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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, 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.

  2. 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.

  3. Laser Ablation/Ionisation Mass Spectrometry: Sensitive and Quantitative Chemical Depth Profiling of Solid Materials.

    PubMed

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

    2016-01-01

    Direct quantitative and sensitive chemical analysis of solid materials with high spatial resolution, both in lateral and vertical direction is of high importance in various fields of analytical research, ranging from in situ space research to the semiconductor industry. Accurate knowledge of the chemical composition of solid materials allows a better understanding of physical and chemical processes that formed/altered the material and allows e.g. to further improve these processes. So far, state-of-the-art techniques such as SIMS, LA-ICP-MS or GD-MS have been applied for chemical analyses in these fields of research. In this report we review the current measurement capability and the applicability of our Laser Ablation/Ionisation Mass Spectrometer (instrument name LMS) for the chemical analysis of solids with high spatial resolution. The most recent chemical analyses conducted on various solid materials, including e.g. alloys, fossils and meteorites are discussed. PMID:27131112

  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. PMID:26988473

  5. Direct atmospheric pressure chemical ionisation ion trap mass spectrometry for aroma analysis: Speed, sensitivity and resolution of isobaric compounds

    NASA Astrophysics Data System (ADS)

    Jublot, Lionel; Linforth, Robert S. T.; Taylor, Andrew J.

    2005-06-01

    Atmospheric pressure chemical ionisation (APCI) sources were developed for real time analysis of volatile release from foods using an ion trap (IT) mass spectrometer (MS). Key objectives were spectral simplicity (minimal fragmentation), response time and signal to noise ratio. The benefits of APCI-IT-MS were assessed by comparing the performance for in vivo and headspace analyses with that obtained using APCI coupled to a quadrupole mass analyser. Using MS-MS, direct APCI-IT-MS was able to differentiate mixtures of some C6 and terpene isobaric aroma compounds. Resolution could be achieved for some compounds by monitoring specific secondary ions. Direct resolution was also achieved with two of the three isobaric compounds released from chocolate with time as the sample was eaten.

  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.

    2013-09-01

    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.

  7. 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.

  8. Determination of sulfonamides by packed column supercritical fluid chromatography with atmospheric pressure chemical ionisation mass spectrometric detection.

    PubMed

    Dost, K; Jones, D C; Davidson, G

    2000-07-01

    Sulfonamide antibiotics are widely used to prevent bacterial infections in livestock, and residues are commonly found in milk and meat. Packed column supercritical fluid chromatography (pSFC) with detection using ultra violet (UV) and atmospheric pressure chemical ionisation (APCI) mass spectrometry (MS) provides a versatile method for the detection and quantification of six major sulfonamides. The APCI mass spectra for all the sulfonamides consisted of protonated molecules at low cone voltages. Increasing the cone voltage led to informative fragmentation patterns, which provided structural information for identification purposes. The pSFC-APCI-MS technique was shown to be linear (r2 > or = 0.999) over the concentration range 0.1-50 micrograms ml-1 using total ion current. The precision and the accuracy of the system and validation of sample preparation are acceptable, with RSD < 2% and relative error 8%. Selected ion monitoring gave detection limits as follows: sulfadiazine 41, sulfamethoxazole 45, sulfamerazine 47, sulfamethizole 59, sulfamethazine 181 and sulfadimethoxine 96 micrograms l-1, which are lower than the amounts permitted in milk products. The APCI pSFC-MS system was shown to have a high degree of reproducibility. The technique was then applied to determine the above sulfonamides in milk. The results obtained show that there are no matrix effects from the milk and that the detection limits remained as stated for the standard solutions. PMID:10984919

  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. Identification of main corticosteroids as illegal feed additives in milk replacers by liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry.

    PubMed

    Fiori, M; Pierdominici, E; Longo, F; Brambilla, G

    1998-05-22

    Corticosteroids were proposed as growth promoting agents to improve commercial quality of meat. We developed a liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry (LC-APCI-MS) method able to identify the presence in milk replacers, when given by mouth, of dexamethasone, betamethasone, flumethasone, triamcinolone, predinisotone, prednisolone, methylprednisolone, fludrocortisone and beclomethasone, at levels in the range of 20-100 ppb. C18 solid-phase extraction, LC-RP C8 column separation, data acquisition (positive ions) in the scan range m/z 200-550 allowed us to differentiate and identify compounds by protonated molecules, their methanolic adducts and fragmentation patterns. PMID:9646497

  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. PMID:24468241

  12. Novel characterisation of minor α-linolenic acid isomers in linseed oil by gas chromatography and covalent adduct chemical ionisation tandem mass spectrometry.

    PubMed

    Gómez-Cortés, P; Brenna, J T; Lawrence, P; de la Fuente, M A

    2016-06-01

    Discrimination between polyunsaturated fatty acid isomers with three double bonds is a great challenge, due to structural similarities and similar polarities. In this study, we report the identification of four minor geometrical isomers of α-linolenic acid (ALA) present in linseed oil samples: (9E,12Z,15E)-, (9Z,12Z,15E)-, (9Z,12E,15Z)- and (9E,12Z,15Z)-octadeca-9,12,15-trienoic acids, chromatographically resolved by gas chromatography (GC) using a new and highly polar ionic phase column (SLB-IL111). Gas chromatography-electron ionisation mass spectrometry (GC-EIMS) determined that the four unknown compounds were C18:3 n-3 isomers. The positional 9-12-15 C18:3 configuration was achieved by covalent adduct chemical ionisation tandem mass spectrometry (CACI-MS/MS) while geometrical configuration was established with analytical standards based on relative retention. We hypothesised that these isomers are formed during linseed oil deodorisation and postulate preferred and unfavoured isomerisation pathways of ALA. PMID:26830571

  13. Structural elucidation of monoterpene oxidation products by ion trap fragmentation using on-line atmospheric pressure chemical ionisation mass spectrometry in the negative ion mode.

    PubMed

    Warscheid, B; Hoffmann, T

    2001-01-01

    Based on ion trap mass spectrometry, an on-line method is described which provides valuable information on the molecular composition of structurally complex organic aerosols. The investigated aerosols were generated from the gas-phase ozonolysis of various C(10)H(16)-terpenes (alpha-pinene, beta-pinene, 3-carene, sabinene, limonene), and directly introduced into the ion source of the mass spectrometer. Negative ion chemical ionisation at atmospheric pressure (APCI(-)) enabled the detection of multifunctional carboxylic acid products by combining inherent sensitivity and molecular weight information. Sequential low-energy collision-induced product ion fragmentation experiments (MS(n)) were performed in order to elucidate characteristic decomposition pathways of the compounds. Dicarboxylic acids, oxocarboxylic acids and hydroxyketocarboxylic acid products could be clearly distinguished by multistage on-line MS. Furthermore, sabinonic acid and two C(9)-ether compounds were tentatively identified for the first time by applying on-line APCI(-)-MS(n). PMID:11746892

  14. Chemical study of triterpenoid resinous materials in archaeological findings by means of direct exposure electron ionisation mass spectrometry and gas chromatography/mass spectrometry.

    PubMed

    Modugno, Francesca; Ribechini, Erika; Colombini, Maria Perla

    2006-01-01

    A systematic study of standard triterpenes (alpha-amyrine, oleanolic acid, betulin, lupeol, betulinic acid and lupenone) and of raw resinous materials (frankincense resin, mastic resin and birch bark pitch) was performed using direct exposure electron ionisation mass spectrometry (DE-MS) and gas chromatography/mass spectrometry (GC/MS). DE-MS provides a mass spectral fingerprint of organic materials in a few minutes which highlights the compounds that are the main components in the sample. The application of principal component analysis (PCA) on DE-MS data in the mass ranges m/z 181-260 and m/z 331-500, corresponding to the fragmentation of triterpenoid molecules, enabled us to distinguish between different triterpenoid materials such as mastic resin, frankincense resin and birch bark pitch, and to graphically plot the resinous substances in three separate clusters, retaining 89% of the total variance. GC/MS analysis of the same materials has permitted us to elucidate in detail the molecular composition and to identify minor components and species that act as markers of the degradation undergone by the materials. The paper also reports the results for the organic residues contained in an Egyptian censer (5th-7th century AD) which was recovered in the excavation of the Necropolis of Antinoe (Egypt), and for the hafting material found on a Palaeolithic tool recovered at the site of Campitello (Arezzo, Tuscany), dating back to the Mid-Pleistocene period. Although DE-MS was found to be a fast analytical tool, it failed to give any information on the presence of less abundant compounds when applied to mixtures of different materials: only mastic resin was found in the residues from the Roman censer, whereas GC/MS analysis identified the presence of a vegetable oil from Brassicaceae seeds and Pinaceae resin. Birch bark pitch as a pure material was identified in the sample from the Palaeolithic flint flake using both procedures. PMID:16676320

  15. 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

  16. 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

  17. The analysis of beta-agonists by packed-column supercritical fluid chromatography with ultra-violet and atmospheric pressure chemical ionisation mass spectrometric detection.

    PubMed

    Jones, D C; Dost, K; Davidson, G; George, M W

    1999-06-01

    Packed-column supercritical fluid chromatography (pSFC) using ultra-violet (UV) and atmospheric pressure chemical ionisation (APCI) mass spectrometry (MS) provides a versatile method for the identification and quantification of beta-agonists. We have achieved good separation of clenbuterol, salbutamol, terbutaline and fenoterol with good resolution and reasonable retention times using a high concentration of methanol modifier in the supercritical CO2, together with small amounts of both acidic (trifluoroacetic acid, TFAA) and basic (triethylamine, TEA, or diethylamine, DEA) additives. APCI-MS gave unambiguous identification of the 4 analytes, and increasing cone voltage provided informative fragmentation patterns. The pSFC-MS technique was shown to be linear (R2 > or = 0.996) over the concentration range 1-50 micrograms ml-1. Single ion monitoring (SIM) gave detection limits (on-column) of 2.5 ng (clenbuterol), 0.83 ng (terbutaline), 7.6 ng (salbutamol) and 2.7 ng (fenoterol). The pSFC-MS system was shown to be reproducible within a day, between days, and between restrictors. Analysis of milk samples 'spiked' with beta-agonists showed that the matrix caused no interference, with detection limits of approximately 500 micrograms l-1 of beta-agonists. More dilute solutions could be analysed by pre-concentration before the SFC stage. PMID:10736867

  18. On-line measurements of α-pinene ozonolysis products using an atmospheric pressure chemical ionisation ion-trap mass spectrometer

    NASA Astrophysics Data System (ADS)

    Warscheid, Bettina; Hoffmann, Thorsten

    An on-line technique to investigate complex organic oxidation reactions in environmental chamber experiments is presented. The method is based on the direct introduction of the chamber air into an atmospheric pressure ion source of a commercial ion-trap mass spectrometer. To demonstrate the analytical potential of the method (atmospheric pressure chemical ionisation/mass spectrometry, APCI/MS), the ozonolysis of α-pinene was investigated in a series of experiments performed in various sized reaction chambers at atmospheric pressure and 296 K in synthetic air. Investigations were focussed on the influence of the water vapour concentration on the formation of the predominant oxidation product, pinonaldehyde, derived from the α-pinene/ozone reaction. Quantification of pinonaldehyde was achieved by conducting a standard addition technique. The molar yield of pinonaldehyde was found to depend strongly on the actual water vapour concentration between <1 and 80% relative humidity. Starting with an average yield of 0.23±0.05 at dry conditions, pinonaldehyde formation was approximately doubled by reaching a yield of 0.53±0.05 at a relative humidity of around 60%. Furthermore, the formation mechanism of pinonaldehyde was investigated in greater detail using isotopically labelled water. Applying on-line APCI/MS, pinonaldehyde formation under incorporation of 18O was observed, strongly supporting the reaction of the stabilised Criegee radical with water in the gas phase as suggested by Alvarado et al. (Journal of Geophysical Research 103 (1998) 25541-25551). Furthermore, the mass spectra recorded on-line were used to perform a semi-quantitative estimation of the decomposition pathway of the primary ozonide, indicating a branching ratio of 0.35/0.65.

  19. 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.

  20. 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

  1. 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

  2. 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. PMID:23736664

  3. 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. PMID:23498998

  4. 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.

  5. Desorption electrospray ionisation mass spectrometry and tandem mass spectrometry of low molecular weight synthetic polymers.

    PubMed

    Jackson, Anthony T; Williams, Jonathan P; Scrivens, James H

    2006-01-01

    A range of low molecular weight synthetic polymers has been characterised by means of desorption electrospray ionisation (DESI) combined with both mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Accurate mass experiments were used to aid the structural determination of some of the oligomeric materials. The polymers analysed were poly(ethylene glycol) (PEG), polypropylene glycol (PPG), poly(methyl methacrylate) (PMMA) and poly(alpha-methyl styrene). An application of the technique for characterisation of a polymer used as part of an active ingredient in a pharmaceutical tablet is described. The mass spectra and tandem mass spectra of all of the polymers were obtained in seconds, indicating the sensitivity of the technique. PMID:16912984

  6. 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.

  7. 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.

  8. Application of positive mode atmospheric chemical ionisation to distinguish epimeric oleanolic and ursolic acids.

    PubMed

    Townley, Chloe; Brettell, Rhea C; Bowen, Richard D; Gallagher, Richard T; Martin, William H C

    2015-01-01

    A new and more reliable method is reported for distinguishing the equatorial and axial epimers of oleanolic and ursolic acids and related triterpenoids based primarily on the relative abundance of the [M+H](+) and [M+-H(2)O](+) signals in their positive mode atmospheric pressure chemical ionisation mass spectra. The rate of elimination of water, which is the principal primary fragmentation of protonated oleanolic and ursolic acids, depends systematically on the stereochemistry of the hydroxyl group in the 3 position. For the b-epimer, in which the 3-hydroxyl substituent is in an equatorial position,[M+-H(2)O](+) is the base peak. In contrast, for the α-epimer, where the 3-hydroxyl group is axial, [M + H](+) is the base peak. This trend, which is general for a range of derivatives of oleanolic and ursolic acids, including the corresponding methyl esters, allows epimeric triterpenoids in these series to be securely differentiated. Confirmatory information is available from the collision-induced dissociation of the [M+-H(2)O](+) primary fragment ions, which follow different pathways for the species derived from axial and equatorial epimers of oleanolic and ursolic acids. These two pieces of independent spectral information permit the stereochemistry of epimeric oleanolic and ursolic acids (and selected derivatives) to be assigned with confidence without relying either on chromatographic retention times or referring to the spectra or other properties of authentic samples of these triterpenoids. PMID:26307724

  9. Analysis of oak tannins by liquid chromatography-electrospray ionisation mass spectrometry.

    PubMed

    Mämmelä, P; Savolainen, H; Lindroos, L; Kangas, J; Vartiainen, T

    2000-09-01

    Extractable tannins were analysed by liquid chromatography-electrospray ionisation mass spectrometry in two oak species, North American white oak (Quercus alba) and European red oak (Quercus robur). They mainly included various glucose gallic and ellagic acid esters. The structures were partially determined, and they included grandinin/roburin E, castalagin/vescalagin, gallic acid, valoneic acid bilactone, monogalloyl glucose, digalloyl glucose, trigalloyl glucose, ellagic acid rhamnose, quercitrin and ellagic acid. PMID:10999626

  10. 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

  11. Matrix-free mass spectrometric imaging using laser desorption ionisation Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Goodwin, Richard J A; Pitt, Andrew R; Harrison, David; Weidt, Stefan K; Langridge-Smith, Pat R R; Barrett, Michael P; Logan Mackay, C

    2011-04-15

    Mass spectrometry imaging (MSI) is a powerful tool in metabolomics and proteomics for the spatial localization and identification of pharmaceuticals, metabolites, lipids, peptides and proteins in biological tissues. However, sample preparation remains a crucial variable in obtaining the most accurate distributions. Common washing steps used to remove salts, and solvent-based matrix application, allow analyte spreading to occur. Solvent-free matrix applications can reduce this risk, but increase the possibility of ionisation bias due to matrix adhesion to tissue sections. We report here the use of matrix-free MSI using laser desorption ionisation performed on a 12 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. We used unprocessed tissue with no post-processing following thaw-mounting on matrix-assisted laser desorption ionisation (MALDI) indium-tin oxide (ITO) target plates. The identification and distribution of a range of phospholipids in mouse brain and kidney sections are presented and compared with previously published MALDI time-of-flight (TOF) MSI distributions. PMID:21416534

  12. Rapid screening of illicit additives in weight loss dietary supplements with desorption corona beam ionisation (DCBI) mass spectrometry.

    PubMed

    Wang, H; Wu, Y; Zhao, Y; Sun, W; Ding, L; Guo, B; Chen, B

    2012-08-01

    Desorption corona beam ionisation (DCBI), the relatively novel ambient mass spectrometry (MS) technique, was utilised to screen for illicit additives in weight-loss food. The five usually abused chemicals - fenfluramine, N-di-desmethyl sibutramine, N-mono-desmethyl sibutramine, sibutramine and phenolphthalein - were detected with the proposed DCBI-MS method. Fast single-sample and high-throughput analysis was demonstrated. Semi-quantification was accomplished based on peak areas in the ion chromatograms. Four illicit additives were identified and semi-quantified in commercial samples. As there was no tedious sample pre-treatment compared with conventional HPLC methods, high-throughput analysis was achieved with DCBI. The results proved that DCBI-MS is a powerful tool for the rapid screening of illicit additives in weight-loss dietary supplements. PMID:22784191

  13. 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. PMID:24992564

  14. Investigating the degradation of the sympathomimetic drug phenylephrine by electrospray ionisation-mass spectrometry.

    PubMed

    Trommer, Hagen; Raith, Klaus; Neubert, Reinhard H H

    2010-06-01

    The frequently used sympathomimetic drug phenylephrine has been studied by electrospray ionisation-mass spectrometry. The stability of the adrenoceptor agonist was examined by investigations of the pharmaceutically used salts phenylephrine hydrochloride and phenylephrine bitartrate. Photostability has been studied by use of an irradiation equipment emitting a solar radiation spectrum. The experiments were carried out by analysis of aqueous drug solutions before and after irradiation treatment. The phenylephrine derivative with unsaturated side chain originating from the drug by loss of one water molecule has been detected as the major degradation product of both phenylephrine salts the hydrochloride and the bitartrate. Further degradation and oxidation products were detectable already in the full scan mode demonstrating a low stability of the drug. Tandem mass spectrometry and multiple stage mass spectrometry experiments enabled the establishment of fragmentation schemes of both salts for the first time. Irradiation treatment indicated that phenylephrine bitartrate is more prone to degradation than the hydrochloride because of an additional decomposition sensitivity of the tartaric acid counter ion. An interaction between phenylephrine and its counter ion degradation products via a nucleophilic addition mechanism is suggested to be the explanation for the detected ion signals after irradiation treatment of phenylephrine bitartrate. PMID:20122809

  15. 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

  16. 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. PMID:22868116

  17. High-performance liquid chromatographic, capillary electrophoretic and capillary electrophoretic-electrospray ionisation mass spectrometric analysis of selected alkaloid groups.

    PubMed

    Stöckigt, Joachim; Sheludk, Yuri; Unger, Matthias; Gerasimenko, Irina; Warzecha, Heribert; Stöckigt, Detlef

    2002-08-16

    Systems for efficient separation of selected alkaloid groups by high performance liquid chromatography (HPLC), capillary electrophoresis (CE) and capillary electrophoresis coupled with electrospray ionisation mass spectrometry (CE-ESI-MS) are described. The optimized HPLC system was applied for the separation of 23 standard indole alkaloids as well as for qualitative and quantitative analyses of crude alkaloid extracts of Rauvolfia serpentina X Rhazya stricta hybrid cell cultures. The developed conditions for CE analysis proved to be efficient for separation of mixtures of standard indole and beta-carboline alkaloids. The described buffer system is also applicable in the combination of CE with electrospray ionisation mass spectrometry. This analytical technique allowed the separation and identification of components of standard indole alkaloid mixture as well as crude extracts of R. serpentina roots, R. serpentina cell suspension cultures and cortex of Aspidosperma quebracho-blanco. The influence of buffer composition and analyte structures on separation is discussed. PMID:12219932

  18. The use of particle beam mass spectrometry for the measurement of impurities in a nabumetone drug substance, not easily amenable to atmospheric pressure ionisation techniques.

    PubMed

    Wolff, J C; Hawtin, P N; Monté, S; Balogh, M; Jones, T

    2001-01-01

    Liquid chromatography/particle beam mass spectrometry (LC/PB-MS) was used for the structural elucidation of some impurities in nabumetone as this compound poorly ionises by atmospheric pressure ionisation (API) techniques. PB-MS was optimised for nabumetone and a sensitivity study was carried out. To obtain full scan electron ionisation spectra a minimum of 100 ng of compound on column was needed. By using 20 mg/mL solutions of nabumetone, impurities at levels of about 250 ppm mass fraction relative to nabumetone could be detected. Results were compared with LC/API-MS and previous GC/MS. PMID:11223957

  19. 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)

  20. 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. PMID:22284496

  1. 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)

  2. Chemotaxonomy of bacteria by comprehensive GC and GC-MS in electron impact and chemical ionisation mode.

    PubMed

    David, Frank; Tienpont, Bart; Sandra, Pat

    2008-10-01

    The analysis of the cellular lipidic fraction of bacteria is described. After hydrolysis and methylation, the fatty acid methyl esters (FAMEs) are determined by 1-D GC using the Sherlock MIDI bacteria identification system, by comprehensive GC (GC x GC) and by GC-MS in electron impact (EI) and positive chemical ionisation (PCI) mode. With GC x GC, the enhanced selectivity and group type separation provides a more complete elucidation of the fatty acids in microorganisms. GC-EI-MS and GC-PCI-MS were helpful for confirmation. The bacteria selected in this study are Brevundimonas diminuta, Chryseobacterium gleum and Stenotrophomonas maltophilia. PMID:18792008

  3. 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

  4. 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.

  5. 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

  6. Thermally annealed gold nanoparticles for surface-assisted laser desorption ionisation-mass spectrometry of low molecular weight analytes.

    PubMed

    Pilolli, Rosa; Ditaranto, Nicoletta; Di Franco, Cinzia; Palmisano, Francesco; Cioffi, Nicola

    2012-10-01

    Metal nanomaterials have an emerging role in surface-assisted laser desorption ionisation-mass spectrometry (SALDI-MS) providing a useful tool to overcome some limitations intrinsically related to the use of conventional organic matrices in matrix-assisted LDI-MS. In this contribution, the possibility to use a stainless-steel-supported gold nanoparticle (AuNP) film as a versatile platform for SALDI-MS was assessed. A sacrificial anode electrosynthetic route was chosen in order to obtain morphologically controlled core-shell AuNPs; the colloidal AuNPs were, thereafter, drop cast onto a stainless-steel sample plate and the resulting AuNP film was thermally annealed in order to improve its effectiveness as LDI-MS promoter. Spectroscopic characterization of the nanostructured film by X-ray photoelectron spectroscopy was crucial for understanding how annealing induced changes in the surface chemistry and influenced the performance of AuNPs as desorption/ionisation promoter. In particular, it was demonstrated that the post-deposition treatments were essential to enhance the AuNP core/analyte interaction, thus resulting in SALDI-MS spectra of significantly improved quality. The AuNP films were applied to the detection of three different classes of low molecular weight (LMW) analytes, i.e. amino acids, peptides and LMW polymers, in order to demonstrate the versatility of this nanostructured material. PMID:22825677

  7. Thin-layer chromatography-matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry using particle suspension matrices.

