SAGA HAT subcomplex. MALDI-MS equipped with high mass detection was used to follow the cross-linking reaction using bis[sulfosuccinimidyl] suberate (BS3) and confirm the heterotetrameric stoichiometry of the specific stabilized subcomplex. Cross-linking with isotopically labeled BS3 d0-d4 followed by trypsin digestion allowed the identification of intra- and intercross-linked peptides using two dedicated search engines: pLink and xQuest. The identified interlinked peptides suggest a strong network of interaction between GCN5, ADA2B and ADA3 subunits; SGF29 is interacting with GCN5 and ADA3 but not with ADA2B. These restraint data were combined to molecular modeling and a low-resolution interacting model for the human SAGA HAT subcomplex could be proposed, illustrating the potential of an integrative strategy using cross-linking and mass spectrometry for addressing the structural architecture of multiprotein complexes.

  17. Analysis of Polycyclic Aromatic Hydrocarbons Using Desorption Atmospheric Pressure Chemical Ionization Coupled to a Portable Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Jjunju, Fred P. M.; Maher, Simon; Li, Anyin; Badu-Tawiah, Abraham K.; Taylor, Stephen; Graham Cooks, R.

    2015-02-01

    Desorption atmospheric pressure chemical ionization (DAPCI) is implemented on a portable mass spectrometer and applied to the direct detection of polycyclic aromatic hydrocarbons (PAHs) and alkyl substituted benzenes. The presence of these compounds in the environment poses a significant threat to the health of both humans and wildlife because of their carcinogenic, toxic, and mutagenic properties. As such, instant detection outside of the laboratory is of particular importance to allow in-situ measurement at the source. Using a rapid, high throughput, miniature, handheld mass spectrometer, several alkyl substituted benzenes and PAHs (i.e., 1,2,3,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, fluoranthene, anthracene, benzo[ k]fluoranthene, dibenz[ a,h]anthracene, acenaphthene, indeno[1,2,3-c,d]pyrene, 9-ethylfluorene, and 1-benzyl-3-methyl-naphthalene) were identified and characterized using tandem mass spectrometry (MS/MS) from ambient surfaces, in the open air. This method can provide almost instantaneous information while minimizing sample preparation, which is advantageous in terms of both cost and simplicity of analysis. This MS-based technique is applicable to a wide range of environmental organic molecules.

  18. An analytical platform for mass spectrometry-based identification and chemical analysis of RNA in ribonucleoprotein complexes.

    PubMed

    Taoka, Masato; Yamauchi, Yoshio; Nobe, Yuko; Masaki, Shunpei; Nakayama, Hiroshi; Ishikawa, Hideaki; Takahashi, Nobuhiro; Isobe, Toshiaki

    2009-11-01

    We describe here a mass spectrometry (MS)-based analytical platform of RNA, which combines direct nano-flow reversed-phase liquid chromatography (RPLC) on a spray tip column and a high-resolution LTQ-Orbitrap mass spectrometer. Operating RPLC under a very low flow rate with volatile solvents and MS in the negative mode, we could estimate highly accurate mass values sufficient to predict the nucleotide composition of a approximately 21-nucleotide small interfering RNA, detect post-transcriptional modifications in yeast tRNA, and perform collision-induced dissociation/tandem MS-based structural analysis of nucleolytic fragments of RNA at a sub-femtomole level. Importantly, the method allowed the identification and chemical analysis of small RNAs in ribonucleoprotein (RNP) complex, such as the pre-spliceosomal RNP complex, which was pulled down from cultured cells with a tagged protein cofactor as bait. We have recently developed a unique genome-oriented database search engine, Ariadne, which allows tandem MS-based identification of RNAs in biological samples. Thus, the method presented here has broad potential for automated analysis of RNA; it complements conventional molecular biology-based techniques and is particularly suited for simultaneous analysis of the composition, structure, interaction, and dynamics of RNA and protein components in various cellular RNP complexes.

  19. An analytical platform for mass spectrometry-based identification and chemical analysis of RNA in ribonucleoprotein complexes

    PubMed Central

    Taoka, Masato; Yamauchi, Yoshio; Nobe, Yuko; Masaki, Shunpei; Nakayama, Hiroshi; Ishikawa, Hideaki; Takahashi, Nobuhiro; Isobe, Toshiaki

    2009-01-01

    We describe here a m