    PubMed

    Crecelius, Anna; Clench, Malcolm R; Richards, Don S; Parr, Vic

    2002-06-01

    Particle suspension matrices have been successfully utilized for the analysis of tetracycline antibiotics by thin-layer chromatography-matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry (TLC-MALDI-TOF-MS). Particles of different materials and sizes have been investigated (Co-UFP, TiN, TiO2, Graphite and Silicon) by applying particle suspensions to eluted TLC plates. Mass spectra and mass chromatograms have been recorded directly from the TLC plates. Strong cationization by sodium and potassium was obtained in the positive ion mode, with [M+Na-NH3]+ ions being the predominant signals. The TLC-MALDI mass spectra recorded from graphite suspensions showed the lowest background noise and the highest peak intensities from the range of suspension matrices studied. The mass accuracy from graphite films was improved by adding the peptide Phe-Phe to the graphite suspensions. This allowed internal recalibration of the TLC-MALDI mass spectra acquired during a run. One major potential advantage of TLC-MALDI-TOF-MS has been demonstrated in the analysis of chlortetracycline and tetracycline in a mixture of oxytetracycline, chlortetracycline, tetracycline and minocycline. Examination of the TLC plate prior to MALDI analysis showed only an unresolved spot for chlortetracycline and tetracycline. However by investigation of the MALDI mass spectra and plotting of single ion chromatograms separate peaks for chlortetracycline and tetracycline could be obtained. PMID:12134822

  8. Characterisation of an inexpensive sonic spray ionisation source using laser-induced fluorescence imaging and mass spectrometry.

    PubMed

    Stindt, Arne; Warschat, Carsten; Bierstedt, Andreas; Panne, Ulrich; Riedel, Jens

    2014-01-01

    A commercially available airbrush gun as a new source for spray ionisation is presented. It is best operated employing moderate stagnation pressures, resulting in a sonic gas flow. A mass spectrometric investigation on the amino acid Lysine and several peptides reveals that this inexpensive approach results in reproducible mass spectra. The ion patterns strongly resemble the results from other studies obtained with custom-made sonic spray vaporisers. The patterns also resemble the mass spectra recorded with electrospray devices. For a better understanding of the vaporisation process, the mass spectrometry experiments are accompanied by laser-induced fluorescence experiments. Inverse Abel Transform of the obtained fluorescence maps allows the determination of the full three-dimensional distribution of the spray cone. Furthermore, via exploitation of the solvatochromism of the used dye the solvation-state distribution can be visualised. In addition, expansion parameters, such as droplet size and velocity, are obtained by laser stroboscopy. The experiments demonstrate that the analyte hardly desolvates throughout the expansion. This indicates a subsequent vaporisation of the residual solvent in the intermediate pressure region of the mass spectrometer. PMID:24881452

  9. 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. PMID:25600686

  10. 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.

  11. Elucidating the structure of carbon nanoparticles by ultra-performance liquid chromatography coupled with electrospray ionisation quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Hu, Qin; Meng, Xiangpeng; Choi, Martin M F; Gong, Xiaojuan; Chan, Wan

    2016-03-10

    A fast and accurate ultra-performance liquid chromatography coupled with electrospray ionisation quadrupole time-of-flight tandem mass spectrometry (UPLC-ESI-Q-TOF-MS/MS) method was developed for the separation and structural elucidation of fluorescent carbon nanoparticles (CNP). The CNP was synthesised from microwave-assisted pyrolysis of citric acid (CA) and 1,2-ethylenediamine (EDA). By using UPLC separation, the CNP product was well separated into ten fractions within 4.0 min. Based on high-accuracy MS and MS/MS analyses, the CNP species were revealed to display six kinds of chemical formulas, including (C10H20N4O5)n, (C8H12N2O5)n, (C16H22N4O9)n, (C6H8O7)n, (C14H18N2O11)n, and (C14H16N2O10)n. In particular, our study revealed for the first time that the CNP species exist as supramolecular clusters with their individual monomers units linked together through non-covalent bonding forces. These findings clearly indicated the usefulness of UPLC-ESI-Q-TOF-MS/MS in identifying the chemical composition of CNP product. It is anticipated that our proposed methodology can be applied to study the structure-property relationships of CNP, facilitating in the production of CNP with desirable spectral features. PMID:26893091

  12. 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

  13. 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

  14. 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

  15. 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

  16. Rapid and simultaneous determination of polychlorinated biphenyls and their main metabolites (hydroxylated and methyl sulfonyl) by gas chromatography coupled to mass spectrometry: comparison of different ionisation modes.

    PubMed

    Castro-Puyana, M; Herrero, L; González, M J; Gómara, B

    2013-07-17

    Instrumental methods based on gas chromatography coupled to mass spectrometry (GC-MS) have been developed and compared using two different MS ionisation modes, electron impact (EI) and electron capture negative ionisation (ECNI), for the fast, quantitative and simultaneous determination of polychlorinated biphenyls (PCBs) and their main metabolites (hydroxylated PCBs, OH-PCBs, and methyl sulfone PCBs, MeSO2-PCBs). Parameters affecting chromatographic separation and MS detection were evaluated in order to achieve the highest selectivity and sensitivity for both operation modes. The analytical characteristics of the developed methods were studied and compared in terms of linear range, limits of detection (LODs), limits of quantification (LOQs), and instrumental precision (repeatability and intermediate precision). Both ionisation methods showed similar precision, being relative standard deviations (RSD, %) lower than 9% and 14% for repeatability and intermediate precision, respectively. However, better LODs (from 0.01 to 0.14 pg injected for the three families of congeners studied) were achieved using ECNI-MS as ionisation mode. The suitability of the developed method was demonstrated through their application to fish liver oil samples. PMID:23830433

  17. 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

  18. Determination of agrochemical compounds in soya plants by imaging matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Mullen, Alexander K; Clench, Malcolm R; Crosland, Susan; Sharples, Kate R

    2005-01-01

    Detection and imaging of the herbicide mesotrione (2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione) and the fungicide azoxystrobin (methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate), on the surface of the soya leaf, and the detection and imaging of azoxystrobin inside the stem of the soya plant, have been achieved using matrix-assisted laser desorption/ionisation quadrupole time-of-flight mass spectrometry. In leaf analysis experiments, the two pesticides were deposited onto the surface of individual soya leaves on growing plants. The soya leaves were removed and prepared for direct and indirect (following blotting onto matrix-coated cellulose membranes) imaging analysis at different periods after initial pesticide application. In stem analysis experiments, azoxystrobin was added to the nutrient solution of a soya plant growing in a hydroponics system. The plant was left for 48 h, and then horizontal and vertical stem sections were prepared for direct imaging analysis. The images obtained demonstrate the applicability of MALDI imaging to the detection and imaging of small organic compounds in plant tissue and further extend the analytical repertoire of the versatile MALDI technique. PMID:16106343

  19. Identification of synthetic dyes in early colour photographs using capillary electrophoresis and electrospray ionisation-mass spectrometry.

    PubMed

    López-Montes, Ana Ma; Dupont, Anne-Laurence; Desmazières, Bernard; Lavédrine, Bertrand

    2013-09-30

    Capillary electrophoresis with photodiode array detection (CE-PDA) and with electrospray ionisation-mass spectrometry (CE-ESI-MS) was used for the separation and the identification of 23 synthetic organic dyes, among those used in early 20th century colour photographs such as autochromes. Both cationic and anionic dyes could be separated within 15min using a single CE-PDA method. The method was used as the basis to develop a CE-ESI-MS methodology through the optimisation of the relevant ESI and MS parameters. Sheath liquid composition, nebulising gas pressure, drying gas flow rate and drying gas temperature were found to influence the sensitivity of the detection. These parameters were optimised in positive and negative ion modes for cationic dyes and anionic dyes, respectively. The two analyses could be carried out successively on a single sample. In view of the application to cultural heritage objects, the CE-ESI-MS analytical procedure was applied to identify the dyes in a Filmcolor artefact, late version of the autochrome. The results complemented and enhanced current knowledge as four cationic dyes and three anionic dyes were identified. Four additional dyes are proposed as possibly present as traces. PMID:23953463

  20. 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

  1. Determination of pharmaceutical compounds in skin by imaging matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Bunch, Josephine; Clench, Malcolm R; Richards, Don S

    2004-01-01

    Matrix-assisted laser desorption/ionisation (MALDI) quadrupole time-of-flight mass spectrometry (Q-TOFMS) has been used to detect and image the distribution of a xenobiotic substance in skin. Porcine epidermal tissue was treated with 'Nizoral', a medicated shampoo containing ketoconazole (+/-)-1-acetyl-4-[p-[[(2R,4S)-2-(2,4-dichlorophenyl)-2-(imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]piperazine) as active ingredient. Following incubation for 1 h at 37 degrees C all excess formulation was washed from the surface. A cross-section of the drug-treated tissue was then blotted onto a cellulose membrane, precoated in matrix (alpha-cyano-4-hydroxycinnamic acid (CHCA)), by airspray deposition. In separate experiments the tissue surface was treated with Nizoral within a triangular former, and subsequently blotted onto a matrix-coated membrane. Sample membranes were then mounted into the recess of specialised MALDI targets with adhesive tape. All samples were analysed by MALDI-TOFMS using an Applied Biosystem 'Q-star Pulsar i' hybrid Q-TOF mass spectrometer fitted with an orthagonal MALDI ion source and imaging software. Detection of the protonated molecule was readily achievable by this technique. Treatment of the tissue within a template gave rise to images depicting the expected distribution of the drug, demonstrating that this technique is capable of producing spatially useful data. Ion images demonstrating the permeation of the applied compound into the skin were achieved by imaging a cross-sectional imprint of treated tissue. A calibration graph for the determination of ketoconazole was prepared using the sodium adduct of the matrix ion as an internal standard. This enabled construction of a quantitative profile of drug in skin. Conventional haematoxylin and eosin staining and microscopy methods were employed to obtain a histological image of the porcine epidermal tissue. Superimposing the mass spectrometric and histological images appeared to indicate drug

  2. Rapid identification of vinca alkaloids by direct-injection electrospray ionisation tandem mass spectrometry and confirmation by high-performance liquid chromatography-mass spectrometry.

    PubMed

    Zhou, Hui; Tai, Yuanpo; Sun, Cuirong; Pan, Yuanjiang

    2005-01-01

    A simple and rapid method for the identification of Vinca alkaloids from a crude extract of Catharanthus roseus G. Don (Apocynaceae) by direct-injection electrospray ionisation (ESI) and tandem mass spectrometry (MS/MS) has been developed. The alkaloids vindoline, vindolidine, vincristine and vinblastine were evaluated in a commercial extract of C. roseus using this method. Catharanthine and its isomers 19S-vindolinine and vindolinine were detected in the commercial product by direct injection ESI/MS/MS and confirmed by preparation and by HPLC-ESI/MS. For the characterisation of different fragment fingerprints, ESI/MS/MS is a sensitive, rapid and convenient technique by which to identify some constituents in complex and mixed plant extracts. PMID:16223089

  3. Determination of chlorinated paraffins in sediments from the Firth of Clyde by gas chromatography with electron capture negative ionisation mass spectrometry and carbon skeleton analysis by gas chromatography with flame ionisation detection.

    PubMed

    Hussy, Ines; Webster, Lynda; Russell, Marie; Moffat, Colin

    2012-07-01

    Short chain chlorinated paraffins (SCCPs) are a group of persistent organic pollutants (POPs) of increasing concern, but are to date not widely investigated in the environment, largely due to the challenges involved in their quantification. Here, SCCPs were quantified in marine sediments from the Firth of Clyde, Scotland, by gas chromatography with electron capture negative ionisation mass spectrometry (GC-ECNIMS) and through carbon skeleton analysis by gas chromatography with flame ionisation detection (GC-FID), and the analytical challenges encountered are discussed. Concentrations in the sediments ranged from 0.4 to 69 μg kg(-1) when determined by GC-ECNIMS, and from 5.6 to 379 μg kg(-1) when determined by GC-FID. For 8 out of 11 samples, analysis by GC-FID gave higher results than analysis by GC-ECNIMS. Unexpected aspects of the analysis, such as the presence of high concentrations of longer chain chlorinated paraffins in the samples, are also presented. PMID:22417782

  4. Measurement of small ion beams by thermal ionisation mass spectrometry using new 10(13) Ohm resistors.

    PubMed

    Koornneef, J M; Bouman, C; Schwieters, J B; Davies, G R

    2014-03-28

    We tested 5 newly manufactured - prototype - 10(13)Ohm resistors in the feedback loop of Faraday cup amplifiers to measure small ion beams by Thermal Ionisation Mass Spectrometry (TIMS). The high Ohmic resistors installed in the TRITON Plus at the VU University Amsterdam theoretically have 10 times lower noise levels relative to the default 10(11)Ohm resistors. To investigate the precision and accuracy of analyses using these new amplifiers we measured Sr and Nd isotopes of reference standards at a range of ion currents (3.2×10(-16) to 1×10(-12) A, corresponding to intensities of 32 μV to 100 mV on a default 10(11)Ohm amplifier) and on small amounts of material (100 and 10 pg). Internal precision and external reproducibility for Sr and Nd isotope ratios are both better when collected on 10(13) compared 10(12)Ohm resistors and to the default 10(11)Ohm resistors. At an (87)Sr ion current of 3×10(-14) A (3 mV on a 10(11)Ohm amplifier) the internal precision (2 SE) of (87)Sr/(86)Sr is 5 times better for 10(13)Ohm resistors compared to 10(11)Ohm resistors. The external reproducibility (2 SD) at this beam intensity is 9 times better. Multiple 100 and 10 pg Sr standards, ran to exhaustion, yielded low (87)Sr/(86)Sr compared to the long term average (e.g. 10 pg average=0.710083±164 (n=11) instead of 0.710244±12, n=73). The average off-set for 10 pg standards can be explained by a loading blank contribution of 1.3 pg. In contrast, Nd data on 100 pg and 10 pg samples are accurate suggesting that Nd loading blanks do not compromise the data. The external reproducibility of (143)Nd/(144)Nd on 100 pg samples is 125 ppm and 3.3‰ on 10 pg samples (2 RSD=relative standard deviation, n=10). Thus, variability in Nd and Sr isotope ratios in the 4th decimal place, e.g. (143)Nd/(144)Nd 0.5110-0.5119 or (87)Sr/(86)Sr 0.7100-0.7109, can be resolved in 10 to 100 pg samples provided that the procedural blanks and chemical separation are optimal. For measurements in the beam

  5. Analysis of the monosaccharide composition of water-soluble polysaccharides from Sargassum fusiforme by high performance liquid chromatography/electrospray ionisation mass spectrometry.

    PubMed

    Wu, Xiaodan; Jiang, Wei; Lu, Jiajia; Yu, Ying; Wu, Bin

    2014-02-15

    Sargassum fusiforme (hijiki) is the well-known edible algae, whose polysaccharides have been proved to possess interesting bioactivities like antitumor, antioxidant, antimicrobial and immunomodulatory activities. A facile and sensitive method based on high-performance liquid chromatography method of pre-column derivatization with 1-phenyl-3-methyl-5-pyrazolone (PMP) coupled with electrospray ionisation mass spectrometry (HPLC/ESI-MS) has been established for the analysis of the monosaccharide composition of polysaccharides in S. fusiforme. Monosaccharides have been converted into PMP-labelled derivatives with aqueous ammonia as a catalyst at 70 °C for 30 min. The optimisation of the pre-column derivatization process was studied. The LODs of the monosaccharides were in the range from 0.01 to 0.02 nmol. PMP-labelled mixture of monosaccharides has been well separated by a reverse-phase HPLC and detected by on-line ESI-MS method under optimised conditions. The mobile phase of elution system was chosen as acetonitrile (solvent A) and 20mM aqueous ammonium acetate (solvent B) (pH 3.0) with Zorbax XDB-C18 column at 30 °C for the separation of the monosaccharide derivatives. Identification of the monosaccharides composition was carried out by analysis with mass spectral behaviour and chromatography characteristics of 1-phenyl-3-methyl-5-pyrazolone (PMP) labelled monosaccharides. All PMP-labelled derivatives display high chemical stabilities, whose regular MS fragmentation is specific for reducing labelled sugars. The result showed that the S. fusiforme polysaccharide consisted of mannose, glucose, galactose, xylose, fucose and glucuronic acid or galacturonic acid, or both uronic acids. PMID:24128572

  6. 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. PMID:27185142

  7. A derivatisation and liquid chromatography/electrospray ionisation multistage mass spectrometry method for the characterisation of naphthenic acids.

    PubMed

    Smith, B E; Rowland, S J

    2008-12-01

    Naphthenic acids (NAs) are partially uncharacterised complex mixtures of carboxylic acids, resulting from the microbial oxidation of petroleum hydrocarbons. They are associated with the fouling of pipelines and process equipment in oil production and with corrosion in oil refineries. As by-products of the rapidly expanding oil (tar) sands industries, NAs are also pollutants and have proved to be toxic to a range of organisms. They also have important beneficial uses as fungicides, tyre additives and, paradoxically, also in the manufacture of corrosion inhibitors. These features make the characterisation of NAs an important goal for analytical chemists. Here we describe the synthesis of amide derivatives of NAs for characterisation by liquid chromatography/electrospray ionisation multistage mass spectrometry (LC/ESI-MS(n)). The method was applied to commercially available carboxylic acids, novel synthetic NAs, commercial NAs refined from crude oils, crude oil NAs and Athabasca oil sands NAs. In addition to confirming the number of alicyclic rings and length of alkyl side chain substituents (confirming information from existing methods), the MS(n) results provided further structural information. Most important of these was the finding that bi- to polycyclic acids containing ethanoate side chains, in addition to alkyl substituents, were widespread amongst the oil and oil sands NAs. The latter NAs are known end members of the beta-oxidation of NAs with even carbon number alkanoate chains. Since such NA mixtures are toxic, they should be targets for bioremediation. Bioremediation of NAs can also be monitored better by application of the methods described herein. PMID:18988206

  8. Quantitative analysis of surfactant deposits on human skin by liquid chromatography/electrospray ionisation tandem mass spectrometry.

    PubMed

    Massey, Karen A; Snelling, Anna M; Nicolaou, Anna

    2010-05-15

    Surfactants are commonly used as cleansing agents and yet there are concerns that they may also have a role in skin irritation. The lack of suitable methods for the quantitative and qualitative analysis of surfactant deposition on skin has hindered the in-depth investigation of such effects. Here, we report the application of reversed-phase liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) assays for two surfactants commonly used in consumer products, namely sodium lauryl ether sulfate (SLES) and laurylamidopropyl betaine (LAPB), to a baseline study aiming to assess deposition levels on human skin. The linearity of the assays was established at 3-20 ng, with coefficient of variation below 5%. The detection limits were 100 pg for LAPB and 1 ng for SLES; quantitation limits were 500 pg for LAPB and 2.5 ng for SLES. The baseline study was conducted using a panel of 40 healthy volunteers. Skin extract samples were taken in triplicate from forearms, using ethanol. SLES was detected on most volunteers, with 75% of them having SLES deposits in the range of 100-600 ng/cm(2). LAPB was detected on the skin of all volunteers with 85% of them having deposit levels within the concentration range of 1-100 ng/cm(2). These results demonstrate the extent to which commonly used surfactants remain on the skin during the day. The analytical methods reported here can be applied to the investigation of surfactants in relation to general skin condition and to the development and optimisation of new consumer wash products. PMID:20391611

  9. 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. PMID:25644523

  10. Analysis of organophosphate flame retardant diester metabolites in human urine by liquid chromatography electrospray ionisation tandem mass spectrometry.

    PubMed

    Van den Eede, Nele; Neels, Hugo; Jorens, Philippe G; Covaci, Adrian

    2013-08-16

    A new analytical method was developed for the determination of dialkyl and diaryl phosphates (DAPs), which are metabolites of organophosphate triesters (PFRs), in human urine. Target DAPs included dibutyl phosphate (DBP), diphenyl phosphate (DPHP), bis(2-butoxyethyl) phosphate (BBOEP), bis(2-chloroethyl) phosphate (BCEP), bis(1-chloro-2-propyl) phosphate (BCPP), and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP). Sample preparation was based on solid phase extraction using a weak anion exchange sorbent (Oasis WAX). Although several instrumental techniques have been tested, best results were obtained with reversed phase liquid chromatography-negative electrospray ionisation tandem mass spectrometry (LC-ESI-MS/MS) taking the total analysis time into account. Method accuracy at 3ng/mL in pooled urine ranged between 69 and 119% (recovery), while inter-day imprecision (as relative standard deviation) was <31%. The performance of the LC-MS/MS method was compared to a method based on gas chromatography-electron impact tandem mass spectrometry (GC-MS/MS) and a good correlation (Pearson r=0.82, p<0.01) between the results of these two methods was obtained for DPHP. LC-MS/MS analysis was more suitable for DPHP and BBOEP with respective method limits of quantification (mLOQ) of 0.3 and 0.15ng/mL. In contrast, GC-MS/MS had a better sensitivity for BCEP, BCIPP, and BDCIPP, their respective mLOQs being 0.1, 0.06, 0.02ng/mL, compared to 1.2, 3.7, and 0.5ng/mL by LC-MS/MS. A set of urine samples from volunteers was analysed, in which DPHP was the major DAP metabolite. A significant increase of DPHP levels was observed in the group of smokers (geometric mean of 1.55ng/mL) compared to the non-smokers (geometric mean of 0.88ng/mL). Metabolic transformation of triphenyl phosphate to DPHP by metabolic enzymes induced in smokers could be an explanation for this observation. PMID:23849782

  11. Identification of N-glycans from Ebola virus glycoproteins by matrix-assisted laser desorption/ionisation time-of-flight and negative ion electrospray tandem mass spectrometry

    PubMed Central

    Ritchie, Gayle; Harvey, David J.; Stroeher, Ute; Feldmann, Friederike; Feldmann, Heinz; Wahl-Jensen, Victoria; Royle, Louise; Dwek, Raymond A.; Rudd, Pauline M.

    2012-01-01

    The larger fragment of the transmembrane glycoprotein (GP1) and the soluble glycoprotein (sGP) of Ebola virus were expressed in human embryonic kidney cells and the secreted products were purified from the supernatant for carbohydrate analysis. The N-glycans were released with PNGase F from within sodium dodecyl sulphate/polyacrylamide gel electrophoresis (SDS-PAGE) gels. Identification of the glycans was made with normal-phase high-performance liquid chromatography (HPLC), matrix-assisted laser desorption/ionisation mass spectrometry, negative ion electrospray ionisation fragmentation mass spectrometry and exoglycosidase digestion. Most glycans were complex bi-, tri-and tetra-antennary compounds with reduced amounts of galactose. No bisected compounds were detected. Triantennary glycans were branched on the 6-antenna; fucose was attached to the core GlcNAc residue. Sialylated glycans were present on sGP but were largely absent from GP1, the larger fragment of the transmembrane glycoprotein. Consistent with this was the generally higher level of processing of carbohydrates found on sGP as evidenced by a higher percentage of galactose and lower levels of high-mannose glycans than were found on GP1. These results confirm and expand previous findings on partial characterisation of the Ebola virus transmembrane glycoprotein. They represent the first detailed data on carbohydrate structures of the Ebola virus sGP. PMID:20131323

  12. Identification of phenolic constituents in red chicory salads (Cichorium intybus) by high-performance liquid chromatography with diode array detection and electrospray ionisation tandem mass spectrometry.

    PubMed

    Carazzone, Chiara; Mascherpa, Dora; Gazzani, Gabriella; Papetti, Adele

    2013-06-01

    Phenolic acids and flavonoids extracted from several types of Cichorium intybus var. silvestre salads ("Chioggia", "Treviso", "Treviso tardivo", and "Verona") were characterised by high-performance liquid chromatography-electrospray ionisation/mass spectrometry. Among the 64 compounds detected, several hydroxycinnamic acid derivatives including 8 mono- and dicaffeoylquinic acids, 3 tartaric acid derivatives, 31 flavonol and 2 flavone glycosides, as well as 10 anthocyanins were characterised based on UV spectra and MS(n) fragmentation patterns. Furthermore, several isomers of caffeic acid derivatives were distinguished for the first time by their specific mass spectral data. This is the first study reporting the glycosylation type and position of mono- and diglycosylated flavonoids in red salads. PMID:23411215

  13. Characterisation of weathered hydrocarbon wastes at contaminated sites by GC-simulated distillation and nitrous oxide chemical ionisation GC-MS, with implications for bioremediation.

    PubMed

    Pollard, Simon J T; Hrudey, Steve E; Rawluk, Marv; Fuhr, Bryan J

    2004-08-01

    An extended analytical characterisation of weathered hydrocarbons isolated from historically contaminated sites in Alberta is presented. The characterisation of soil extracts, chromatographically separated into component classes, by GC-simulated distillation and nitrous oxide (N2O) chemical ionisation (CI) GC-MS provides new insights into the composition of the residual oil at these sites, the principal partition medium for risk critical components. The combined polar and asphaltene content of representative soil extracts ranged from 40% w/w to 70% w/w of the oils encountered. An abundance of C14-C22 2-4 ring alicyclics, alkylbenzenes and benzocycloparaffins is prevalent within the saturate fractions of site soils. Implications for the partitioning of risk critical compounds at sites with weathered hydrocarbons and the practical application of bioremediation technologies are discussed. PMID:15292955

  14. Analysis of peptides and protein digests by reversed phase high performance liquid chromatography-electrospray ionisation mass spectrometry using neutral pH elution conditions.

    PubMed

    Yang, Yuanzhong; Boysen, Reinhard I; Chowdhury, Jamil; Alam, Asif; Hearn, Milton T W

    2015-05-01

    In this study, the advantages of carrying out the analysis of peptides and tryptic digests of proteins under gradient elution conditions at pH 6.5 by reversed-phase liquid chromatography (RP-HPLC) and in-line electrospray ionisation mass spectrometry (ESI-MS) are documented. For these RP separations, a double endcapped, bidentate anchored n-octadecyl wide pore silica adsorbent was employed in a capillary column format. Compared to the corresponding analysis of the same peptides and protein tryptic digests using low pH elution conditions for their RP-HPLC separation, this alternative approach provides improved selectivity and more efficient separation of these analytes, thus allowing a more sensitive identification of proteins at different abundance levels, i.e. more tryptic peptides from the same protein could be confidently identified, enabling higher sequence coverage of the protein to be obtained. This approach was further evaluated with very complex tryptic digests derived from a human plasma protein sample using an online two-dimensional (2D) strong cation-exchange (SCX)-RP-HPLC-ESI-MS/MS system. Again, at pH 6.5, with mobile phases of different compositions, improved chromatographic selectivities were obtained, concomitant with more sensitive on-line electrospray ionisation tandem mass spectrometric (ESI-MS/MS) analysis. As a consequence, more plasma proteins could be confidently identified, highlighting the potential of these RP-HPLC methods with elution at pH 6.5 to extend further the scope of proteomic investigations. PMID:25892073

  15. 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

  16. 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)

  17. 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. PMID:25585886

  18. Structural characterisation of tyrosine-nitrated peptides by ultraviolet and infrared matrix-assisted laser desorption/ionisation Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Petre, Brínduşa-Alina; Youhnovski, Nikolay; Lukkari, Juho; Weber, Reinhold; Przybylski, Michael

    2005-01-01

    Nitration of tyrosine residues in proteins may occur in cells upon oxidative stress and inflammation processes mediated through generation of reactive nitroxyl from peroxynitrite. Tyrosine nitration from oxidative pathways may generate cytotoxic species that cause protein dysfunction and pathogenesis. A number of protein nitrations in vivo have been reported and some specific Tyrosine nitration sites have been recently identified using mass spectrometric methods. High-resolution Fourier transform ion cyclotron resonance mass spectrometry (MALDI) FT-ICR-MS) is shown here to be a highly efficient method in the determination of protein nitrations. Following the identification of nitration of the catalytic site Tyr-430 residue of bovine prostacyclin synthase, we synthesised several model peptides containing both unmodified tyrosine and 3-nitro-tyrosine residues, using solid-phase peptide synthesis (SPPS). The structures of the nitrotyrosine peptides were characterised both by ESI- and by matrix-assisted laser desorption/ionisation (MALDI)-FT-ICR-MS, using a standard ultraviolet (UV) nitrogen nitrogen laser and a 2.97 microm Nd-YAG infrared laser. Using UV-MALDI-MS, 3-nitrotyrosyl-peptides were found to undergo extensive photochemical fragmentation at the nitrophenyl group, which may hamper or prevent the unequivocal identification of Tyr-nitrations in cellular proteins. In contrast, infrared-MALDI-FT-ICR-MS did not produce fragmentation of molecular ions of Tyr-nitrated peptides. PMID:16322657

  19. Comprehensive metabolic profiling of mono- and polyglutamated folates and their precursors in plant and animal tissue using liquid chromatography/negative ion electrospray ionisation tandem mass spectrometry.

    PubMed

    Garratt, Lee C; Ortori, Catharine A; Tucker, Gregory A; Sablitzky, Fred; Bennett, Malcolm J; Barrett, David A

    2005-01-01

    This work reports the use of reversed-phase ion-pair chromatography coupled to electrospray ionisation mass spectrometry for the simultaneous profiling of folate-based metabolites including natural folates, their polyglutamatyl derivatives and their biosynthetic precursors in plant and animal tissue. A simple sample preparation method, using 0.1% citric acid and ascorbic acid in ice-cold methanol, was used to extract and stabilise the folates, and three internal standards were used. Chromatography was on a C18 column using slow gradient elution with a mobile phase consisting of methanol/water with 5 mM dimethylhexylamine. Mass spectrometric detection was performed by multiple reaction monitoring in seven separate time windows in negative ion mode over the 25 min run time. Full, quantitative analysis was obtained for 16 folates and a 'semi-quantitative' analysis was possible for all other folates with up to eight conjugated glutamate residues by reference to structurally related calibration standards. The precision, accuracy and recovery of the method were generally within the accepted guidelines for a quantitative bioanalytical method and the method was linear over the range 0.2 to 10 ng of individual folate per sample. The method was applied to profile mono- and polyglutamated tetrahydrofolates (including subcellular analysis) in a range of plant species, including Arabidopsis, spinach, Brassica and wheat; the technique was also successfully applied to the profiling of folates in mouse tissue. PMID:16047318

  20. The hydroxylase component of soluble methane monooxygenase from Methylococcus capsulatus (Bath) exists in several forms as shown by electrospray-ionisation mass spectrometry.

    PubMed

    Buzy, A; Millar, A L; Legros, V; Wilkins, P C; Dalton, H; Jennings, K R

    1998-06-15

    The hydroxylase of the soluble methane monooxygenase from the bacterium Methylococcus capsulatus (Bath) has been investigated by means of electrospray-ionisation mass spectrometry (ESI-MS) and liquid chromatography ESI-MS (LC/ESI-MS). The hydroxylase is a non-heme diiron protein consisting of three pairs of non-identical subunits (alpha approximately 60 kDa, beta approximately 45 kDa and gamma approximately 20 kDa). Liquid chromatographic separation of the hydroxylase subunits was required before MS analysis in order to detect the alpha-subunit. The masses measured for the three subunits were found to disagree with those calculated from their gene sequences. Experiments involving the use of CNBr and trypsin cleavage followed by LC/ESI-MS and MS/MS analyses permitted the location and correction of errors in the sequences deduced from the use of cDNA. The ESI-MS results also showed that the alpha-subunit of the hydroxylase exists in multiple forms which result from cleavage of the protein. This observation explains a number of enigmatic features of the protein previously reported in the literature and illustrates the pivotal role of ESI-MS in complementing data obtained from molecular biology for the characterisation of the primary sequence of proteins. PMID:9688272

  1. 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

  2. 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

  3. Analysis of the bovine plasma proteome by matrix-assisted laser desorption/ionisation time-of-flight tandem mass spectrometry.

    PubMed

    Henning, Ann-Kristin; Groschup, Martin H; Mettenleiter, Thomas C; Karger, Axel

    2014-01-01

    In this study, the bovine plasma proteome was analysed using a three step protocol: (1) plasma was treated with a combinatorial peptide ligand library (CPLL) to assimilate the differences in concentrations of different proteins in raw plasma; (2) CPLL-treated material was fractionated by three standard electrophoretic separation techniques, and (3) samples were analysed by nano-liquid chromatography (nLC) matrix-assisted laser desorption/ionisation (MALDI) time-of-flight tandem (TOF/TOF) mass spectrometry. The efficiencies of three fractionation protocols for plasma proteome analysis were compared. After size fractionation by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), resolution of proteins was better and yields of identified proteins were higher than after charge-based fractionation by preparative gel-free isoelectric focussing. For proteins with isoelectric points >6 and molecular weights ⩾ 63 kDa, the best results were obtained with a 'shotgun' approach, in which the CPLL-treated plasma was digested and the peptides, rather than the proteins, were fractionated by gel-free isoelectric focussing. However, the three fractionation techniques were largely complementary, since only about one-third of the proteome was identified by each approach. PMID:24268478

  4. 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

  5. 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

  6. 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

  7. Analysis and characterisation of bovine oocyte and embryo biomarkers by matrix-assisted desorption ionisation mass spectrometry imaging.

    PubMed

    Gonçalves, Roseli F; Ferreira, Mónica S; de Oliveira, Diogo N; Canevarolo, Rafael; Achilles, Marcos A; D'Ercole, Daniela L; Bols, Peter E; Visintin, Jose A; Killian, Gary J; Catharino, Rodrigo R

    2016-03-01

    In the field of 'single cell analysis', many classical strategies like immunofluorescence and electron microscopy are the primary techniques of choice. However, these methodologies are time consuming and do not permit direct identification of specific molecular classes, such as lipids. In the present study, a novel mass spectrometry-based analytical approach was applied to bovine oocytes and embryos. This new metabolomics-based application uses mass spectrometry imaging (MSI), efficient data processing and multivariate data analysis. Metabolic fingerprinting (MF) was applied to the analysis of unfertilised oocytes, 2-, 4- and 8-cell embryos and blastocysts. A semiquantitative strategy for sphingomyelin [SM (16:0)+Na](+) (m/z 725) and phosphatidylcholine [PC (32:0)+Na](+) (m/z 756) was developed, showing that lipid concentration was useful for selecting the best metabolic biomarkers. This study demonstrates that a combination of MF, MSI features and chemometric analysis can be applied to discriminate cell stages, characterising specific biomarkers and relating them to developmental pathways. This information furthers our understanding of fertilisation and preimplantation events during bovine embryo development. PMID:25228254

  8. 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

  9. On-line process monitoring of coffee roasting by resonant laser ionisation time-of-flight mass spectrometry: bridging the gap from industrial batch roasting to flavour formation inside an individual coffee bean.

    PubMed

    Hertz-Schünemann, R; Dorfner, R; Yeretzian, C; Streibel, T; Zimmermann, R

    2013-12-01

    Resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOFMS) enables the fast and sensitive on-line monitoring of volatile organic compounds (VOC) formed during coffee roasting. On the one hand, REMPI-TOFMS was applied to monitor roasting gases of an industrial roaster (1500 kg/h capacity), with the aim of determining the roast degree in real-time from the transient chemical signature of VOCs. On the other hand, a previously developed μ-probe sampling device was used to analyse roasting gases from individual coffee beans. The aim was to explore fundamental processes at the individual bean level and link these to phenomena at the batch level. The pioneering single-bean experiments were conducted in two configurations: (1) VOCs formed inside a bean were sampled in situ, i.e. via a drilled μ-hole, from the interior, using a μ-probe (inside). (2) VOCs were sampled on-line in close vicinity of a single coffee bean's surface (outside). The focus was on VOCs originating from hydrolysis and pyrolytic degradation of chlorogenic acids, like feruloyl quinic acid and caffeoyl quinic acid. The single bean experiments revealed interesting phenomena. First, differences in time-intensity profiles between inside versus outside (time shift of maximum) were observed and tentatively linked to the permeability of the bean's cell walls material. Second, sharp bursts of some VOCs were observed, while others did exhibit smooth release curves. It is believed that these reflect a direct observation of bean popping during roasting. Finally, discrimination between Coffea arabica and Coffea canephora was demonstrated based on high-mass volatile markers, exclusively present in spectra of Coffea arabica. PMID:24338878

  10. Matrix-assisted laser desorption/ionisation-time of flight mass spectrometry: rapid identification of bacteria isolated from patients with cystic fibrosis.

    PubMed

    Baillie, S; Ireland, K; Warwick, S; Wareham, D; Wilks, M

    2013-01-01

    Despite extensive research into the diagnosis and management of cystic fibrosis (CF) over the past decades, sufferers still have a median life expectancy of less than 37 years. Respiratory tract infections have a significant role in increasing the morbidity and mortality of patients with CF via a progressive decline in lung function. Rapid identification of organisms recovered from CF sputum is necessary for effective management of respiratory tract infections; however, standard techniques of identification are slow, technically demanding and expensive. The aim of this study is to asses the suitability of matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF MS) in identifying bacteria isolated from the respiratory tract of patients with CF, and is assessed by testing the accuracy of MALDI-TOF MS in identifying samples from a reference collection of rare CF strains in conjunction with comparing MALDI-TOF MS and standard techniques in identifying clinical isolates from sputum samples of CF patients. MALDI-TOF MS accurately identified 100% of isolates from the reference collection of rare CF pathogens (EuroCare CF collection). The isolate identification given by MALDI-TOF MS agreed with that given by standard techniques for 479/481 (99.6%) clinical isolates obtained from respiratory samples provided by patients with CE In two (0.4%) of 481 samples there was a discrepancy in identification between MALDI-TOF MS and standard techniques. One organism was identified as Pseudomonas aeruginosa by MALDI-TOF but could only be identified by the laboratory's standard methods as of the Pseudomonas genus. The second organism was identified as P. beteli by MALDI-TOF MS and Stenotrophomonas maltophilia by standard methods. This study shows that MALDI-TOF MS is superior to standard techniques in providing cheap, rapid and accurate identification of CF sputum isolates. PMID:24400425

  11. Oral brush biopsy analysis by matrix assisted laser desorption/ionisation-time of flight mass spectrometry profiling--a pilot study.

    PubMed

    Remmerbach, Torsten W; Maurer, Katja; Janke, Sebastian; Schellenberger, Wolfgang; Eschrich, Klaus; Bertolini, Julia; Hofmann, Herbert; Rupf, Stefan

    2011-04-01

    Oral squamous cell carcinomas (OSCCs) often present as advanced tumours requiring aggressive local and regional therapy and result in significant functional impairment. The objective is to develop pre-symptomatic screening detection of OSCC by a brush biopsy method which is less invasive than the conventional biopsy for histology. Given the molecular heterogeneity of oral cancer, it is unlikely that even a panel of tumour markers would provide accurate diagnosis. Therefore, approaches such as the matrix-assisted-laser-desorption/ionisation-time-of-flight-mass-spectrometry (MALDI-TOF-MS) allow several biomarkers or peptide profile patterns to be simultaneously assessed. Brush biopsies from 27 patients with histology-proven OSCCs plus 40 biopsies from 10 healthy controls were collected. MALDI-TOF-MS profiling was performed and additional statistical analysis of the data was used to classify the disease status according to the biological behaviour of the lesion. For classification a support vector machine algorithm was trained using spectra of brush biopsy samples to distinguish healthy control patients from patients with histology-proven OSCC. MALDI-TOF-MS was able to distinguish between healthy patients and OSCC patients with a sensitivity of 100% and specificity of 93%. In summary, MALDI-TOF-MS in combination with sophisticated bioinformatic methods can distinguish OSCC patients from non-cancer controls with excellent sensitivity and specificity. Further improvement and validation of this approach is necessary to determine its feasibility to assist the pre-symptomatic detection of head and neck cancer screening in routine daily practice. PMID:21354855

  12. 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

  13. Homogeneous sample preparation for automated high throughput analysis with matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Onnerfjord, P; Ekström, S; Bergquist, J; Nilsson, J; Laurell, T; Marko-Varga, G

    1999-01-01

    This work presents a simple method for obtaining homogeneous sample surfaces in matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) for the automated analysis of peptides and proteins. The sample preparation method is based on applying the sample/matrix mixture onto a pre-deposited highly diluted matrix spot. The pre-deposited crystals act as seeds for the new sample containing crystals which become much smaller in size and more evenly distributed than with conventional methods. This 'seed-layer' method was developed, optimised and compared with the dried-droplet method using peptides and proteins in the 1000-20,000 Da range. The seed-layer method increases the surface homogeneity, spot to spot reproducibility and sample washability as compared with the commonly used dried-droplet method. This methodology is applicable to alpha-cyanohydroxycinnamic acid, sinapinic acid and ferulic acid, which all form homogeneous crystal surfaces. Within-spot variation and between-spot variation was investigated using statistics at a 95% confidence level (n = 36). The statistical values were generated from more than 5000 data points collected from 500 spectra. More than 90% of the sample locations results in high intensity spectra with relatively low standard deviations (RSDs). Typically obtained data showed an RSD of 19-35% within a sample spot as well as in-between spots for proteins, and an RSD of < or = 50% for peptides. Linear calibration curves were obtained within one order of magnitude using internal calibration with a point-RSD of 3% (n = 10). The sample homogeneity allows mass spectra (average of 16 laser shots) to be obtained on each individual sample within 15 sec, whereby a 100 spot target plate can be run in 25 min. High density target plates using the seed-layer method were prepared by spotting approximately 100 picoliter droplets onto the target, resulting in sample spots < or = 500 microns in diameter using a flow

  14. Quaternary structure of the extracellular haemoglobin of the lugworm Arenicola marina: a multi-angle-laser-light-scattering and electrospray-ionisation-mass-spectrometry analysis.

    PubMed

    Zal, F; Green, B N; Lallier, F H; Vinogradov, S N; Toulmond, A

    1997-01-15

    To elucidate the quaternary structure of the extracellular haemoglobin (Hb) of the marine polychaete Arenicola marina (lugworm) it was subjected to multi-angle laser-light scattering (MALLS) and to electrospray-ionisation mass spectrometry (ESI-MS). It was also subjected to SDS/PAGE analysis for comparative purposes. MALLS analysis gave a molecular mass of 3648 +/- 24 kDa and a gyration radius of 11.3 +/- 1.7 nm. Maximum entropy analysis of the multiply charged electrospray spectra of the native, dehaemed, reduced and carbamidomethylated Hb forms, provided its complete polypeptide chain and subunit composition. We found, in the reduced condition, eight globin chains of molecular masses 15952.5 Da (a1), 15974.8 Da (a2), 15920.9 Da (b1), 16020.1 Da (b2), 16036.2 Da (b3), 16664.8 Da (c), 16983.2 Da (d1), 17033.1 Da (d2) and two linker chains L1, 25174.1 Da, and L2, 26829.7 Da. In the native Hb, chains b, c, d occur as five disulphide-bonded trimer subunits T with masses of 49560.4 Da (T1), 49613.9 Da (T2), 49658.6 Da (T3), 49706.8 Da (T4), 49724.5 Da (T5). Linker chains L1 and L2 occur as one disulphide-bonded homodimer 2L1 (D1) of 50323.1 Da and one disulphide-bonded heterodimer L1-L2 (D2) of 51 981.5 Da. Polypeptide chains a and d possess one free cysteine residue and chains d possess an unusual total of five cysteine residues. Semi-quantitative analysis of ESI-MS data allowed us to propose the following model for the one-twelfth protomer: [(3a1)(3a2)2T] (T corresponding to either T3, T4 or T5). From electron micrograph data T1 and T2 are probably located at the centre of the molecule as mentioned in previous studies. The Hb would thus be composed of 198 polypeptide chains with 156 globin chains and 42 linker chains, each twelfth being in contact with 3.5 linker subunits, providing a total mass of 3682 kDa including haems in agreement with the experimental molecular mass determined by MALLS. From ESI-MS relative intensities and the model proposed above, the globin

  15. 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

  16. 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

  17. The ionisation energy of cyclopentadienone: a photoelectron-photoion coincidence study

    NASA Astrophysics Data System (ADS)

    Ormond, Thomas K.; Hemberger, Patrick; Troy, Tyler P.; Ahmed, Musahid; Stanton, John F.; Ellison, G. Barney

    2015-08-01

    Imaging photoelectron photoion coincidence (iPEPICO) spectra of cyclopentadienone (C5H4=O and C5D4=O) have been measured at the Swiss Light Source Synchrotron (Paul Scherrer Institute, Villigen, Switzerland) at the Vacuum Ultraviolet (VUV) Beamline. Complementary to the photoelectron spectra, photoionisation efficiency curves were measured with tunable VUV radiation at the Chemical Dynamics Beamline at the Advanced Light Source Synchrotron (Lawrence Berkeley National Laboratory, Berkeley, CA, USA). For both experiments, molecular beams diluted in argon and helium were generated from the vacuum flash pyrolysis of o-phenylene sulphite in a resistively heated microtubular SiC flow reactor. The Franck-Condon profiles and ionisation energies were calculated at the CCSD(T) level of theory, and are in excellent agreement with the observed iPEPICO spectra. The ionisation energies of both cyclopentadienone-d0, IE(C5H4=O), and cyclopentadienone-d4, IE(C5D4=O), were observed to be the same: 9.41 ± 0.01 eV. The mass-selected threshold photoelectron spectrum (ms-TPES) of cyclopentadienone reveals that the C=C stretch in the ground state of the cation is excited upon ionisation, supporting computational evidence that the ground state of the cation is ? 2A2, and is in agreement with previous studies. However, the previously reported ionisation potential has been improved considerably in this work. In addition, since o-benzoquinone (o-O=C6H4=O and o-O=C6D4=O) is also produced in this process, its ms-TPES has been recorded. From the iPEPICO and photoionisation efficiency spectra, we infer an adiabatic ionisation energy of IE(o-O=C6H4=O) = 9.3 ± 0.1 eV, but the rather structureless spectrum indicates a strong change in geometry upon ionisation making this value less reliable.

  18. Development of a RILIS ionisation scheme for gold at ISOLDE, CERN

    NASA Astrophysics Data System (ADS)

    Marsh, B. A.; Fedosseev, V. N.; Kosuri, P.

    2006-07-01

    At the ISOLDE on-line isotope separation facility, the resonance ionisation laser ion source (RILIS) can be used to ionise reaction products as they effuse from the target. The RILIS process of laser step-wise resonance ionisation of atoms in a hot metal cavity provides a highly element selective stage in the preparation of the radioactive ion beam. As a result, the ISOLDE mass separators can provide beams of a chosen isotope with greatly reduced isobaric contamination. With the addition of a new three-step ionisation scheme for gold, the RILIS is now capable of ionising 26 of the elements. The optimal scheme was determined during an extensive study of the atomic energy levels and auto-ionising states of gold, carried out by means of in-source resonance ionisation spectroscopy. Details of the ionisation scheme and a summary of the spectroscopy study are presented.

  19. Development of a RILIS ionisation scheme for gold at ISOLDE, CERN

    NASA Astrophysics Data System (ADS)

    Marsh, B. A.; Fedosseev, V. N.; Kosuri, P.

    At the ISOLDE on-line isotope separation facility, the resonance ionisation laser ion source (RILIS) can be used to ionise reaction products as they effuse from the target. The RILIS process of laser step-wise resonance ionisation of atoms in a hot metal cavity provides a highly element selective stage in the preparation of the radioactive ion beam. As a result, the ISOLDE mass separators can provide beams of a chosen isotope with greatly reduced isobaric contamination. With the addition of a new three-step ionisation scheme for gold, the RILIS is now capable of ionising 26 of the elements. The optimal scheme was determined during an extensive study of the atomic energy levels and auto-ionising states of gold, carried out by means of in-source resonance ionisation spectroscopy. Details of the ionisation scheme and a summary of the spectroscopy study are presented.

  20. 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

  1. Chemically assisted laser ablation ICP mass spectrometry.

    PubMed

    Hirata, Takafumi

    2003-01-15

    A new laser ablation technique combined with a chemical evaporation reaction has been developed for elemental ratio analysis of solid samples using an inductively coupled plasma mass spectrometer (ICPMS). Using a chemically assisted laser ablation (CIA) technique developed in this study, analytical repeatability of the elemental ratio measurement was successively improved. To evaluate the reliability of the CLA-ICPMS technique, Pb/U isotopic ratios were determined for zircon samples that have previously been analyzed by other techniques. Conventional laser ablation for Pb/U shows a serious elemental fractionation during ablation mainly due to the large difference in elemental volatility between Pb and U. In the case of Pb/U ratio measurement, a Freon R-134a gas (1,1,1,2-tetrafluoroethane) was introduced into the laser cell as a fluorination reactant. The Freon gas introduced into the laser cell reacts with the ablated sample U, and refractory U compounds are converted to a volatile U fluoride compound (UF6) under the high-temperature condition at the ablation site. This avoids the redeposition of U around the ablation pits. Although not all the U is reacted with Freon, formation of volatile UF compounds improves the transmission efficiency of U. Typical precision of the 206Pb/238U ratio measurement is 3-5% (2sigma) for NIST SRM 610 and Nancy 91500 zircon standard, and the U-Pb age data obtained here show good agreement within analytical uncertainties with the previously reported values. Since the observed Pb/U ratio for solid samples is relatively insensitive to laser power and ablation time, optimization of ablation conditions or acquisition parameters no longer needs to be performed on a sample-to-sample basis. PMID:12553756

  2. Automated chemical mass balance receptor modeling

    SciTech Connect

    Hanrahan, P.L.; Core, J.E.

    1986-09-01

    Chemical mass balance (CMB) receptor modeling provides alternative or complementary methods to dispersion models for apportioning particulate source impacts. This method estimates particulate source contributions at a receptor by comparing the chemistry of the ambient aerosol to the chemistry of the emissions from the various sources. To minimize demands on the analyst and facilitate the processing of large volumes of data, an initial version of an automated CMB model has been developed and is operational on an IBM personal computer as well as on a Harris mini-mainframe computer. Although it currently does not have all the features of the more interactive manual model, it does show promise for reducing man-power demands. The automated model is based on an early version of the EPA CMB model, which has been converted to run on an IBM-PC or compatible microcomputer. It uses the effective variance method. The interactive manual model is also undergoing modifications under an EPA contract. Some of these new features of the EPA model have been included in one version of the automated model.

  3. Mass spectrometric approaches for chemical characterisation of atmospheric aerosols: critical review of the most recent advances

    SciTech Connect

    Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2012-06-29

    This manuscript presents an overview of the most recent instrument developments for the field and laboratory applications of mass spectrometry (MS) to investigate the chemistry and physics of atmospheric aerosols. A range of MS instruments, employing different sample introduction methods, ionisation and mass detection techniques are used both for ‘online’ and ‘offline’ characterisation of aerosols. Online MS techniques enable detection of individual particles with simultaneous measurement of particle size distributions and aerodynamic characteristics and are ideally suited for field studies that require high temporal resolution. Offline MS techniques provide a means for detailed molecular-level analysis of aerosol samples, which is essential to gain fundamental knowledge regarding aerosol chemistry, mechanisms of particle formation and atmospheric aging. Combined, complementary MS techniques provide comprehensive information on the chemical composition, size, morphology and phase of aerosols – data of key importance for evaluating hygroscopic and optical properties of particles, their health effects, understanding their origins and atmospheric evolution. Over the last few years, developments and applications of MS techniques in aerosol research have expanded remarkably as evident by skyrocketing publication statistics. Finally, the goal of this review is to present the most recent developments in the field of aerosol mass spectrometry for the time period of late 2010 to early 2012, which have not been conveyed in previous reviews.

  4. 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. PMID:22644155

  5. A peptidomic approach for monitoring and characterising peptide cyanotoxins produced in Italian lakes by matrix-assisted laser desorption/ionisation and quadrupole time-of-flight mass spectrometry.

    PubMed

    Ferranti, Pasquale; Nasi, Antonella; Bruno, Milena; Basile, Adriana; Serpe, Luigi; Gallo, Pasquale

    2011-05-15

    In recent years, the occurrence of cyanobacterial blooms in eutrophic freshwaters has been described all over the world, including most European countries. Blooms of cyanobacteria may produce mixtures of toxic secondary metabolites, called cyanotoxins. Among these, the most studied are microcystins, a group of cyclic heptapeptides, because of their potent hepatotoxicity and activity as tumour promoters. Other peptide cyanotoxins have been described whose structure and toxicity have not been thoroughly studied. Herein we present a peptidomic approach aimed to characterise and quantify the peptide cyanotoxins produced in two Italian lakes, Averno and Albano. The procedure was based on matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry mass spectrometry (MALDI-TOF-MS) analysis for rapid detection and profiling of the peptide mixture complexity, combined with liquid chromatography/electrospray ionisation quadrupole time-of- flight tandem mass spectrometry (LC/ESI-Q-TOF-MS/MS) which provided unambiguous structural identification of the main compounds, as well as accurate quantitative analysis of microcystins. In the case of Lake Averno, a novel variant of microcystin-RR and two novel anabaenopeptin variants (Anabaenopeptins B(1) and Anabaenopeptin F(1)), presenting homoarginine in place of the commonly found arginine, were detected and characterised. In Lake Albano, the peculiar peptide patterns in different years were compared, as an example of the potentiality of the peptidomic approach for fast screening analysis, prior to fine structural analysis and determination of cyanotoxins, which included six novel aeruginosin variants. This approach allows for wide range monitoring of cyanobacteria blooms, and to collect data for evaluating possible health risks to consumers, through the panel of the compounds produced along different years. PMID:21488115

  6. 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

  7. Strong ionisation in carbon nanowires

    NASA Astrophysics Data System (ADS)

    Kaymak, V.; Pukhov, A.; Shlyaptsev, V. N.; Rocca, J. J.

    2016-04-01

    Surfaces covered with nanostructures, such as nanowire arrays, are shown to facilitate a significantly higher absorption of laser energy as compared to flat surfaces. Due to the efficient coupling of the laser energy, highly energetic electrons are produced, which in turn can emit intense ultrafast X-ray pulses. Full three dimensional PIC simulations are used to analyse the behaviour of arrays of carbon nanowires 400 nm in diameter, irradiated by a 400-nm laser pulse of 60-fs duration at FWHM and a vector potential of α0 = 18. We analyse the ionisation dynamics of the nanowires. The difference of the ionisation strength and structure between linearly and circularly polarised laser beam is investigated. The nanowires are found to be fully ionised after about 30 laser cycles. Circularly polarised light reveals a slightly stronger ionisation effect.

  8. Supersonic molecular beam-hyperthermal surface ionisation coupled with time-of-flight mass spectrometry applied to trace level detection of polynuclear aromatic hydrocarbons in drinking water for reduced sample preparation and analysis time.

    PubMed

    Davis, S C; Makarov, A A; Hughes, J D

    1999-01-01

    Analysis of sub-ppb levels of polynuclear aromatic hydrocarbons (PAHs) in drinking water by high performance liquid chromatography (HPLC) fluorescence detection typically requires large water samples and lengthy extraction procedures. The detection itself, although selective, does not give compound identity confirmation. Benchtop gas chromatography/mass spectrometry (GC/MS) systems operating in the more sensitive selected ion monitoring (SIM) acquisition mode discard spectral information and, when operating in scanning mode, are less sensitive and scan too slowly. The selectivity of hyperthermal surface ionisation (HSI), the high column flow rate capacity of the supersonic molecular beam (SMB) GC/MS interface, and the high acquisition rate of time-of-flight (TOF) mass analysis, are combined here to facilitate a rapid, specific and sensitive technique for the analysis of trace levels of PAHs in water. This work reports the advantages gained by using the GC/HSI-TOF system over the HPLC fluorescence method, and discusses in some detail the nature of the instrumentation used. PMID:10097402

  9. Chemical mass transfer in magmatic processes

    NASA Astrophysics Data System (ADS)

    Ghiorso, Mark S.

    1987-07-01

    Lasaga's (1982) Master Equation for crystal growth is solved for multicomponent systems in situations which allow for coupled diffusion of melt species. The structure of the solution is explored in some detail for the case of a constant diffusion coefficient matrix. Incorporating these results, the growth of plagioclase is modeled in undercooled tholeiitic melts by approximating interface growth rates with (1) a reduced growth rate function and with (2) calculated solid-liquid solution properties obtained from the silicate liquid solution model of Ghiorso et al. (1983; appendix of Ghiorso 1985). For this purpose algorithms are provided for estimating the liquidus temperature or the chemical affinity of a multicomponent solid solution precipitating from a complex melt of specified bulk composition. Compositional trends in initial solids produced by successive degrees of undercooling are opposite to those predicted in the binary system NaAlSi3O8-CaAl2Si2O8. Calculations suggest that the solid phase and interface melt compositions rapidly approach a “steady state” for a given degree of undercooling. Consequently, the overall isothermal growth rate of plagioclase forming from tholeiitic melts appears to be entirely diffusion controlled. In magmatic systems the multicomponent growth equations allow for the formation of oscillatory zoned crystals as a consequence of the “couplingr” between interface reaction kinetics and melt diffusion. The magnitude of this effect is largely dependent upon the asymmetry of the diffusion coefficient matrix. Methods are described to facilitate the calibration of diffusion matrices from experimental data on multicomponent penetration curves. Experimental results (Lesher and Walker 1986) on steady state Soret concentration profiles resulting from thermal diffusion in MORB and andesitic liquids are analyzed using the theory of multicomponent linear irreversible thermodynamics. Under conditions where the entropy production is

  10. 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

  11. Meson mass at real and imaginary chemical potentials

    NASA Astrophysics Data System (ADS)

    Kashiwa, Kouji; Matsuzaki, Masayuki; Kouno, Hiroaki; Sakai, Yuji; Yahiro, Masanobu

    2009-04-01

    Chemical-potential dependence of pi and sigma meson masses is analyzed at both real and imaginary chemical potentials, μR and μI, by using the Polyakov-loop extended Nambu-Jona-Lasinio (PNJL) model that possesses both the extended Z3 symmetry and chiral symmetry. In the μI region, the meson masses have the Roberge-Weiss periodicity. The μI dependence of the meson masses becomes stronger as temperature increases. We argue that meson masses and physical quantities in the μR region will be determined from lattice QCD data on meson masses in the μI region by using the PNJL model, if the data are measured in the future.

  12. Meson mass at real and imaginary chemical potentials

    SciTech Connect

    Kashiwa, Kouji; Sakai, Yuji; Yahiro, Masanobu; Matsuzaki, Masayuki; Kouno, Hiroaki

    2009-04-01

    Chemical-potential dependence of pi and sigma meson masses is analyzed at both real and imaginary chemical potentials, {mu}{sub R} and {mu}{sub I}, by using the Polyakov-loop extended Nambu-Jona-Lasinio (PNJL) model that possesses both the extended Z{sub 3} symmetry and chiral symmetry. In the {mu}{sub I} region, the meson masses have the Roberge-Weiss periodicity. The {mu}{sub I} dependence of the meson masses becomes stronger as temperature increases. We argue that meson masses and physical quantities in the {mu}{sub R} region will be determined from lattice QCD data on meson masses in the {mu}{sub I} region by using the PNJL model, if the data are measured in the future.

  13. Analysis of the volatile compounds of Teucrium flavum L. subsp. flavum (Lamiaceae) by headspace solid-phase microextraction coupled to gas chromatography with flame ionisation and mass spectrometric detection.

    PubMed

    Sagratini, Gianni; Maggi, Filippo; Bílek, Tomas; Papa, Fabrizio; Vittori, Sauro

    2012-01-01

    In this study, a headspace solid-phase microextraction (HS-SPME) method, in combination with gas chromatography flame ionisation detector and gas chromatography-mass spectrometry, has been developed for use in the analysis of the volatile compounds of Teucrium flavum L. subsp. flavum, a plant whose particular fragrance is used in the preparation of flavoured wines, bitters and liqueurs, or as a substitute for hops in the flavouring of beer. The tested fibres were 100 µm poly(dimethylsiloxane) (PDMS), the 65 µm PDMS/divinylbenzene (DVB) and 50/30 µm DVB-carboxen-PDMS. The best fibre was found to be PDMS when working in the following conditions: 60°C temperature, 30 min extraction time, 30 mg sample amount, 1 mm sample particle size. The HS-SPME method permitted the identification (95.8-97.8%) of 76 (dry) and 66 (fresh) different volatiles. In addition, we discovered that the presence of water in the sample can enhance the absolute quantity of alcoholic compounds such as 1-octen-3-ol and reduce the presence of esters such as methyl geranate. PMID:22077422

  14. 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...

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. Characterisation of serum transthyretin by electrospray ionisation-ion mobility mass spectrometry: Application to familial amyloidotic polyneuropathy type I (FAP-I).

    PubMed

    Pont, Laura; Benavente, Fernando; Vilaseca, Marta; Giménez, Estela; Sanz-Nebot, Victoria

    2015-11-01

    Transthyretin (TTR) is a homotetrameric protein which is known to misfold and aggregate causing different types of amyloidosis, such as familial amyloidotic polyneuropathy type I (FAP-I). FAP-I is associated with a specific TTR mutant variant (TTR (Met30)) that can be easily detected analysing the monomeric forms of the mutant protein. Meanwhile, the mechanism of protein aggregation onset, which could be triggered by structural changes on the native tetrameric protein complex, remains uncertain. We developed and described herein a new sample pretreatment based on immunoprecipitation (IP) to purify TTR from serum under non-denaturing conditions. Later, a nano-electrospray ionization-ion mobility mass spectrometry (nano-ESI-IM-MS or IM-MS) method was optimised to analyse the protein complexes in serum samples from healthy controls and FAP-I patients. IM-MS allowed separation and characterisation of tetrameric, trimeric and dimeric TTR gas ions due to their differential drift time, which is related to ion size and charge. The tetramer-to-dimer abundance ratio was differential between healthy controls and FAP-I patients (asymptomatic, symptomatic and an iatrogenic patient originally without the mutation who received a liver transplant from an FAP-I patient), and was also indicative of the effectiveness of liver transplantation as a treatment for FAP-I. PMID:26452950

  20. 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. PMID:23585910

  1. 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

  2. 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.

  3. 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.

  4. Aerosol chemical components in Alaska air masses: 1. Aged pollution

    NASA Astrophysics Data System (ADS)

    Shaw, Glenn E.

    1991-12-01

    A 4-year Alaska chemical data set of aerosols or "dust" in the air clearly reveals a mixture of distinct aerosol components with different and interesting chemical composition, one or two being ascribed to pollution imported to Alaska by winds all the way from other continents. Of particular note is a strong chemical contrast between what we imagine to be highly scavenged, orographically lifted, northern Pacific air (Pacific marine air mass) and stagnant Arctic air (polar air mass), the latter containing seasonal average concentrations of between 2-4 times the concentration of the former, at least for pollution markers noncrustal vanadium, noncrustal manganese, arsenic, selenium, bromine, and antimony. The findings concur our old discovery that Arctic air is persistently polluted (Arctic haze), but Pacific air is relatively clean, in spite of the fact that Alaska is downwind of major pollution sources in the Orient. This is remarkable. In this the first of a two-part paper, we concentrate on the pollution component found primarily during incursion of Arctic polar air. Two major occurrences of visual haze with optical depths of approximately 0.2 and elevated aerosol concentration lasting about a month (spring 1985 and 1986) were affiliated with strong incoming transport of polar air, temperatures ranging from 10° to 20°C below normal (polar air) and air trajectory hindcasts leading back to industrial pollution sources in Eurasia. These long-range transport pollution events brought metal-rich aerosol of removal-resistant submicron particles. The size, chemistry, and meteorology all strongly suggest the presence of a well-aged (10-100 day) polluted air mass. An important implication is that in spring a large fraction of the Arctic polar air mass becomes charged with by-products of industrial pollution. In this multiyear chemical data set one finds a notable summer-winter contrast, changing by factors of 2 to 4 for pollution markers As, Se, Sb, and noncrustal

  5. Application of gas chromatography-mass spectrometry and gas chromatography-tandem mass spectrometry to the analysis of chemical warfare samples, found to contain residues of the nerve agent sarin, sulphur mustard and their degradation products.

    PubMed

    Black, R M; Clarke, R J; Read, R W; Reid, M T

    1994-02-25

    Samples of clothing, grave debris, soil and munition fragments, collected from the Kurdish village of Birjinni, were analysed by GC-MS with selected ion monitoring (SIM) for traces of chemical warfare agents and their degradation products. Positive analyses were confirmed, where possible, by full scan mass spectra, or at low concentrations by additional GC-MS-SIM analysis using chemical ionisation, by higher resolution GC-MS-SIM, and by GC-tandem mass spectrometry using multiple reaction monitoring. Sulphur mustard and/or thiodiglycol were detected in six soil samples; isopropyl methylphosphonic acid and methylphosphonic acid, the hydrolysis products of the nerve agent sarin, were detected in six different soil samples. Trace amounts of intact sarin were detected on a painted metal fragment associated with one of these soil samples. The results demonstrate the application of different GC-MS and GC-MS-MS techniques to the unequivocal identification of chemical warfare agent residues in the environment at concentrations ranging from low ppb to ppm (w/w). They also provide the first documented unequivocal identification of nerve agent residues in environmental samples collected after a chemical attack. PMID:8143028

  6. Recombination processes in ionised plasmas

    NASA Astrophysics Data System (ADS)

    Bastin, Robert

    The observational analysis of astrophysical plasmas relies on accurate calculations of the atomic processes involved. The recombination spectra of singly ionised oxygen (O il) and carbon (C il) present excellent tools for investigating regions such as planetary nebulae and H II regions. In this thesis, detailed treatments of the recombination processes of both O II and C II are presented. Using the R-matrix solution to the close coupling equations, I present the results of accurate photoionisation calculations. Bound state energy levels are determined and oscillator strengths calculated for both species. Recombination coefficients were evalu ated for low n and 1, for C II in LS-coupling, and 0 II in intermediate coupling, taking particular care to treat resonances effectively. Sample photoionisation cross-sections are presented for both species, and compared to previous work. A complete radiative-cascade model is treated for both species, in order to determine line emissivities under nebular conditions at a wide range of temperatures and densities. Collisional effects are treated for C II, along with, for the first time, the effects of high temperature dielectronic recombination, allowing the modelling of regions of much higher electron temperature than previous work. The O II calculations were performed under intermediate coupling for the first time, allowing the effects of non-statistical popula tions of the parent ion fine-structure levels and dielectronic recombination onto bound states within this fine-structure to be taken into account in line emissivities. Detailed comparison with previous theoretical work was made for both species. The application of the C II and 0 n recombination spectra to determining tempera ture and densities from the observed spectra of a number of ionised nebulae is considered. The potential for using the new recombination spectra as diagnostic tools to solve some of the key problems in the study of ionised nebulae is demonstrated.

  7. Monitoring of human chemical signatures using membrane inlet mass spectrometry.

    PubMed

    Giannoukos, Stamatios; Brkić, Boris; Taylor, Stephen; France, Neil

    2014-01-21

    This work is an attempt to assist border security crackdown on illegal human immigration, by providing essential results on human chemical signatures. Data was obtained using a portable quadrupole mass spectrometer coupled with a membrane probe for volunteers of both genders and under different conditions in a container simulator. During experiments, participants were asked to follow various protocols while volatile organic compounds emitted from their breath, sweat, skin, and other biological excretes were continuously being monitored. Experimental setups using different membrane materials (both hydrophilic and hydrophobic) including heating of the sampling probe and sampling flow rates were examined. From our measurements, significant information was obtained for NH3, CO2, water, and volatile organic compounds levels, illustrating a human chemical profile and indicating human presence in a confined space. PMID:24377277

  8. 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. PMID:18321130

  9. 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

  10. Ionisation of C60: is it temperature dependent?

    NASA Astrophysics Data System (ADS)

    Baba, M. Sai; Narasimhan, T. S. Lakshmi; Balasubramanian, R.; Mathews, C. K.

    1994-01-01

    In a recent paper, Drewello [T. Drewello, W. Kratschmer, M. Fieber-Erdmann and A. Ding, Int. J. Mass Spectrom. Ion Processes, 124 (1993) R1] reported a temperature dependent ionisation cross section for the formation of C2+60 in their photoionisation dynamic studies on C60 using synchrotron radiation. To check this, the ratio of ion intensities of C2+60 to that of C60 was determined as a function of temperature of C60 samples using a Knudsen effusion mass spectrometer. Our results indicate the absence of any temperature dependence of cross section for the formation of C2+60 in the temperature range of measurement (600-800 K) using electron impact ionisation.

  11. 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.

  12. 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.

  13. A VLT VIMOS IFU study of the ionisation nebula surrounding the supersoft X-ray source CAL 83

    NASA Astrophysics Data System (ADS)

    Gruyters, P.; Exter, K.; Roberts, T. P.; Rappaport, S.

    2012-08-01

    Context. CAL 83 is a prototype of the class of Super Soft X-ray Sources (SXS). It is a binary consisting of a low mass secondary that is transferring mass onto a white dwarf primary and is the only known SXS surrounded by an ionisation nebula, made up of the interstellar medium (ISM) ionised by the source itself. We study this nebula using integral field spectroscopy. Aims: The study of ionised material can inform us about the source that is responsible for the ionisation, in a way that is complementary to studying the source directly. Since CAL 83 is the only SXS known with an ionisation nebula, we have an opportunity to see if such studies are as useful for SXSs as they have been for other X-ray ionised nebulae. We can use these data to compare to models of how CAL 83 should ionise its surroundings, based on what we know about the source emission spectrum and the physical conditions of the surrounding ISM. Methods: With the VIMOS integral field spectrograph we obtained spectra over a 25 × 25'' field of view, encompassing one quarter of the nebula. Emission line maps - H i, He II λ4686, [OIII] λλ4959,5007, [NII] λλ6548,5683, and [SII] λλ6716,6731 - are produced in order to study the morphology of the ionised gas. We include CAL 83 on diagrams of various diagnostic ion ratios to compare it to other X-ray ionised sources. Finally we computed some simple models of the ionised gas around CAL 83 and compare the predicted to the observed spectra. Results: CAL 83 appears to have a fairly standard ionisation nebula as far as the morphology goes: the edges where H is recombining are strong in the low stage ionisation lines and the central, clumpy regions are stronger in the higher stage ionisation lines. But the He ii emission is unusual in being confined to one side of CAL 83 rather than being homogeneously distributed as with the other ions. We model the CAL 83 nebula with cloudy using model parameters for SXSs found in the literature. The He ii emission does not

  14. Ionised outflows in z ~ 2.4 quasar host galaxies

    NASA Astrophysics Data System (ADS)

    Carniani, S.; Marconi, A.; Maiolino, R.; Balmaverde, B.; Brusa, M.; Cano-Díaz, M.; Cicone, C.; Comastri, A.; Cresci, G.; Fiore, F.; Feruglio, C.; La Franca, F.; Mainieri, V.; Mannucci, F.; Nagao, T.; Netzer, H.; Piconcelli, E.; Risaliti, G.; Schneider, R.; Shemmer, O.

    2015-08-01

    Aims: Outflows driven by active galactic nuclei (AGN) are invoked by galaxy evolutionary models to quench star formation and to explain the origin of the relations observed locally between super-massive black holes and their host galaxies. We here aim to detect extended ionised outflows in luminous quasars, where we expect the highest activity both in star formation and in black-hole accretion. Currently, there are only a few studies based on spatially resolved observations of outflows at high redshift, z > 2. Methods: We analysed a sample of six luminous (L > 1047 erg/s) quasars at z ~ 2.4, observed in H-band using the near-IR integral field spectrometer SINFONI at the VLT. We performed a kinematic analysis of the [Oiii] emission line at λ = 5007 Å. Results: We detect fast, spatially extended outflows in five out of six targets. [Oiii]λ5007 has a complex gas kinematic, with blue-shifted velocities of a few hundreds of km s-1 and line widths up to 1500 km s-1. Using the spectroastrometric method, we infer a size of the ionised outflows of up to ~2 kpc. The properties of the ionised outflows, mass outflow rate, momentum rate, and kinetic power, are correlated with the AGN luminosity. The increase in outflow rate with increasing AGN luminosity is consistent with the idea that a luminous AGN pushes away the surrounding gas through fast outflows that are driven by radiation pressure, which depends on the emitted luminosity. Conclusions: We derive mass outflow rates of about 6-700 M⊙ yr-1 for our sample, which are lower than those observed in molecular outflows. The physical properties of ionised outflows show dependences on AGN luminosity that are similar to those of molecular outflows, but indicate that the mass of ionised gas is lower than that of molecular outflows. Alternatively, this discrepancy between ionised and molecular outflows could be explained with different acceleration mechanisms. Based on Observations collected at the European Organisation for

  15. Profiling Reactive Metabolites via Chemical Trapping and Targeted Mass Spectrometry.

    PubMed

    Chang, Jae Won; Lee, Gihoon; Coukos, John S; Moellering, Raymond E

    2016-07-01

    Metabolomic profiling studies aim to provide a comprehensive, quantitative, and dynamic portrait of the endogenous metabolites in a biological system. While contemporary technologies permit routine profiling of many metabolites, intrinsically labile metabolites are often improperly measured or omitted from studies due to unwanted chemical transformations that occur during sample preparation or mass spectrometric analysis. The primary glycolytic metabolite 1,3-bisphosphoglyceric acid (1,3-BPG) typifies this class of metabolites, and, despite its central position in metabolism, has largely eluded analysis in profiling studies. Here we take advantage of the reactive acylphosphate group in 1,3-BPG to chemically trap the metabolite with hydroxylamine during metabolite isolation, enabling quantitative analysis by targeted LC-MS/MS. This approach is compatible with complex cellular metabolome, permits specific detection of the reactive (1,3-) instead of nonreactive (2,3-) BPG isomer, and has enabled direct analysis of dynamic 1,3-BPG levels resulting from perturbations to glucose processing. These studies confirmed that standard metabolomic methods misrepresent cellular 1,3-BPG levels in response to altered glucose metabolism and underscore the potential for chemical trapping to be used for other classes of reactive metabolites. PMID:27314642

  16. 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.

  17. Chemically peculiar stars as seen with 2MASS

    NASA Astrophysics Data System (ADS)

    Herdin, A.; Paunzen, E.; Netopil, M.

    2016-01-01

    Context. The chemically peculiar (CP) stars of the upper main sequence are well suited for investigating the impact of magnetic fields and diffusion on the surface layers of slowly rotating stars. They can even be traced in the Magellanic Clouds and are important to the understanding of the stellar formation and evolution. Aims: A systematic investigation of the near-infrared (NIR), 2MASS JHKs, photometry for the group of CP stars has never been performed. Nowadays, there is a great deal of data available in the NIR that reach very large distances. It is therefore very important for CP stars to be unambiguously detected in the NIR region and for these detections to be used to derive astrophysical parameters (age and mass) by applying isochrone fitting. Furthermore, we investigated whether the CP stars behave in a different way to normal-type stars in the various photometric diagrams. Methods: For our analysis, we carefully compiled a sample of CP and apparently normal (non-peculiar) type stars. Only stars for which high-quality (i.e. with low error levels), astrometric, and photometric data are available were chosen. In total, 639 normal and 622 CP stars were selected and further analysed. All stars were dereddened and calibrated in terms of the effective temperature and absolute magnitude (luminosity). Finally, isochrone fitting was applied. Results: No differences in the astrophysical parameters derived from 2MASS and Johnson UBV photometry were found. Furthermore, no statistical significant deviations from the normal type stars within several colour-colour and colour-magnitude diagrams were discovered. Therefore, it is not possible to detect new CP stars with the help of the photometric 2MASS colours only. A new effective temperature calibration, valid for all CP stars, using the (V - KS)0 colour was derived.

  18. Medical experimentation concerning chemical and biological weapons for mass destruction.

    PubMed

    Deutsch, Erwin

    2003-04-01

    This article is the text of a speech originally presented at the Second World Conference on Medical Ethics at Gijon, Spain, on 2 October 2002 under the title "Medical Experimentation Concerning Chemical and Biological Weapons for Mass Destruction: Clinical Design for New Smallpox Vaccines: Ethical and Legal Aspects." Experimentation on vaccines such as smallpox is subject to the usual ethical rules such as the need for informed consent. However, the participants will not often be at risk of catching the disease but expose themselves by taking part in the experimentation. Professor Deutsch explores the implications of this, including the position of vulnerable groups such as children, those with mental handicaps, and those acting under orders such as the miliary, the policy and fire officers. PMID:16211734

  19. 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.

  20. Peroxy radical observations using chemical ionization mass spectrometry during TOPSE

    NASA Astrophysics Data System (ADS)

    Cantrell, Christopher A.; Edwards, G. D.; Stephens, S.; Mauldin, L.; Kosciuch, E.; Zondlo, M.; Eisele, F.

    2003-03-01

    Peroxy radicals (HO2 + RO2) were measured by chemical conversion-chemical ionization mass spectroscopy in the TOPSE (Tropospheric Ozone Production about the Spring Equinox) campaign that took place February through May 2000. Instrumentation for these measurements was deployed on the NCAR/NSF C-130 aircraft that flew at latitudes from 40 to 85°N, and altitudes from the surface to 7.5 km over the North American continent. The measurements demonstrate the evolution of photochemical activity as time progresses through the study period due to increases in free radical source rates. The increase in average peroxy radical concentration moves northward as the maximum solar elevation and length of sunlit days increase. HOxROx (HO2 + RO2) concentrations are distributed lognormally with means of 11.5 and 7.8 pptv for the middle-latitude band (MLB) and high-latitude band (HLB), respectively. The observations agree well on average with steady state derived concentrations; measurement-model concentration ratios are 1.04 (MLB) and 0.94 (HLB). Concentrations within a given latitude band and altitude region sometimes appear to increase with NOx concentrations, but this correlation nearly disappears at low and moderate NOx levels when the data are parsed by radical production rate; lower radical levels are observed at the highest NOx levels measured (near 1 ppbv). These data are compared with results from other recent observations utilizing a variety of platforms.

  1. 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

  2. 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

  3. 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

  4. 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.

  5. Chemical tracers of episodic accretion in low-mass protostars

    NASA Astrophysics Data System (ADS)

    Visser, Ruud; Bergin, Edwin A.; Jørgensen, Jes K.

    2015-05-01

    Aims: Accretion rates in low-mass protostars can be highly variable in time. Each accretion burst is accompanied by a temporary increase in luminosity, heating up the circumstellar envelope and altering the chemical composition of the gas and dust. This paper aims to study such chemical effects and discusses the feasibility of using molecular spectroscopy as a tracer of episodic accretion rates and timescales. Methods: We simulate a strong accretion burst in a diverse sample of 25 spherical envelope models by increasing the luminosity to 100 times the observed value. Using a comprehensive gas-grain network, we follow the chemical evolution during the burst and for up to 105 yr after the system returns to quiescence. The resulting abundance profiles are fed into a line radiative transfer code to simulate rotational spectra of C18O, HCO+, H13CO+, and N2H+ at a series of time steps. We compare these spectra to observations taken from the literature and to previously unpublished data of HCO+ and N2H+ 6-5 from the Herschel Space Observatory. Results: The bursts are strong enough to evaporate CO throughout the envelope, which in turn enhances the abundance of HCO+ and reduces that of N2H+. After the burst, it takes 103-104 yr for CO to refreeze and for HCO+ and N2H+ to return to normal. The H2O snowline expands outwards by a factor of ~10 during the burst; afterwards, it contracts again on a timescale of 102-103 yr. The chemical effects of the burst remain visible in the rotational spectra for as long as 105 yr after the burst has ended, highlighting the importance of considering luminosity variations when analyzing molecular line observations in protostars. The spherical models are currently not accurate enough to derive robust timescales from single-dish observations. As follow-up work, we suggest that the models be calibrated against spatially resolved observations in order to identify the best tracers to be used for statistically significant source samples. Herschel

  6. Large Scale Chemical Cross-linking Mass Spectrometry Perspectives

    PubMed Central

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

    2014-01-01

    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

  7. CMB8: New software for chemical mass balance receptor modeling

    SciTech Connect

    Lewis, C.W.

    1997-12-31

    The Chemical Mass Balance (CMB) method for receptor modeling of ambient air pollutants has been in use for over two decades. over the past year the U.S. Environmental Protection Agency`s Office of Research and Development and Office of Air Quality Planning and standards have jointly sponsored the development of a new generation of CMB software, CMB8. Developmental work has been performed by the Desert Research Institute, Reno, NV. Changes embodied in CMB8 include (1) switch from a DOS-based to a Windows-based environment, (2) increased attention to volatile organic compounds (VOC) applications, (3) correction of some flaws in the previous version (CMB7), (4) more options for input and output data formats, (5) addition of a more accurate least squares computational algorithm, (6) a new treatment of source collinearity, (7) multiple defaults for sources and fitting species, and (8) choice of fitting criteria. Details of the changes and the procedure for obtaining CMB8 are given.

  8. Some characteristics of the glutathione cycle revealed by ionising and non-ionising electromagnetic radiation.

    PubMed

    Holt, J A

    1995-10-01

    The cyclic reaction of GSH-->GSSG-->GSH (designated R(exp) or R(e)) obeys the three specific features of life by producing energy in exponential quantities relative to time, is in effect irreversible and is inherited from generation to generation. In multicellular life, this reaction produces the energy for mitosis and is kept in controlled inactivity until needed to maintain perfection of form and function by energising mitosis. The immediate control of Re appears to be feedback process-dependent on the concentration of GSSG. Ultra high-frequency electromagnetic radiation of 434 MHz (UHF) will change Re from inactive to active and, in so doing, it causes resonance and/or fluorescence of the glutathione cycle which changes its radiosensitivity. Re is the primary direct target of ionising radiation and produces the energy for mitosis. Clinical observations suggest that, in the normal cell, Re is inactive and is not killed by 3 x 2700 rads or 6 x 1650 rads yet, when active, its sensitivity value (DO) is approximately 160 rads. Using the standard radiobiological equation of response to ionising radiation, it can be deduced that radiosensitive cancers have two or three Re units active per cell and radioresistance increases in proportion to the number of potentially active Re units per cell. Re appears to be the main cause of cancers' increased conductivity of electricity compared with normal tissue. In cancer therapy, UHF is the best radiosensitiser ever discovered (up to two or more decades). Re is also intelligent compared with non-exponential reactions but cannot be the basis of intellectual brain functions which must be based on non-electrical chemical processes. PMID:8577298

  9. PULSED POSITIVE ION NEGATIVE ION CHEMICAL IONIZATION MASS SPECTROMETRIC APPLICATONS TO ENVIRONMENTAL AND HAZARDOUS WASTE ANALYSIS

    EPA Science Inventory

    The simultaneous acquisition of both positive ion and negative ion data under chemical ionization mass spectrometric conditions can aid in the confirmation of assignments made by electron impact gas chromatography mass spectrometry or electron capture gas chromatography. Pulsed p...

  10. Study of the mechanism of direct laser desorption/ionisation for some small organic molecules (M < 400 Daltons).

    PubMed

    Benazouz; Hakim; Debrun; Strivay; Weber

    1999-12-15

    Aspects of direct laser desorption/ionisation have been studied for three molecules, aminotriazole (positive ion), dinoterb and ioxynil (negative ion). The samples are deposited on metallic substrates, and a nitrogen laser is used for desorption/ionisation; ion yields are measured with a time-of-flight mass spectrometer. Previous work had shown that ion yields can strongly vary from one substrate to another, and that this variation does not reflect the (calculated) metal surface temperatures. New results obtained in this work indicate that the desorption/ionisation mechanism is linked to the physical state of the substrate surface. Copyright 1999 John Wiley & Sons, Ltd. PMID:10567927

  11. 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...

  12. Violation of the mass-action law in dilute chemical systems.

    PubMed

    Brogioli, Doriano

    2013-11-14

    The mass-action law, which predicts the rates of chemical reactions, is widely used for modeling the kinetics of the chemical reactions and their stationary states, also for complex chemical reaction networks. However, violations of the mass-action equations have been reported in various cases: in confined systems with a small number of molecules, in non-ideally-stirred systems, when the reactions are limited by the diffusion, at high concentrations of reactants, or in chemical reaction networks with marginally stable mass-action equations. In this paper, I describe a new mechanism, leading to the violation of the mass-action equations, that takes place at a low concentration of at least one of the reactants; in this limit, the reaction rates can be easily inferred from the chemical reaction network. I propose that this mechanism underlies the replication stability of the hypercycles, a class of chemical reaction networks hypothetically connected with abiogenesis. I provide two simple examples of chemical reaction networks in which the mechanism leading to the violation of the mass-action law is present. I study the two chemical reaction networks by means of a simulation performed with a cellular automaton model. The results have a general validity and represent a limitation of the validity of the mass-action law, which has been overlooked up to now in the studies about the chemical reaction networks. PMID:24320249

  13. Violation of the mass-action law in dilute chemical systems

    NASA Astrophysics Data System (ADS)

    Brogioli, Doriano

    2013-11-01

    The mass-action law, which predicts the rates of chemical reactions, is widely used for modeling the kinetics of the chemical reactions and their stationary states, also for complex chemical reaction networks. However, violations of the mass-action equations have been reported in various cases: in confined systems with a small number of molecules, in non-ideally-stirred systems, when the reactions are limited by the diffusion, at high concentrations of reactants, or in chemical reaction networks with marginally stable mass-action equations. In this paper, I describe a new mechanism, leading to the violation of the mass-action equations, that takes place at a low concentration of at least one of the reactants; in this limit, the reaction rates can be easily inferred from the chemical reaction network. I propose that this mechanism underlies the replication stability of the hypercycles, a class of chemical reaction networks hypothetically connected with abiogenesis. I provide two simple examples of chemical reaction networks in which the mechanism leading to the violation of the mass-action law is present. I study the two chemical reaction networks by means of a simulation performed with a cellular automaton model. The results have a general validity and represent a limitation of the validity of the mass-action law, which has been overlooked up to now in the studies about the chemical reaction networks.

  14. Ionisation as indicator for cosmic ray acceleration

    NASA Astrophysics Data System (ADS)

    Schuppan, F.; Röken, C.; Fedrau, N.; Becker Tjus, J.

    2014-06-01

    Astrospheres and wind bubbles of massive stars are believed to be sources of cosmic rays with energies E ≲ 1 TeV. These particles are not directly detectable, but their impact on surrounding matter, in particular ionisation of atomic and molecular hydrogen, can lead to observable signatures. A correlation study of both gamma ray emission, induced by proton-proton interactions of cosmic ray protons with kinetic energies Ep ≥ 280 MeV with ambient hydrogen, and ionisation induced by cosmic ray protons of kinetic energies Ep < 280 MeV can be performed in order to study potential sources of (sub)TeV cosmic rays.

  15. EDDIX--a database of ionisation double differential cross sections.

    PubMed

    MacGibbon, J H; Emerson, S; Liamsuwan, T; Nikjoo, H

    2011-02-01

    The use of Monte Carlo track structure is a choice method in biophysical modelling and calculations. To precisely model 3D and 4D tracks, the cross section for the ionisation by an incoming ion, double differential in the outgoing electron energy and angle, is required. However, the double differential cross section cannot be theoretically modelled over the full range of parameters. To address this issue, a database of all available experimental data has been constructed. Currently, the database of Experimental Double Differential Ionisation Cross sections (EDDIX) contains over 1200 digitalised experimentally measured datasets from the 1960s to present date, covering all available ion species (hydrogen to uranium) and all available target species. Double differential cross sections are also presented with the aid of an eight parameter functions fitted to the cross sections. The parameters include projectile species and charge, target nuclear charge and atomic mass, projectile atomic mass and energy, electron energy and deflection angle. It is planned to freely distribute EDDIX and make it available to the radiation research community for use in the analytical and numerical modelling of track structure. PMID:21113060

  16. [Thyroid cancer following exposure to ionising radiation].

    PubMed

    Schlumberger, M; Chevillard, S; Ory, K; Dupuy, C; Le Guen, B; de Vathaire, F

    2011-08-01

    Exposure to ionising radiations during childhood increases the risk of thyroid cancer. Similar risk factors have been found after external radiation exposure or internal contamination with radioactive iodine isotopes. In case of contamination with radioiodines, administration of potassium iodide can prevent thyroid irradiation. PMID:21723770

  17. Mass deaths by gas or chemical poisoning. A historical perspective.

    PubMed

    Eckert, W G

    1991-06-01

    This review chronicles the characteristics of deliberate and accidental mass poisonings that occurred in World Wars I and II, in Bhopal, and in other historical cases up to and including modern wars. It also considers approaches to the investigation of such cases from the medicolegal as well as general standpoints. PMID:1882776

  18. Sensitivity of LHC experiments to exotic highly ionising particles

    NASA Astrophysics Data System (ADS)

    De Roeck, A.; Katre, A.; Mermod, P.; Milstead, D.; Sloan, T.

    2012-04-01

    The experiments at the Large Hadron Collider (LHC) are able to discover or set limits on the production of exotic particles with TeV-scale masses possessing values of electric and/or magnetic charge such that they behave as highly ionising particles (HIPs). In this paper the sensitivity of the LHC experiments to HIP production is discussed in detail. It is shown that a number of different detection methods are required to investigate as fully as possible the charge-mass range. These include direct detection as the HIPs pass through either passive or active detectors and, in the case of magnetically charged objects, the so-called induction method with which magnetic monopoles which stop in accelerator and detector material could be observed. The benefit of using complementary approaches to HIP detection is discussed.

  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. 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

  1. 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.

  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. PMID:22184221

  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. 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.

  5. Plasma mass spectrometry as a detector for chemical speciation studies.

    PubMed

    Tomlinson, M J; Lin, L; Caruso, J A

    1995-03-01

    Inductively coupled plasma mass spectrometry (ICP-MS), when coupled with the unique separating power of various chromatographic techniques, allows the detection of various elements at ultra-trace levels. The investigation of various toxic elements of environmental concern coupling relatively recent techniques, such as supercritical fluid chromatography (SFC) and capillary zone electrophoresis (CZE), to ICP-MS, is discussed. Comparisons have been made with detection limits obtained by using the flame ionization detector. The conventional technique of liquid chromatography for the speciation of vanadium, chromium and nickel is also discussed. PMID:7741220

  6. 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. PMID:17517363

  7. REVIEW OF VOLATILE ORGANIC COMPOUND SOURCE APPORTIONMENT BY CHEMICAL MASS BALANCE. (R826237)

    EPA Science Inventory

    The chemical mass balance (CMB) receptor model has apportioned volatile organic compounds (VOCs) in more than 20 urban areas, mostly in the United States. These applications differ in terms of the total fraction apportioned, the calculation method, the chemical compounds used ...

  8. 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

  9. 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.

  10. 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

  11. Aerosol chemical elemental mass concentration at lower free troposphere

    NASA Astrophysics Data System (ADS)

    do Carmo Freitas, Maria; Dionísio, Isabel; Fialho, Paulo; Barata, Filipe

    2007-08-01

    This paper shows the use of Instrumental neutron activation analysis (INAA) technique to determine elemental masses collected by a seven-wavelength Aethalometer instrument at the summit of Pico mountain in the Azorean archipelago, situated in the Central North Atlantic Ocean. Each sample corresponds to air particulate matter measured continuously for periods of approximately 24 h taken from 14th July 2001 through 14th July 2002. The statistical analysis of the coefficients of correlation between all the elements identified, permitted to establish six groups that could potentially be associated with the type of source responsible for the aerosol sampled in the lower free troposphere at the Azorean archipelago. Calculation of the synoptic back trajectories helped to corroborate the use of the iron/cesium relation as a tracer for the Saharan dust aerosol. It was demonstrated that INAA constituted an important tool to identify these events.

  12. Applications of Mass Spectrometry in Investigations of Alleged Use of Chemical Warfare Agents

    NASA Astrophysics Data System (ADS)

    Read, Robert W.

    Chemical warfare agents were used extensively throughout the twentieth century. Many such uses are well documented; however some allegations of use of chemical warfare agents were not easily confirmed. During the early 1980s interest developed into investigation of alleged use by analytical techniques, particularly mass spectrometry. Since that time, many combined chromatographic - mass spectrometric methods have been developed, both for application to the analysis of environmental and biomedical samples and for investigation of physiological interactions of chemical warfare agents. Examples are given of some of the investigations in which the author has been involved, including those into Yellow Rain and uses of chemical warfare agents in Iraq and Iran. These examples illustrate the use of combined chromatographic-mass spectrometric methods and emphasise the importance of controls in analytical investigations.

  13. 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. PMID:16024060

  14. 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.

  15. 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

  16. Coupled sulfur isotopic and chemical mass transfer modeling: Approach and application to dynamic hydrothermal processes

    SciTech Connect

    Janecky, D.R.

    1988-09-21

    A computational modeling code (EQPSreverse arrowS) has been developed to examine sulfur isotopic distribution pathways coupled with calculations of chemical mass transfer pathways. A post processor approach to EQ6 calculations was chosen so that a variety of isotopic pathways could be examined for each reaction pathway. Two types of major bounding conditions were implemented: (1) equilibrium isotopic exchange between sulfate and sulfide species or exchange only accompanying chemical reduction and oxidation events, and (2) existence or lack of isotopic exchange between solution species and precipitated minerals, parallel to the open and closed chemical system formulations of chemical mass transfer modeling codes. All of the chemical data necessary to explicitly calculate isotopic distribution pathways is generated by most mass transfer modeling codes and can be input to the EQPS code. Routines are built in to directly handle EQ6 tabular files. Chemical reaction models of seafloor hydrothermal vent processes and accompanying sulfur isotopic distribution pathways illustrate the capabilities of coupling EQPSreverse arrowS with EQ6 calculations, including the extent of differences that can exist due to the isotopic bounding condition assumptions described above. 11 refs., 2 figs.

  17. Chemical Aspects of the Extractive Methods of Ambient Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Badu-Tawiah, Abraham K.; Eberlin, Livia S.; Ouyang, Zheng; Cooks, R. Graham

    2013-04-01

    Ambient ionization techniques allow complex chemical samples to be analyzed in their native state with minimal sample preparation. This brings the obvious advantages of simplicity, speed, and versatility to mass spectrometry: Desorption electrospray ionization (DESI), for example, is used in chemical imaging for tumor margin diagnosis. This review on the extractive methods of ambient ionization focuses on chemical aspects, mechanistic considerations, and the accelerated chemical reactions occurring in charged liquid droplets generated in the spray process. DESI uses high-velocity solvent droplets to extract analytes from surfaces. Nano-DESI employs liquid microjunctions for analyte dissolution, whereas paper-spray ionization uses DC potentials applied to wet porous material such as paper or biological tissue to field emit charged analyte-containing solvent droplets. These methods also operate in a reactive mode in which added reagents allow derivatization during ionization. The accelerated reaction rates seen in charged microdroplets are useful in small-scale rapid chemical synthesis.

  18. 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

  19. Field-deployed underwater mass spectrometers for investigations of transient chemical systems.

    PubMed

    Kibelka, Gottfried P G; Timothy Short, R; Toler, Strawn K; Edkins, John E; Byrne, Robert H

    2004-11-15

    The mass spectrometer developments and underwater deployments described in this work are directed toward observations of important reactive and influential inorganic and organic chemicals. Mass spectrometer systems for measurement of dissolved gases and volatile hydrocarbons were created by coupling a membrane analyte-introduction system with linear quadrupole and ion trap mass analyzers. For molecular masses up to 100amu, the in situ quadrupole system has detection limits on the order of 1-5ppb. For masses up to approximately 300amu, the underwater ion trap system detects many volatile hydrocarbons at concentrations below 1ppb. Both instruments can function autonomously or via interactive communications from a remote control site. Continuous operations can be sustained for up to approximately 12 days. Deployments have initially involved shallow water proof-of-concept operations at depths less than 30m. Future modifications are planned that will allow operational depths to 200m. PMID:18969697

  20. 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.

  1. MICHTOX: A MASS BALANCE AND BIOACCUMULATION MODEL FOR TOXIC CHEMICALS IN LAKE MICHIGAN

    EPA Science Inventory

    MICHTOX is a toxic chemical mass balance and bioaccumulation model for Lake Michigan. It was developed for USEPA's Region V in support of the Lake Michigan Lake-wide Management Plan (LaMP) to provide guidance on expected water quality improvements in response to critical pollutan...

  2. PENTACHLOROPHENOL IN THE ENVIRONMENT: EVIDENCE FOR ITS ORIGIN FROM COMMERCIAL PENTACHLOROPHENOL BY NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY

    EPA Science Inventory

    Commercial pentachlorophenol (PCP) contains significant quantities of tetrachlorophenol (TCP). The occurrence of TCP in environmental samples provides a chemical marker for PCP originating from commercial formulations. Negative chemical ionization mass spectrometry has been used ...

  3. PENTACHLOROPHENOL IN THE ENVIRONMENT. EVIDENCE FOR ITS ORIGIN FROM COMMERCIAL PENTACHLOROPHENOL BY NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY

    EPA Science Inventory

    Commercial pentachlorophenol (PCP) contains significant quantities of tetrachlorophenol (TCP). The occurrence of TCP in environmental samples provides a chemical marker for PCP originating from commercial formulations. Negative chemical ionization mass spectrometry has been used ...

  4. Phase diagram of dynamical twisted-mass Wilson fermions at finite isospin chemical potential

    NASA Astrophysics Data System (ADS)

    Janssen, Oliver; Kieburg, Mario; Splittorff, K.; Verbaarschot, Jacobus J. M.; Zafeiropoulos, Savvas

    2016-05-01

    We consider the phase diagram of twisted-mass Wilson fermions of two-flavor QCD in the parameter space of the quark mass, the isospin chemical potential, the twist angle and the lattice spacing. This work extends earlier studies in the continuum and those at zero chemical potential. We evaluate the phase diagram as well as the spectrum of the (pseudo-)Goldstone bosons using the chiral Lagrangian for twisted-mass Wilson fermions at nonzero isospin chemical potential. The phases are obtained from a mean field analysis. At zero twist angle we find that already an infinitesimal isospin chemical potential destroys the Aoki phase. The reason is that in this phase we have massless Goldstone bosons with a nonzero isospin charge. At finite twist angle, only two different phases are present—one phase which is continuously connected to the Bose condensed phase at nonzero chemical potential, and another phase which is continuously connected to the normal phase. For either zero or maximal twist, the phase diagram is more complicated, as the saddle-point equations allow for more solutions.

  5. The delayed contribution of low and intermediate mass stars to chemical galactic enrichment: An analytical approach

    NASA Astrophysics Data System (ADS)

    Franco, I.; Carigi, L.

    2008-10-01

    We find a new analytical solution for the chemical evolution equations, taking into account the delayed contribution of all low and intermediate mass stars (LIMS) as one representative star that enriches the interstellar medium. This solution is built only for star formation rate proportional to the gas mass in a closed box model. We obtain increasing C/O and N/O ratios with increasing O/H, behavior impossible to match with the Instantaneous Recycling Approximation (IRA). Our results, obtained by two analytical equations, are very similar to those found by numerical models that consider the lifetimes of each star. This delayed model reproduces successfully the evolution of the C/O-O/H and Y - O relations in the solar vicinity. This analytical approximation is a useful tool to study the chemical evolution of elements produced by LIMS when a galactic chemical evolutionary code is not available.

  6. Quantification of dimethindene in plasma by gas chromatography-mass fragmentography using ammonia chemical ionization.

    PubMed

    Kauert, G; Herrle, I; Wermeille, M

    1993-08-11

    A gas chromatographic-mass fragmentographic method using ammonia chemical ionization for the determination of dimethindene in human plasma is described. The drug was isolated from plasma by liquid-liquid extraction with hexane-2-methylbutanol. Plasma components were separated on a capillary column coated with chemically bonded methyl silicone. For detection of dimethindene, its quasi-molecular ion (M + H+) was mass fragmentographically monitored after chemical ionization with ammonia as reagent gas. Dimethindene was quantified using methaqualone as the internal standard: the quantification limit in plasma was 0.2 ng/ml, the within-run precision was 8.0% and the inter-run precision 5.6%. The plasma concentration-time profile was established after a single dose of 4 mg of dimethindene with an average maximum concentration of 5.5 ng/ml, detectable up to 48 h post application. PMID:8408399

  7. Determination of structure parameters in molecular tunnelling ionisation model

    NASA Astrophysics Data System (ADS)

    Wang, Jun-Ping; Zhao, Song-Feng; Zhang, Cai-Rong; Li, Wei; Zhou, Xiao-Xin

    2014-04-01

    We extracted the accurate structure parameters in a molecular tunnelling ionisation model (the so-called MO-ADK model) for 23 selected linear molecules including some inner orbitals. The molecular wave functions with the correct asymptotic behaviour are obtained by solving the time-independent Schrödinger equation with B-spline functions and molecular potentials numerically constructed using the modified Leeuwen-Baerends (LBα) model. We show that the orientation-dependent ionisation rate reflects the shape of the ionising orbitals in general. The influences of the Stark shifts of the energy levels on the orientation-dependent ionisation rates of the polar molecules are studied. We also examine the angle-dependent ionisation rates (or probabilities) based on the MO-ADK model by comparing with the molecular strong-field approximation calculations and with recent experimental measurements.

  8. 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.

  9. 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.

  10. Theoretical investigation of the ultrafast dissociation of ionised biomolecules immersed in water: direct and indirect effects.

    PubMed

    Gaigeot, M-P; Lopez-Tarifa, P; Martin, F; Alcami, M; Vuilleumier, R; Tavernelli, I; Hervé du Penhoat, M-A; Politis, M-F

    2010-01-01

    Theoretical simulations are particularly well suited to investigate, at a molecular level, direct and indirect effects of ionising radiations in DNA, as in the particular case of irradiation by swift heavy ions such as those used in hadron therapy. In the past recent years, we have developed the modeling at the microscopic level of the early stages of the Coulomb explosion of DNA molecules immersed in liquid water that follows the irradiation by swift heavy ions. To that end, Time-Dependent Density Functional Theory molecular dynamics simulations (TD-DFT MD) have been developed where localised Wannier orbitals are propagated. This latter enables to separate molecular orbitals of each water molecule from the molecular orbitals of the biomolecule. Our main objective is to demonstrate that the double ionisation of one molecule of the liquid sample, either one water molecule from the solvent or the biomolecule, may be in some cases responsible for the formation of an atomic oxygen as a direct consequence of the molecule Coulomb explosion. Our hypothesis is that the molecular double ionisation arising from irradiation by swift heavy ions (about 10% of ionisation events by ions whose velocity is about the third of speed of light), as a primary event, though maybe less probable than other events resulting from the electronic cascading (for instance, electronic excitations, electron attachments), may be systematically more damageable (and more lethal), as supported by experiments that have been carried out in our group in the 1990s (in studies of damages created by K holes in DNA). The chemical reactivity of the produced atomic oxygen with other radicals present in the medium will ultimately lead to chemical products that are harmful to DNA. In the present paper, we review our theoretical methodology in an attempt that the community be familiar with our new approach. Results on the production of atomic oxygen as a result of the double ionisation of water or as a result of

  11. Non Ionising Radiation as a Non Chemical Strategy in Regenerative Medicine: Ca2+-ICR “In Vitro” Effect on Neuronal Differentiation and Tumorigenicity Modulation in NT2 Cells

    PubMed Central

    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 (Ca2+-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 Ca2+-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 Ca2+-ICR frequency is able to induce differentiation and reduction of tumorigenicity in NT2 exposed cells suggesting a new potential therapeutic use in regenerative medicine. PMID:23585910

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. Ionising radiation: are orthopaedic surgeons at risk?

    PubMed Central

    Smith, G. L.; Briggs, T. W.; Lavy, C. B.; Nordeen, H.

    1992-01-01

    Modern orthopaedic trauma practice involves increased exposure of the surgeon to ionising radiation. However, there have been no studies to investigate whether the doses received are within limits for non-classified workers. In this study, whole body, eye and extremity, namely hand, doses were measured in six orthopaedic surgeons during trauma cases requiring the use of X-rays in theatre. None of the subjects approached the recommended maximum dose levels for either the whole body, eyes or hands. This finding is reassuring. In orthopaedics, the limiting dose is that to the hands. This differs from previously studied groups, such as radiologists and cardiologists, in whom the limiting factor is the dose to the lens of the eye. Although current precautions appear to be adequate, safe practice in the future will depend on continuing vigilance and repetition of studies similar to this one as techniques and workloads change. PMID:1416705

  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. Small molecule ambient mass spectrometry imaging by infrared laser ablation metastable-induced chemical ionization.

    PubMed

    Galhena, Asiri S; Harris, Glenn A; Nyadong, Leonard; Murray, Kermit K; Fernández, Facundo M

    2010-03-15

    Presented here is a novel ambient ion source termed infrared laser ablation metastable-induced chemical ionization (IR-LAMICI). IR-LAMICI integrates IR laser ablation and direct analysis in real time (DART)-type metastable-induced chemical ionization for open air mass spectrometry (MS) ionization. The ion generation in the IR-LAMICI source is a two step process. First, IR laser pulses impinge the sample surface ablating surface material. Second, a portion of ablated material reacts with the metastable reactive plume facilitating gas-phase chemical ionization of analyte molecules generating protonated or deprotonated species in positive and negative ion modes, respectively. The successful coupling of IR-laser ablation with metastable-induced chemical ionization resulted in an ambient plasma-based spatially resolved small molecule imaging platform for mass spectrometry (MS). The analytical capabilities of IR-LAMICI are explored by imaging pharmaceutical tablets, screening counterfeit drugs, and probing algal tissue surfaces for natural products. The resolution of a chemical image is determined by the crater size produced with each laser pulse but not by the size of the metastable gas jet. The detection limits for an active pharmaceutical ingredient (acetaminophen) using the IR-LAMICI source is calculated to be low picograms. Furthermore, three-dimensional computational fluid dynamic simulations showed improvements in the IR-LAMICI ion source are possible. PMID:20155978

  20. [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. PMID:16037657

  1. 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/).

  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. PMID:27260452

  3. 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

  4. 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.

  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. Generating Porosity in the Critical Zone: Does Volumetric Strain Dominate Chemical Mass Loss?

    NASA Astrophysics Data System (ADS)

    Hayes, J. L.; Riebe, C. S.; Holbrook, W. S.; Hartsough, P. C.

    2015-12-01

    The opening of pore space by weathering near Earth's surface influences a broad array of hydrological and biogeochemical processes, including water storage, surface-groundwater interactions, and nutrient cycling. Understanding how porosity is generated by physical and chemical processes is therefore a fundamental challenge in critical zone science. However, the relative importance and spatial variability of mechanisms that generate porosity remain poorly understood, because the subsurface is hidden from direct observation except by drilling and geophysical measurements. Here we use observations from both drilling and geophysics to quantify the relative importance of volumetric strain and chemical mass loss in the Southern Sierra Critical Zone Observatory. Our results from cores of saprolite show that porosity decreases with depth from 0.65 to 0.35 in the top 11 meters of saprolite. Although seismic refraction surveys reveal velocities that correctly predict the porosity variations, they cannot distinguish between volumetric strain and chemical mass losses. To overcome this limitation, we quantified bulk density and immobile element concentrations in our samples of saprolite. We found that volumetric strain decreases with depth from 1.1 to 0.3. Conversely, the overall mass loss due to chemical weathering shows no trend with depth. Together these results suggest that the changes in porosity are due to physical rather than chemical processes in the upper 11 meters. However neither bioturbation nor frost cracking are likely to extend so deep. Moreover, the paucity of hydrous minerals in the bedrock implies that mineral expansion cannot explain the high volumetric strain in the saprolite. Our results are consistent with porosity generated by the opening of fractures due to the release of confining stress during exhumation of bedrock.

  7. Toward a Chemical Evolutionary Sequence in High-Mass Star Formation

    NASA Astrophysics Data System (ADS)

    Gerner, Thomas; Beuther, Henrik; Semenov, Dmitry; Linz, Hendrik; Vasyunina, Tatiana; Henning, Thomas

    Understanding the chemical evolution of young (high-mass) star-forming regions is a central topic in star formation research. The chemistry plays two main roles here: to study the evolution from simple to complex molecules, and to investigate the underlying physical processes. With these aims in mind, we observed a diverse sample of 60 high-mass star-forming regions in different evolutionary stages. In the early phase, quiescent Infrared Dark Clouds (IRDCs), consisting of cold and dense gas and dust, and emitting mainly at (sub-)millimeter wavelength, are formed. In the next phase, the so called High Mass Protostellar Objects (HMPOs) form, which host a central, likely still accreting protostar and already show emission at mid-infrared wavelengths. In the Hot Molecular Core phase (HMC) the central source heats up the surrounding environment, evaporating molecular-rich ices, which gives rise to a rich chemistry leading to complex molecules such as long carbon chains. Finally the UV-radiation from the embedded protostars ionizes the gas around and forms an Ultra Compact HII (UCHII) region. In these objects many of the previously formed complex molecules are not longer detected as they got destroyed by the ionizing radiation. For our observations, we used the IRAM 30m telescope with the total bandpass of 16 GHz and good spectral resolution (˜0.3/0.7 km/s at 1/3 mm). We derived their large-scale chemical abundances, assuming LTE and optically thin emission. To set these results into context, we model the chemical evolution in such environments with a state-of-the-art chemical model. This enables us to put constraints on the chemical evolution, the age and parameters such as the temperature and the density of the molecular clouds.

  8. 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.

  9. 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.

  10. 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.

  11. Estimation of useful yield in surface analysis using single photon ionisation

    NASA Astrophysics Data System (ADS)

    King, B. V.; Pellin, M. J.; Moore, J. F.; Veryovkin, I. V.; Savina, M. R.; Tripa, C. E.

    2003-01-01

    Secondary ion mass spectrometry (SIMS), laser sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation (LDPI) have been used to investigate the desorption of molecules from self-assembled monolayers of phenylsulphides. LDPI, using an F 2 excimer laser to single photon ionise gave the lowest fragmentation. A useful yield greater than 0.5% was found for analysis of diphenyldisulphide self-assembled monolayers. It is shown that using a free electron laser to postionise will lead, in the future, to analysis of many atoms and molecules with useful yields approaching 30%.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Amonia gas: an improved reagent for chemical ionization mass spectrometry of bile acid methyl ester acetates

    SciTech Connect

    DeMark, B.R.; Klein, P.D.

    1981-01-01

    The ammonia chemical ionization mass spectra of 28 methyl ester acetate derivatives of bile acids and related compounds have been determined by gas-liquid chromatography-mass spectrometry. Advantages of ammonia ionization over the previously studied isobutane ionization include a 130 to 270% enhancement in the sensitivity of base peak monitoring, and direct determination of molecular weight from the base peak (M + NH/sub 4//sup +/) in the mass spectrum of any of the derivatives. Minor ions in the ammonia spectra also allow selective detection of 3-keto compounds and can indicate unsaturation or double bond conjugation in the molecule. The significance of these studies for the detection and quantitation of bile acids is discussed. 2 tables.

  17. Carbon disulfide reagent allows the characterization of nonpolar analytes by atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Owen, Benjamin C; Gao, Jinshan; Borton, David J; Amundson, Lucas M; Archibold, Enada F; Tan, Xiaoli; Azyat, Khalid; Tykwinski, Rik; Gray, Murray; Kenttämaa, Hilkka I

    2011-07-30

    While atmospheric pressure ionization methodologies have revolutionized the mass spectrometric analysis of nonvolatile analytes, limitations native to the chemistry of these methodologies hinder or entirely inhibit the analysis of certain analytes, specifically, many nonpolar compounds. Examination of various analytes, including asphaltene and lignin model compounds as well as saturated hydrocarbons, demonstrates that atmospheric pressure chemical ionization (APCI) using CS(2) as the reagent produces an abundant and stable molecular ion (M(+•)) for all model compounds studied, with the exception of completely saturated aliphatic hydrocarbons and the two amino acids tested, arginine and phenylalanine. This reagent substantially broadens the applicability of mass spectrometry to nonvolatile nonpolar analytes and also facilitates the examination of radical cation chemistry by mass spectrometry. PMID:21698674

  18. Stagnation Point Flow and Mass Transfer with Chemical Reaction past a Stretching/Shrinking Cylinder

    PubMed Central

    Najib, Najwa; Bachok, Norfifah; Arifin, Norihan Md.; Ishak, Anuar

    2014-01-01

    This paper is about the stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder. The governing partial differential equations in cylindrical form are transformed into ordinary differential equations by a similarity transformation. The transformed equations are solved numerically using a shooting method. Results for the skin friction coefficient, Schmidt number, velocity profiles as well as concentration profiles are presented for different values of the governing parameters. Effects of the curvature parameter, stretching/shrinking parameter and Schmidt number on the flow and mass transfer characteristics are examined. The study indicates that dual solutions exist for the shrinking cylinder but for the stretching cylinder, the solution is unique. It is observed that the surface shear stress and the mass transfer rate at the surface increase as the curvature parameter increases. PMID:24569547

  19. 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.

  20. Detailed mass size distributions of elements and species, and aerosol chemical mass closure during fall 1999 at Gent, Belgium

    NASA Astrophysics Data System (ADS)

    Maenhaut, Willy; Cafmeyer, Jan; Dubtsov, Sergei; Chi, Xuguang

    2002-04-01

    A 10-stage microorifice uniform deposit impactor (MOUDI) and a 12-stage small deposit area low pressure impactor (SDI) were operated at Gent from 6 September to 30 October 1999. Thirty-four parallel samples (of typically 24 h) were collected. The MOUDI samples were analysed for the particulate mass (PM) by weighing, and for organic carbon (OC) and elemental carbon (EC) by a thermal-optical transmission technique. The SDI samples were analysed for 27 elements by PIXE. PM and OC exhibited typically a rather similar bimodal size distribution, with most of their mass in the submicrometer size range. EC was predominantly associated with fine particles, with maximum typically at around 0.2 μm equivalent aerodynamic diameter (EAD). Sulphur was also mainly in the fine size range, but with maximum at 0.5 μm EAD. Other elements with mainly a fine mode were V, Ni, As, Se and Pb. The crustal elements (Al, Si, Ti, Fe, Zr) exhibited mostly a unimodal coarse mode size distribution, with maximum at about 4 μm EAD. Other elements with mainly a coarse mode were Na, Mg, P, Ca, Cr, Mn, Cu, Ga and Sr. The elements K, Zn and Rb were generally bimodal. Aerosol chemical mass closure calculations indicated that organic aerosol and crustal matter were the major aerosol types in the supermicrometer size range, and that the dominant aerosol types in the submicrometer fraction were organic aerosol and sulphate. On average, 74% of the gravimetric PM was accounted for by the aerosol types considered.

  1. 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.

  2. 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.

  3. Chemical Changes During Star Formation: High vs. Low-mass YSOs

    NASA Astrophysics Data System (ADS)

    van Dishoeck, Ewine F.

    An overview of recent single-dish surveys of molecular species at infrared and submillimeter wavelengths in a set of high- and low-mass young stellar objects will be presented. The importance of flexible radiative transfer tools for deriving reliable abundances will be emphasized. The temperature and density structures of the envelopes ---an essential ingredient in the analysis--- are constrained from observations of the dust continuum and CS excitation. In high mass objects, clear evidence is seen for abundance jumps of various molecules in the inner warm part of the envelopes. Systematic trends in the abundances and gas/solid ratios with enhanced dust and gas temperatures are found, which may be related to the evolutionary state of the objects. Recent results on combined ISO-SWS, ISO-LWS and SWAS observations of H2O are summarized. The results for high-mass objects will be compared with those for low-mass class 0 and I objects, with special emphasis on the deeply embedded IRAS 16293 -2422 protostar. Geometry appears to play a more important role in the analysis of data for low-mass objects. The observations are interpreted with detailed time-dependent chemical models using the inferred physical structure as input. The importance of freeze-out in the outer envelope as well as ice evaporation and high-temperature reactions in the inner envelope are discussed. See: astro-ph/0205457; astro-ph/0205292; astro-ph/0205068; astro-ph/0201317.

  4. Atmospheric pressure laser-induced acoustic desorption chemical ionization mass spectrometry for analysis of saturated hydrocarbons.

    PubMed

    Nyadong, Leonard; Quinn, John P; Hsu, Chang S; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2012-08-21

    We present atmospheric pressure laser-induced acoustic desorption chemical ionization (AP/LIAD-CI) with O(2) carrier/reagent gas as a powerful new approach for the analysis of saturated hydrocarbon mixtures. Nonthermal sample vaporization with subsequent chemical ionization generates abundant ion signals for straight-chain, branched, and cycloalkanes with minimal or no fragmentation. [M - H](+) is the dominant species for straight-chain and branched alkanes. For cycloalkanes, M(+•) species dominate the mass spectrum at lower capillary temperature (<100 °C) and [M - H](+) at higher temperature (>200 °C). The mass spectrum for a straight-chain alkane mixture (C(21)-C(40)) shows comparable ionization efficiency for all components. AP/LIAD-CI produces molecular weight distributions similar to those for gel permeation chromatography for polyethylene polymers, Polywax 500 and Polywax 655. Coupling of the technique to Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for the analysis of complex hydrocarbon mixtures provides unparalleled mass resolution and accuracy to facilitate unambiguous elemental composition assignments, e.g., 1754 peaks (rms error = 175 ppb) corresponding to a paraffin series (C(12)-C(49), double-bond equivalents, DBE = 0) and higher DBE series corresponding to cycloparaffins containing one to eight rings. Isoabundance-contoured plots of DBE versus carbon number highlight steranes (DBE = 4) of carbon number C(27)-C(30) and hopanes of C(29)-C(35) (DBE = 5), with sterane-to-hopane ratio in good agreement with field ionization (FI) mass spectrometry analysis, but performed at atmospheric pressure. The overall speciation of nonpolar, aliphatic hydrocarbon base oil species offers a promising diagnostic probe to characterize crude oil and its products. PMID:22881221

  5. 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. PMID:25813029

  6. Mass Transfer from Gas Bubbles to Impinging Flow of Biological Fluids with Chemical Reaction

    PubMed Central

    Yang, Wen-Jei; Echigo, R.; Wotton, D. R.; Ou, J. W.; Hwang, J. B.

    1972-01-01

    The rates of mass transfer from a gas bubble to an impinging flow of a biological fluid such as whole blood and plasma are investigated analytically and experimentally. Gases commonly found dissolved in body fluids are included. Consideration is given to the effects of the chemical reaction between the dissolved gas and the liquid on the rate of mass transfer. Through the application of boundary layer theory the over-all transfer is found to be Sh/(Re)1/2 = 0.845 Sc1/3 in the absence of chemical reaction, and Sh/(Re) 1/2 = F′ (0) in the presence of chemical reaction, where Sh, Re, and Sc are the Sherwood, Reynolds, and Schmidt numbers, respectively, and F′ (0) is a function of Sc and the dimensionless reaction rate constant. Analytical results are also obtained for the bubble lifetime and the bubble radius-time history. These results, which are not incompatible with experimental results, can be applied to predict the dissolution of the entrapped gas emboli in the circulatory system of the human body. PMID:4642218

  7. 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

  8. 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.

  9. Surface topology of Minibody by selective chemical modifications and mass spectrometry.

    PubMed

    Zappacosta, F; Ingallinella, P; Scaloni, A; Pessi, A; Bianchi, E; Sollazzo, M; Tramontano, A; Marino, G; Pucci, P

    1997-09-01

    The surface topology of the Minibody, a small de novo-designed beta-protein, has been probed by a strategy that combines selective chemical modification with a variety of reagents and mass spectrometric analysis of the modified fragments. Under appropriate conditions, the susceptibility of individual residues primarily depends on their surface accessibility so that their relative reactivities can be correlated with their position in the tertiary structure of the protein. Moreover, this approach provides information on interacting residues, since intramolecular interactions might greatly affect the reactivity of individual side chains by altering their pKa values. The results of this study indicate that, while overall the Minibody model is correct, the beta-sheet formed by the N- and C-terminal segments is most likely distorted. This is also in agreement with previous results that were obtained using a similar approach where mass spectrometry was used to identify Minibody fragments from limited proteolysis (Zappacosta F, Pessi A, Bianchi E, Venturini S, Sollazzo M, Tramontano A. Marino G, Pucci P. 1996. Probing the tertiary structure of proteins by limited proteolysis and mass spectrometry: The case of Minibody. Protein Sci 5:802-813). The chemical modification approach, in combination with limited proteolysis procedures, can provide useful, albeit partial, structural information to complement simulation techniques. This is especially valuable when, as in the Minibody case, an NMR and/or X-ray structure cannot be obtained due to insufficient solubility of the molecule. PMID:9300490

  10. 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

  11. Quantification of Absolute Fat Mass by Magnetic Resonance Imaging: a Validation Study against Chemical Analysis

    PubMed Central

    Hu, Houchun H.; Li, Yan; Nagy, Tim R.; Goran, Michael I.; Nayak, Krishna S.

    2011-01-01

    Objective To develop a magnetic resonance imaging (MRI)-based approach for quantifying absolute fat mass in organs, muscles, and adipose tissues, and to validate its accuracy against reference chemical analysis (CA). Methods Chemical-shift imaging can accurately decompose water and fat signals from the acquired MRI data. A proton density fat fraction (PDFF) can be computed from the separated images, and reflects the relative fat content on a voxel-by-voxel basis. The PDFF is mathematically closely related to the fat mass fraction and can be converted to absolute fat mass in grams by multiplying by the voxel volume and the mass density of fat. In this validation study, 97 freshly excised and unique samples from four pigs, comprising of organs, muscles, and adipose and lean tissues were imaged by MRI and then analyzed independently by CA. Linear regression was used to assess correlation, agreement, and measurement differences between MRI and CA. Results Considering all 97 samples, a strong correlation and agreement was obtained between MRI and CA-derived fat mass (slope = 1.01, intercept = 1.99g, r2 = 0.98, p < 0.01). The mean difference d between MRI and CA was 2.17±3.40g. MRI did not exhibit any tendency to under or overestimate CA (p > 0.05). When considering samples from each pig separately, the results were (slope = 1.05, intercept = 1.11g, r2 = 0.98, d = 2.66±4.36g), (slope = 0.99, intercept = 2.33g, r2 = 0.99, d = 1.88±2.68g), (slope = 1.07, intercept = 1.52g, r2 = 0.96, d = 2.73±2.50g), and (slope=0.92, intercept=2.84g, r2 = 0.97, d = 1.18±3.90g), respectively. Conclusion Chemical-shift MRI and PDFF provides an accurate means of determining absolute fat mass in organs, muscles, and adipose and lean tissues. PMID:23204926

  12. 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

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. Radical-neutral chemical reactions studied at low temperature with VUV synchrotron photoionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Soorkia, Satchin; Leone, Stephen R.; Wilson, Kevin R.

    2012-11-01

    A pulsed Laval nozzle apparatus employing tunable VUV synchrotron photoionization and quadrupole mass spectrometry for the study of radical-neutral chemical reactions of importance for modeling the atmosphere of Titan and the outer planets is described. The apparatus enables the study of low-temperature kinetics and isomer-resolved product branching of highly reactive radicals with unsaturated hydrocarbons reactions. The low-temperature branching ratio for the reaction of the ethynyl radical (C2H) with allene (C3H4) has been measured for the first time at 79 K. This reaction is found to yield 1,4-pentadiyne as the major reaction product (50+10%), followed by ethynylallene (28+10%) and methyldiacetylene (22+10%) via H-atom elimination from the initially formed C5H5 adduct. The derived branching ratios can be directly used to predict the chemical evolution of Titan's atmosphere.

  18. 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. PMID:16920155

  19. Evaluating the Utility of an Atmospheric Pressure Chemical Ionization Mass Spectrometer for Analyzing Organic Peroxides

    NASA Astrophysics Data System (ADS)

    Jameer, A.; Hastie, D. R.

    2013-12-01

    Secondary organic aerosols (SOA) are known to affect the earth's radiation budget through its ability to scatter and absorb radiation. Consequently, the mechanisms and factors that influence SOA composition and formation are poorly understood. However, recent modeling studies coupled with smog chamber experiments suggest that organic peroxides (organic hydroperoxides and peroxyhemiacetals) might be a major component of SOA composition under low NOx conditions. This study utilized an atmospheric pressure chemical ionization mass spectrometer (APCI-MS) in the positive mode to detect organic peroxides. Mass spectra of organic peroxides analyzed in this study show excessive fragmentation during ionization with protonated water clusters. It was believed that intact ions were not found due to decomposition in the ion source. Future work will explore new reagents for ionization to reduce fragmentation during analysis.

  20. 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

  1. Chemical composition and mass closure of particulate matter at six urban sites in Europe

    NASA Astrophysics Data System (ADS)

    Sillanpää, Markus; Hillamo, Risto; Saarikoski, Sanna; Frey, Anna; Pennanen, Arto; Makkonen, Ulla; Spolnik, Zoya; Van Grieken, René; Braniš, Martin; Brunekreef, Bert; Chalbot, Marie-Cecile; Kuhlbusch, Thomas; Sunyer, Jordi; Kerminen, Veli-Matti; Kulmala, Markku; Salonen, Raimo O.

    The chemical composition of fine (PM 2.5) and coarse (PM 2.5-10) particulate matter was investigated in 7-week field campaigns of contrasting air pollution at six urban background sites in Europe. The campaigns were scheduled to include seasons of local public health concern due to high particulate concentrations or findings in previously conducted epidemiological studies. The sampling campaigns were carried out as follows: Duisburg/Germany October-November 2002 (autumn), Prague/Czech Republic November 2002-January 2003 (winter), Amsterdam/Netherlands January-March 2003 (winter), Helsinki/Finland March-May 2003 (spring), Barcelona/Spain March-May 2003 (spring) and Athens/Greece June-July 2003 (summer). Aerosol samples were collected in 3+4-day periods per week ( N=14) using two identical virtual impactors (VI). All the filter samples were analysed with the same instruments to obtain particulate mass, inorganic ions, total and watersoluble elements, and elemental and organic carbon content. The campaign means of PM 2.5 and PM 2.5-10 ranged from 8.3 to 30 and 5.4 to 29 μg m -3, respectively. The "wet and cool" seasons favoured a low coarse-to-fine particulate mass ratio (<1), whereas the ratio was high (>1) during the warmer and drier spring and summer campaigns. According to chemical mass closure, the major components in PM 2.5 were carbonaceous compounds (organic matter+elemental carbon), secondary inorganic ions and sea salt, whereas those in PM 2.5-10 were soil-derived compounds, carbonaceous compounds, sea salt and nitrate. The major and minor components together accounted for 79-106% and 77-96% of the gravimetrically measured PM 2.5 and PM 2.5-10 mass, respectively. In conclusion, the measured PM 2.5 and PM 2.5-10 in the campaigns could be reconstructed to a large extent with the help of harmonized particulate sampling and analysis of the selected chemical constituents. The health significance of the observed differences in chemical composition and emission

  2. 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

  3. 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

  4. 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. PMID:25947046

  5. 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.

  6. Isotopic analysis of single uranium and plutonium particles by chemical treatment and mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shinonaga, T.; Esaka, F.; Magara, M.; Klose, D.; Donohue, D.

    2008-11-01

    The isotopic composition of single uranium and plutonium particles was measured with an inductively coupled plasma mass spectrometer (ICP-MS) and a thermal ionization mass spectrometer (TIMS). Particles deposited on a carbon planchet were first analyzed with an energy dispersive X-ray spectrometer (EDX) attached to a scanning electron microscope (SEM) and then transferred on to a silicon wafer using a manipulator. The particle on the silicon wafer was dissolved with nitric acid and the isotopic ratios of U and Pu were measured with ICP-MS and TIMS. The results obtained by both methods for particles of certified reference materials showed good agreement with the certified values within the expected uncertainty. The measurement uncertainties obtained in this study were similar for both mass spectrometric methods. This study was performed to establish the method of particle analysis with SEM, EDX, the particle manipulation and chemical preparation technique, and the measurement of isotopic ratios of U and Pu in a single particle by mass spectrometry.

  7. 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

  8. Liquid chromatographic tandem mass spectrometric determination of five coccidiostats in poultry eggs and feed.

    PubMed

    Mortier, Leen; Daeseleire, Els; Van Peteghem, Carlos

    2005-06-25

    A method is described which permits the quantitative detection of the chemical coccidiostats halofuginone, robenidine, diclazuril, nicarbazin and dimetridazole and its main metabolite 2-hydroxydimetridazole in poultry eggs and feed. Sample preparations were kept very simple and are based upon extraction with an organic solvent. Sample extracts were injected into the liquid chromatography tandem mass spectrometry (LC-MS/MS) system on a C18 column and a gradient elution was performed. Dimetridazole-D3 and diclazuril-bis, a structural analogue of diclazuril, were used as internal standards. Detection was performed on a triple quadrupole mass spectrometer in the selected reaction monitoring mode after ionisation in the positive or negative electrospray ionisation mode. Argon was applied as collision gas for collision induced dissociation. Validation of the methods was performed based on Commission Decision 2002/657/EC [Official Journal of the European Communities L221 (2002) 8]. PMID:15893963

  9. 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

  10. Single site double core level ionisation of OCS

    NASA Astrophysics Data System (ADS)

    Hedin, L.; Tashiro, M.; Linusson, P.; Eland, J. H. D.; Ehara, M.; Ueda, K.; Zhaunerchyk, V.; Karlsson, L.; Feifel, R.

    2014-08-01

    Single site O1s, C1s and S2p double ionisation of the OCS molecule has been investigated using a magnetic bottle multi-electron coincidence time-of-flight spectrometer. Photon energies of 1300, 750 and 520 eV, respectively, were used for the ionisation, and spectra were obtained from which the double core ionisation energies could be determined. The energies measured for 1s double ionisation are 1172 eV (O1s-2) and 659 eV (C1s-2). For the S2p double ionisation three dicationic states are expected, 3P, 1D and 1S. The ionisation energies obtained for these states are 373 eV (3P), 380 eV (1D) and 388 eV (1S). The ratio between the double and single core ionisation energies are in all cases equal or close to 2.20. Auger spectra of OCS, associated with the O1s-2, C1s-2 and S2p-2 dicationic states, were also recorded incorporating both electrons emitted as a result of the filling of the two core vacancies. As for other small molecules, the spectra show an atomic-like character with Auger bands located in the range 480-560 eV for oxygen, 235-295 eV for carbon and 100-160 eV for sulphur. The interpretation of the spectra is supported by CASSCF and CASCI calculations. The cross section ratio between double and single core hole creation was estimated as 3.7 × 10-4 for oxygen at 1300 eV, 3.7 × 10-4 for carbon at 750 eV and as 2.2 × 10-3 for sulphur at 520 eV.

  11. Photochemistry of limonene secondary organic aerosol studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, Xiang

    Limonene is one of the most abundant monoterpenes in the atmosphere. Limonene easily reacts with gas-phase oxidants in air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products condense into particles. Chemicals in SOA particles can undergo further reactions with oxidants and with solar radiation that significantly change SOA composition over the course of several days. The goal of this work was to characterize radiation induced reaction in SOA. To perform experiments, we have designed and constructed an Atmospheric Pressure Chemical Ionization Mass Spectrometer (APCIMS) coupled to a photochemical cell containing SOA samples. In APCIMS, (H2O)nH 3O+ clusters are generated in a 63Ni source and react with gaseous organic analytes. Most organic chemicals are not fragmented by the ionization process. We have focused our attention on limonene SOA prepared in two different ways. The first type of SOA is produced by oxidation of limonene by ozone; and the second type of SOA is formed by the NO3-induced oxidation of limonene. They model the SOA formed under daytime and nighttime conditions, respectively. Ozone initiated oxidation is the most important chemical sink for limonene both indoors, where it is used for cleaning purposes, and outdoors. Terpenes are primarily oxidized by reactions with NO3 at night time. We generated limonene SOA under different ozone and limonene concentrations. The resulting SOA samples were exposed to wavelength-tunable radiation in the UV-Visible range between 270 nm and 630 nm. The results show that the photodegradation rates strongly depend on radiation wavelengths. Gas phase photodegradation products such as acetone, formaldehyde, acetaldehyde, and acetic acid were shown to have different production rates for SOA formed in different concentration conditions. Even for SOA prepared under the lowest concentrations, the SOA photodegradation was efficient. The conclusion is that exposure of SOA to

  12. 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.

  13. Chemical Imaging of Lipid Domains by High-Resolution Secondary Ion Mass Spectrometry

    SciTech Connect

    Kraft, M L; Weber, P K; Longo, M L; Hutcheon, I D; Boxer, S G

    2005-09-30

    Lipid microdomains within supported lipid bilayers composed of binary phosphocholine mixtures were chemically imaged by high-resolution secondary ion mass spectrometry performed with the NanoSIMS 50 (Cameca Instruments). This instrument images the sample components based on the elemental or isotopic composition of their atomic and small molecular secondary ions. Up to five different secondary ions can be simultaneously detected, and a lateral resolution of 50 nm can be achieved with high sensitivity at high mass resolution. In our experiments, the NanoSIMS 50 extensively fragmented the supported membrane, therefore an isotopic labeling strategy was used to encode the identities of the lipid components. Supported lipid membranes that contained distinct lipid microdomains were freeze-dried to preserve their lateral organization and analyzed with the NanoSIMS 50. Lipid microdomains as small as 100 nm in diameter were successfully imaged, and this was validated by comparison to AFM images taken at the same region prior to chemical imaging. Quantitative information on the lipid distribution within the domain was also determined by calibrating against supported membranes of known composition. We believe this will be a valuable approach for analyzing the composition of complex membrane domains with high spatial resolution.

  14. Molecular Surface Sampling and Chemical Imaging using Proximal Probe Thermal Desorption/Secondary Ionization Mass Spectrometry

    SciTech Connect

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

    2011-01-01

    Proximal probe thermal desorption/secondary ionization mass spectrometry was studied and applied to molecular surface sampling and chemical imaging using printed patterns on photopaper as test substrates. With the use of a circular cross section proximal probe with a tip diameter of 50 m and fixed temperature (350 C), the influence of probe-to-surface distance, lane scan spacing, and surface scan speed on signal quality and spatial resolution were studied and optimized. As a compromise between signal amplitude, signal reproducibility, and data acquisition time, a surface scan speed of 100 m/s, probe-to-paper surface distance of 5 m, and lane spacing of 10 m were used for imaging. Under those conditions the proximal probe thermal desorption/secondary ionization mass spectrometry method was able to achieve a spatial resolution of about 50 m as determined by the ability to distinguish surface patterns of known dimensions that were printed on the paper substrate. It is expected that spatial resolution and chemical image quality could be further improved by using probes of smaller cross section size and by incorporating a means to maintain a fixed optimal probe-to-surface distance real time, continuously adapting to the changing topography of the surface during a lane scan.

  15. Gas chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Ostman, Pekka; Luosujärvi, Laura; Haapala, Markus; Grigoras, Kestas; Ketola, Raimo A; Kotiaho, Tapio; Franssila, Sami; Kostiainen, Risto

    2006-05-01

    An atmospheric pressure chemical ionization (APCI) microchip is presented for combining a gas chromatograph (GC) to a mass spectrometer (MS). The chip includes capillary insertion channel, stopper, vaporizer channel, nozzle and nebulizer gas inlet fabricated on the silicon wafer, and a platinum heater sputtered on a glass wafer. These two wafers are joined by anodic bonding creating a two-dimensional version of an APCI microchip. The sample from GC is directed via heated transfer line capillary to the vaporizer channel of the APCI chip. The etched nozzle forms narrow sample plume, which is ionized by an external corona discharge needle, and the ions are analyzed by a mass spectrometer. The GC-microchip APCI-MS combination provides an efficient method for qualitative and quantitative analysis. The spectra produced by microchip APCI show intensive protonated molecule and some fragmentation products as in classical chemical ionization for structure elucidation. In quantitative analysis the GC-microchip APCI-MS showed good linearity (r(2) = 0.9989) and repeatability (relative standard deviation 4.4%). The limits of detection with signal-to-noise ratio of three were between 0.5 and 2 micromol/L with MS mode using selected ion monitoring and 0.05 micromol/L with MS/MS using multiple reaction monitoring. PMID:16642989

  16. Mass and energy balance constraints on the biological production of chemicals from coal

    SciTech Connect

    Andrews, G.

    1990-01-01

    Several organic chemicals, including methane and ethanol, may be produced by the bioprocessing of coal. This may be done either by direct microbial attack on the coal, or indirectly by the bioprocessing of solubilized coal. As in chemical liquefaction and gasification, the relative amounts of the various products that can be produced are severely constrained by mass and energy balance considerations. The main differences in biological processing are that water is a ubiquitous reactant, carbon dioxide a common product, and that some of the carbon and nitrogen in the coal may go to the synthesis of new biomass rather than products. The conventional biotechnological yield analysis applied to coal processing has several interesting consequences. The mass balance reduces to a balance of available electrons, and coal has a similar oxidation/reduction state to both carbohydrates and biomass. This makes high product yields feasible particularly under anaerobic conditions, although leaving open the question of whether the relevant hydrolase enzymes exist. Recommendations are made on products, and combinations of two products, that may be made with high yields and economic return. The energy balance provides little extra information. A general intracellular energy balance can be written in terms of the production and consumption of ATP, but much of the necessary information on the metabolic pathways is currently not available for coal processing microorganisms. 9 refs., 2 figs., 2 tabs.

  17. A mass weighted chemical elastic network model elucidates closed form domain motions in proteins

    PubMed Central

    Kim, Min Hyeok; Seo, Sangjae; Jeong, Jay Il; Kim, Bum Joon; Liu, Wing Kam; Lim, Byeong Soo; Choi, Jae Boong; Kim, Moon Ki

    2013-01-01

    An elastic network model (ENM), usually Cα coarse-grained one, has been widely used to study protein dynamics as an alternative to classical molecular dynamics simulation. This simple approach dramatically saves the computational cost, but sometimes fails to describe a feasible conformational change due to unrealistically excessive spring connections. To overcome this limitation, we propose a mass-weighted chemical elastic network model (MWCENM) in which the total mass of each residue is assumed to be concentrated on the representative alpha carbon atom and various stiffness values are precisely assigned according to the types of chemical interactions. We test MWCENM on several well-known proteins of which both closed and open conformations are available as well as three α-helix rich proteins. Their normal mode analysis reveals that MWCENM not only generates more plausible conformational changes, especially for closed forms of proteins, but also preserves protein secondary structures thus distinguishing MWCENM from traditional ENMs. In addition, MWCENM also reduces computational burden by using a more sparse stiffness matrix. PMID:23456820

  18. 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

  19. Chemical Attribution of Fentanyl Using Multivariate Statistical Analysis of Orthogonal Mass Spectral Data.

    PubMed

    Mayer, Brian P; DeHope, Alan J; Mew, Daniel A; Spackman, Paul E; Williams, Audrey M

    2016-04-19

    Attribution of the origin of an illicit drug relies on identification of compounds indicative of its clandestine production and is a key component of many modern forensic investigations. The results of these studies can yield detailed information on method of manufacture, starting material source, and final product, all critical forensic evidence. In the present work, chemical attribution signatures (CAS) associated with the synthesis of the analgesic fentanyl, N-(1-phenylethylpiperidin-4-yl)-N-phenylpropanamide, were investigated. Six synthesis methods, all previously published fentanyl synthetic routes or hybrid versions thereof, were studied in an effort to identify and classify route-specific signatures. A total of 160 distinct compounds and inorganic species were identified using gas and liquid chromatographies combined with mass spectrometric methods (gas chromatography/mass spectrometry (GC/MS) and liquid chromatography-tandem mass spectrometry-time of-flight (LC-MS/MS-TOF)) in conjunction with inductively coupled plasma mass spectrometry (ICPMS). The complexity of the resultant data matrix urged the use of multivariate statistical analysis. Using partial least-squares-discriminant analysis (PLS-DA), 87 route-specific CAS were classified and a statistical model capable of predicting the method of fentanyl synthesis was validated and tested against CAS profiles from crude fentanyl products deposited and later extracted from two operationally relevant surfaces: stainless steel and vinyl tile. This work provides the most detailed fentanyl CAS investigation to date by using orthogonal mass spectral data to identify CAS of forensic significance for illicit drug detection, profiling, and attribution. PMID:27010913

  20. Chemical mass balances in metalliferous deposits from the Atlantis II Deep, Red Sea

    NASA Astrophysics Data System (ADS)

    Anschutz, Pierre; Blanc, Gérard

    1995-10-01

    In order to assess the quantitative distribution of mineral species within the sedimentary series of the Atlantis II Deep, we have examined the chemical composition, mineralogy, and physical properties of 120 sediment samples from two cores that sampled the entire sediment sequences in the West and South-West basins. Biostratigraphic correlations and chemical budget calculations indicate that the nonmetalliferous solid fractions (i.e., detrital and biogenic particles) in the older sedimentary unit (unit 1 in the West basin) represent 46% wt of the total, and that they were deposited between 23,000 and 15-12,000 years BP with a mass accumulation rate between 109 and 150 kg per thousand years per square metre. The muddy sediment in the upper part of the West basin core (units 2, 3, and 4) consists mainly of metalliferous particles which account for less than 15% wt of the mud, and yield a mass accumulation rate (130-162 kg/k.y./M 2) close to that of nonmetalliferous particles deposited simultaneously. Nonmetalliferous particles were probably the major source of Si and a significant source of Pb through dissolution in the brine system and diagenesis in the metalliferous mud. The metalliferous sediments in the upper unit of the South-West basin (unit U, 1100 cm) were deposited at the same time as those of the upper unit in the West basin (unit 4,335 cm). The calculated mass accumulation rate is about 700 kg/k.y./m 2 for unit U. The recent sediments of the South-West basin are more enriched in Zn and Cu, and more depleted in Mn relative to Fe than the contemporary sediments in the West basin, suggesting that the hydrothermal source has been in, or near, the South-West basin during the last 2,250 years. Assuming that a Salton Sea-like solution supplies all the Fe contained in the West basin metalliferous sedimentary pile, the mineralizing brine flowed at a minimum rate of 30 L/s. Except for the period of Mn-oxide deposition, the difference between the metal/Fe ratios in

  1. 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...

  2. 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

  3. 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.

  4. On slide chemical modification as a means to improve confidence in protein identifications made by peptide mass finger prints

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The identification of proteins from large protein databases such as NCBInr using peptide mass finger prints (PMFs) obtained on a MALDI-TOF mass spectrometer continues to be a challenge. A strategy that can be used to improve confidence in these identifications is to carry out some form of chemical ...

  5. Atmospheric amines and ammonia measured with a chemical ionization mass spectrometer (CIMS)

    NASA Astrophysics Data System (ADS)

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, A. B.; Madronich, S.; Sierra-Hernández, M. R.; Lawler, M.; Smith, J. N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, E. S.; Porcelli, L.; Brune, W. H.; Goldstein, A. H.; Lee, S.-H.

    2014-11-01

    We report measurements of ambient amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a southeastern US forest and a moderately polluted midwestern site during the summer. At the forest site, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected, and they both showed temperature dependencies. Aerosol-phase amines measured thermal-desorption chemical ionization mass spectrometer (TDCIMS) showed a higher mass fraction in the evening with cooler temperatures and lower in the afternoon with warmer temperatures, a trend opposite to the gas-phase amines. Concentrations of aerosol-phase primary amines measured with Fourier transform infrared spectroscopy (FTIR) from micron and submicron particles were 2 orders of magnitude higher than the gas-phase amines. These results indicate that gas to particle conversion is one of the major processes that control the ambient amine concentrations at this forest site. Temperature dependencies of C3-amines and ammonia also imply reversible processes of evaporation of these nitrogen-containing compounds from soil surfaces in daytime and deposition to soil surfaces at nighttime. During the transported biomass burning plume events, various amines (C1-C6) appeared at the pptv level, indicating that biomass burning is a substantial source of amines in the southeastern US. At the moderately polluted Kent site, there were higher concentrations of C1- to C6-amines (pptv to tens of pptv) and ammonia (up to 6 ppbv). C1- to C3-amines and ammonia were well correlated with the ambient temperature. C4- to C6-amines showed frequent spikes 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. Higher amine concentrations measured at the polluted site than at the rural forested site highlight the importance of constraining anthropogenic emission

  6. Aerosol chemical mass closure during the EUROTRAC-2 AEROSOL Intercomparison 2000

    NASA Astrophysics Data System (ADS)

    Maenhaut, Willy; Schwarz, Jaroslav; Cafmeyer, Jan; Chi, Xuguang

    2002-04-01

    The field work for the AEROSOL Intercomparison 2000 took place from 4 to 14 April 2000 at Melpitz, Germany. One objective was to assess to which extent aerosol chemical mass closure could be obtained for the site. For this purpose, we operated four filter samplers in parallel (mostly using 12-h collections): two Gent PM10 stacked filter unit (SFU) samplers (one with coarse and fine Nuclepore polycarbonate filters, the other with a Gelman Teflo filter as fine filter) and two single filter holders (one with PM2.5 inlet, the other with PM10 inlet) with Whatman QM-A quartz fibre filters. All samples were analysed for the particulate mass (PM) by weighing; the samples from the first SFU were analysed for 42 elements by a combination of particle-induced X-ray emission spectroscopy and instrumental neutron activation analysis, those from the other SFU for major anions and cations by ion chromatography. All quartz filters were analysed for organic carbon and elemental carbon by a thermal-optical transmission technique. Aerosol chemical mass closure calculations were done for the separate fine (PM2) and coarse (2-10 μm) size fractions. As gravimetric PM data we used the averages from the parallel SFU collections. For reconstituting this PM, nine aerosol types (or components) were considered. Crustal matter, organic aerosol and nitrate were the major aerosol types in the coarse size fraction; the dominant aerosol types in the fine fraction were organic aerosol, nitrate and sulphate. The included components explained 116% and 86% of the gravimetric PM in the coarse and fine size fractions, respectively.

  7. 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.

  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. 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. PMID:20809628

  10. 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

  11. 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.

  12. Quark-mass dependence of the three-flavor QCD phase diagram at zero and imaginary chemical potential: Model prediction

    SciTech Connect

    Sasaki, Takahiro; Sakai, Yuji; Yahiro, Masanobu; Kouno, Hiroaki

    2011-11-01

    We draw the three-flavor phase diagram as a function of light- and strange-quark masses for both zero and imaginary quark-number chemical potential, using the Polyakov-loop extended Nambu-Jona-Lasinio model with an effective four-quark vertex depending on the Polyakov loop. The model prediction is qualitatively consistent with 2+1 flavor lattice QCD prediction at zero chemical potential and with degenerate three-flavor lattice QCD prediction at imaginary chemical potential.

  13. 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

  14. 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

  15. 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

  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. 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.

  18. 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.

  19. 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

  20. 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.

  1. Single photon ionisation of self assembled monolayers

    NASA Astrophysics Data System (ADS)

    King, B. V.; Savina, M. R.; Tripa, C. E.; Calaway, W. F.; Veryovkin, I. V.; Moore, J. F.; Pellin, M. J.

    2002-05-01

    Self assembled monolayers formed from benzenethiol, diphenylsulphide and diphenyldisulphide have been analysed using secondary ion mass spectrometry (SIMS), sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation mass spectrometry (LDPI). The peak corresponding to the parent ion was much stronger in LDPI than with SIMS or SNMS analysis and fragmentation was lower. A useful yield of order 0.5% was obtained for LDPI from diphenyldisulphide.

  2. 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.

  3. 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

  4. 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. PMID:24053016

  5. 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

  6. Determination of double bond position in conjugated dienes by chemical ionization mass spectrometry with isobutane

    SciTech Connect

    Doolittle, R.E.; Tumlinson, J.H.; Proveaux, A.

    1985-07-01

    The chemical ionization (CI) mass spectra of a series of functionalized conjugated dienes, including aldehydes, alcohols, formates, acetates, and hydrocarbons were investigated to determine whether fragmentations occur that are characteristic of the position of the conjugated system within the hydrocarbon chain. CI with isobutane as ionizing gas produces structure-specific fragment ions with m/z ratios that can be used to locate the positions of the double bonds in most of the cases studied. When the conjugated system is proximal to the functional group or conjugated with the functional group, other fragmentation processes take precedence. These patterns of fragmentations constitute a very useful analytical tool for the location of conjugated double bonds in a variety of natural products. 34 references, 3 tables, 3 figures.

  7. Investigation of protein-protein interactions in living cells by chemical crosslinking and mass spectrometry.

    PubMed

    Sinz, Andrea

    2010-08-01

    The identification of protein-protein interactions within their physiological environment is the key to understanding biological processes at the molecular level. However, the artificial nature of in vitro experiments, with their lack of other cellular components, may obstruct observations of specific cellular processes. In vivo analyses can provide information on the processes within a cell that might not be observed in vitro. Chemical crosslinking combined with mass spectrometric analysis of the covalently connected binding partners allows us to identify interacting proteins and to map their interface regions directly in the cell. In this paper, different in vivo crosslinking strategies for deriving information on protein-protein interactions in their physiological environment are described. PMID:20076950

  8. 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.

  9. 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

  10. Determination of nicarbazin in eggs by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Blanchflower, W J; Hughes, P J; Kennedy, D G

    1997-01-01

    A method was developed to determine in eggs 2 components [4,6-dimethyl-2-hydroxypyrimidine and 1,3-bis(4-nitrophenyl)urea] of the anticoccidial drug nicarbazin, used to treat poultry. Samples were extracted with acetonitrile, and the extracts were washed with hexane and evaporated to dryness before analysis by liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization. By switching from positive to negative ion monitoring and using gradient elution, both components were measured within one run. The limit of quantitation of the assay was 10 ng/g for each component. The results of a preliminary feeding trial in which chickens were fed contamination levels of the drug are also reported. PMID:9419856

  11. Analysis of mass transport in an atmospheric pressure remote plasma-enhanced chemical vapor deposition process

    SciTech Connect

    Cardoso, R. P.; Belmonte, T.; Henrion, G.; Gries, T.; Tixhon, E.

    2010-01-15

    In remote microwave plasma enhanced chemical vapor deposition processes operated at atmospheric pressure, high deposition rates are associated with the localization of precursors on the treated surface. We show that mass transport can be advantageously ensured by convection for the heavier precursor, the lighter being driven by turbulent diffusion toward the surface. Transport by laminar diffusion is negligible. The use of high flow rates is mandatory to have a good mixing of species. The use of an injection nozzle with micrometer-sized hole enables us to define accurately the reaction area between the reactive species. The localization of the flow leads to high deposition rates by confining the reactive species over a small area, the deposition yield being therefore very high. Increasing the temperature modifies nonlinearly the deposition rates and the coating properties.

  12. 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.

  13. Qualitative Gas Chromatography-Mass Spectrometry Analyses Using Amines as Chemical Ionization Reagent Gases

    NASA Astrophysics Data System (ADS)

    Little, James L.; Howard, Adam S.

    2013-12-01

    Ammonia is a very useful chemical ionization (CI) reagent gas for the qualitative analyses of compounds by positive ion gas chromatography-mass spectrometry (GCMS). The gas is readily available, inexpensive, and leaves no carbon contamination in the MS source. Compounds of interest to our laboratory typically yield abundant protonated or ammoniated species, which are indicative of a compound's molecular weight. Nevertheless, some labile compounds fragment extensively by substitution and elimination reactions and yield no molecular weight information. In these cases, a CI reagent gas mixture of methylamine in methane prepared dynamically was found to be very useful in obtaining molecular weight data. Likewise, deuterated ammonia and deuterated methylamine are useful CI reagent gases for determining the exchangeable protons in organic compounds. Deuterated methylamine CI reagent gas is conveniently prepared by dynamically mixing small amounts of methylamine with excess deuterated ammonia.

  14. 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

  15. Measurement error models in chemical mass balance analysis of air quality data

    NASA Astrophysics Data System (ADS)

    Christensen, William F.; Gunst, Richard F.

    The chemical mass balance (CMB) equations have been used to apportion observed pollutant concentrations to their various pollution sources. Typical analyses incorporate estimated pollution source profiles, estimated source profile error variances, and error variances associated with the ambient measurement process. Often the CMB model is fit to the data using an iteratively re-weighted least-squares algorithm to obtain the effective variance solution. We consider the chemical mass balance model within the framework of the statistical measurement error model (e.g., Fuller, W.A., Measurement Error Models, Wiley, NewYork, 1987), and we illustrate that the models assumed by each of the approaches to the CMB equations are in fact special cases of a general measurement error model. We compare alternative source contribution estimators with the commonly used effective variance estimator when standard assumptions are valid and when such assumptions are violated. Four approaches for source contribution estimation and inference are compared using computer simulation: weighted least squares (with standard errors adjusted for source profile error), the effective variance approach of Watson et al. (Atmos, Environ., 18, 1984, 1347), the Britt and Luecke (Technometrics, 15, 1973, 233) approach, and a method of moments approach given in Fuller (1987, p. 193). For the scenarios we consider, the simplistic weighted least-squares approach performs as well as the more widely used effective variance solution in most cases, and is slightly superior to the effective variance solution when source profile variability is large. The four estimation approaches are illustrated using real PM 2.5 data from Fresno and the conclusions drawn from the computer simulation are validated.

  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. Binary-Encounter-Bethe ionisation cross sections for simulation of DNA damage by the direct effect of ionising radiation.

    PubMed

    Plante, I; Cucinotta, F A

    2015-09-01

    DNA damage is of crucial importance in the understanding of the effects of ionising radiation. To refine existing DNA damage models, an approach using the Binary-Encounter-Bethe (BEB) cross sections was developed. The differential cross sections for ionisation of the molecular orbitals of the DNA bases, sugars and phosphates are calculated using the electron binding energy, the mean kinetic energy and the occupancy number of each orbital as parameters. The resulting cross section has an analytic form which is quite convenient to use for Monte-Carlo codes that randomly sample the energy loss occurring during an ionisation event. We also describe an algorithm to simulate the interactions of electrons with DNA in the radiation transport code RITRACKS using the integrated BEB cross section for the bases, sugar and phosphates. PMID:25870431

  18. 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...

  19. 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

  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. PMID:25292296

  1. 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

    2014-01-01

    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

  2. Characterization of recycled mushroom compost leachate by chemical analysis and thermogravimetry-mass spectrometry.

    PubMed

    Lyons, Gary; Kilpatrick, Mairead; Sharma, H S Shekhar; Noble, Ralph; Dobrovin-Pennington, Andreja; Hobbs, Phil; Andrews, Fiona; Carmichael, Eugene

    2008-08-13

    Recycled compost leachate (RCL or euphemistically named "goody water") can be a potent source of foul odor on mushroom substrate production sites and contributes to composting smells. A complex mixture of sulfur compounds, fatty acids, and nitrogen containing compounds is responsible for odor production. Fifty samples, collected from 14 compost production sites in Ireland and the U.K. over a 2 year period, were analyzed for chemical properties and by thermogravimetry-mass spectrometry (TG-MS) for compositional differences. Results indicated that aerated samples had lower values of electrical conductivity, redox potential, and dry matter content than nonaerated samples and that the higher thermal stability of aerated samples measured by TGA could be attributed to greater mineralization of the substrate due to aerobic processes. The lower temperatures noted for peak evolution of methane, water, and carbon dioxide from TG-MS analysis suggested that a more energetic process had occurred in aerated RCL storage facilities, producing greater decomposition of macromolecules that volatilized at lower temperatures. Chemical composition, thermal stability of the freeze-dried leachate, pyrolysis profiles, and relative amounts of pyrolysis products were all markers of as to how effective control measures could influence RCL quality. PMID:18593181

  3. Identification of "Known Unknowns" Utilizing Accurate Mass Data and Chemical Abstracts Service Databases

    NASA Astrophysics Data System (ADS)

    Little, James L.; Cleven, Curtis D.; Brown, Stacy D.

    2011-02-01

    In many cases, an unknown to an investigator is actually known in the chemical literature. We refer to these types of compounds as "known unknowns." Chemical Abstracts Service (CAS) Registry is a particularly good source of these substances as it contains over 54 million entries. Accurate mass measurements can be used to query the CAS Registry by either molecular formulae or average molecular weights. Searching the database by the web-based version of SciFinder is the preferred approach when molecular formulae are available. However, if a definitive molecular formula cannot be ascertained, searching the database with STN Express by average molecular weights is a viable alternative. The results from either approach are refined by employing the number of associated references or minimal sample history as orthogonal filters. These approaches were shown to be successful in identifying "known unknowns" noted in LC-MS and even GC-MS analyses in our laboratory. In addition, they were demonstrated in the identification of a variety of compounds of interest to others.

  4. Protein surface topology-probing by selective chemical modification and mass spectrometric peptide mapping.

    PubMed Central

    Suckau, D; Mak, M; Przybylski, M

    1992-01-01

    Aminoacetylation of lysine residues and the modification of arginine by 1,2-cyclohexanedione to N7,N8-(dihydroxy-1,2-cyclohexylidene)arginine were used for probing the surface topology of hen-eggwhite lysozyme as a model protein. The molecular identification of lysine and arginine modification sites was provided by molecular weight determinations of modified and unmodified tryptic peptide mixtures (peptide mapping) using 252Cf plasma desorption mass spectrometry. At conditions of limited chemical modification, mass-spectrometric peptide-mapping analyses of lysozyme derivatives enabled the direct assignment of relative reactivities of lysine and arginine residues at different reaction times and reagent concentrations. The relative reactivities of lysine residues showed a direct correlation with their surface accessibilities from x-ray structure data. For the reaction with 1,2-cyclohexanedione, a selective modification at Arg-5, -125, -112, and -73 was identified, and an inverse correlation of relative reactivities with the surface accessibility ratios of the N7- and the N8-guanidino functions was obtained. By examination of the x-ray structural data of lysozyme, this selective modification was attributed to intramolecular catalysis because of the presence of neighboring proton acceptor groups, such as the Asp-119 carboxylate group for Arg-125 and the Trp-123 and Arg-125 carbonyl groups for Arg-5. PMID:1608973

  5. Ambient diode laser desorption dielectric barrier discharge ionization mass spectrometry of nonvolatile chemicals.

    PubMed

    Gilbert-López, Bienvenida; Schilling, Michael; Ahlmann, Norman; Michels, Antje; Hayen, Heiko; Molina-Díaz, Antonio; García-Reyes, Juan F; Franzke, Joachim

    2013-03-19

    In this work, the combined use of desorption by a continuous wave near-infrared diode laser and ionization by a dielectric barrier discharge-based probe (laser desorption dielectric barrier discharge ionization mass spectrometry (LD-DBDI-MS)) is presented as an ambient ionization method for the mass spectrometric detection of nonvolatile chemicals on surfaces. A separation of desorption and ionization processes could be verified. The use of the diode laser is motivated by its low cost, ease of use, and small size. To achieve an efficient desorption, the glass substrates are coated at the back side with a black point (target point, where the sample is deposited) in order to absorb the energy offered by the diode laser radiation. Subsequent ionization is accomplished by a helium plasmajet generated in the dielectric barrier discharge source. Examples on the application of this approach are shown in both positive and negative ionization modes. A wide variety of multiclass species with low vapor pressure were tested including pesticides, pharmaceuticals and explosives (reserpine, roxithromycin, propazine, prochloraz, spinosad, ampicillin, dicloxacillin, enrofloxacin, tetracycline, oxytetracycline, erythromycin, spinosad, cyclo-1,3,5,7-tetramethylene tetranitrate (HMX), and cyclo-1,3,5-trimethylene trinitramine (RDX)). A comparative evaluation revealed that the use of the laser is advantageous, compared to just heating the substrate surface. PMID:23419061

  6. Quantitative Metabolome Analysis Based on Chromatographic Peak Reconstruction in Chemical Isotope Labeling Liquid Chromatography Mass Spectrometry.

    PubMed

    Huan, Tao; Li, Liang

    2015-07-21

    Generating precise and accurate quantitative information on metabolomic changes in comparative samples is important for metabolomics research where technical variations in the metabolomic data should be minimized in order to reveal biological changes. We report a method and software program, IsoMS-Quant, for extracting quantitative information from a metabolomic data set generated by chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS). Unlike previous work of relying on mass spectral peak ratio of the highest intensity peak pair to measure relative quantity difference of a differentially labeled metabolite, this new program reconstructs the chromatographic peaks of the light- and heavy-labeled metabolite pair and then calculates the ratio of their peak areas to represent the relative concentration difference in two comparative samples. Using chromatographic peaks to perform relative quantification is shown to be more precise and accurate. IsoMS-Quant is integrated with IsoMS for picking peak pairs and Zero-fill for retrieving missing peak pairs in the initial peak pairs table generated by IsoMS to form a complete tool for processing CIL LC-MS data. This program can be freely downloaded from the www.MyCompoundID.org web site for noncommercial use. PMID:26086729

  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. 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

  9. Nonreductive chemical release of intact N-glycans for subsequent labeling and analysis by mass spectrometry.

    PubMed

    Yuan, Jiangbei; Wang, Chengjian; Sun, Yujiao; Huang, Linjuan; Wang, Zhongfu

    2014-10-01

    A novel strategy is proposed, using cost-saving chemical reactions to generate intact free reducing N-glycans and their fluorescent derivatives from glycoproteins for subsequent analysis. N-Glycans without core α-1,3-linked fucose are released in reducing form by selective hydrolysis of the N-type carbohydrate-peptide bond of glycoproteins under a set of optimized mild alkaline conditions and are comparable to those released by commonly used peptide-N-glycosidase (PNGase) F in terms of yield without any detectable side reaction (peeling or deacetylation). The obtained reducing glycans can be routinely derivatized with 2-aminobenzoic acid (2-AA), 1-phenyl-3-methyl-5-pyrazolone (PMP), and potentially some other fluorescent reagents for comprehensive analysis. Alternatively, the core α-1,3-fucosylated N-glycans are released in mild alkaline medium and derivatized with PMP in situ, and their yields are comparable to those obtained using commonly used PNGase A without conspicuous peeling reaction or any detectable deacetylation. Using this new technique, the N-glycans of a series of purified glycoproteins and complex biological samples were successfully released and analyzed by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS), demonstrating its general applicability to glycomic studies. PMID:24912132

  10. Heat and mass transfer from a baby manikin: impact of a chemical warfare protective bag.

    PubMed

    Danielsson, Ulf

    2004-09-01

    A chemical warfare (CW) protective bag for babies, younger than 1 year, has been evaluated in respect of thermal load. Heat and water vapour dissipating from the baby make the climate in the protective bag more demanding than outside. The thermal strain on a baby was estimated from heat and mass transfer data using an electrically heated baby manikin and a water-filled tray. Furthermore, a theoretical baby model was developed based on relations valid for heat and mass transfer rates from a cylinder and flat surface. Convective and radiative (dry) and evaporative heat transfer coefficients calculated from this model agreed well with the measured values. The maximum heat dissipation from a baby was calculated for combinations of air temperatures (22-30 degrees C) and relative humidities (70-90% rh). The results indicate that a naked baby can dissipate about 100% more heat than is produced during basal conditions when the bag is ventilated (70 1 min(-1)) and the ambient climate is 30 degrees C and 90% rh. If the ventilation rate is 40 1 min(-1), the margin is reduced to 50%. Clothing reduces the margin further. Ventilating the bag with 70 1 min(-1), a dressed baby can dissipate only 10-20% more heat than is produced during basal conditions in a climate (27 degrees C and 80% rh) that is obtained in a crowded shelter after about 24 h of occupation. PMID:15150661

  11. 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.

  12. 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

  13. 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.

  14. Fast extraction and dilution flow injection mass spectrometry method for quantitative chemical residue screening in food.

    PubMed

    Nanita, Sergio C; Stry, James J; Pentz, Anne M; McClory, Joseph P; May, John H

    2011-07-27

    A prototype multiresidue method based on fast extraction and dilution of samples followed by flow injection mass spectrometric analysis is proposed here for high-throughput chemical screening in complex matrices. The method was tested for sulfonylurea herbicides (triflusulfuron methyl, azimsulfuron, chlorimuron ethyl, sulfometuron methyl, chlorsulfuron, and flupyrsulfuron methyl), carbamate insecticides (oxamyl and methomyl), pyrimidine carboxylic acid herbicides (aminocyclopyrachlor and aminocyclopyrachlor methyl), and anthranilic diamide insecticides (chlorantraniliprole and cyantraniliprole). Lemon and pecan were used as representative high-water and low-water content matrices, respectively, and a sample extraction procedure was designed for each commodity type. Matrix-matched external standards were used for calibration, yielding linear responses with correlation coefficients (r) consistently >0.99. The limits of detection (LOD) were estimated to be between 0.01 and 0.03 mg/kg for all analytes, allowing execution of recovery tests with samples fortified at ≥0.05 mg/kg. Average analyte recoveries obtained during method validation for lemon and pecan ranged from 75 to 118% with standard deviations between 3 and 21%. Representative food processed fractions were also tested, that is, soybean oil and corn meal, yielding individual analyte average recoveries ranging from 62 to 114% with standard deviations between 4 and 18%. An intralaboratory blind test was also performed; the method excelled with 0 false positives and 0 false negatives in 240 residue measurements (20 samples × 12 analytes). The daily throughput of the fast extraction and dilution (FED) procedure is estimated at 72 samples/chemist, whereas the flow injection mass spectrometry (FI-MS) throughput could be as high as 4.3 sample injections/min, making very efficient use of mass spectrometers with negligible instrumental analysis time compared to the sample homogenization, preparation, and data

  15. Sensitivity of a Chemical Mass Balance model to different molecular marker traffic source profiles

    NASA Astrophysics Data System (ADS)

    Pant, Pallavi; Yin, Jianxin; Harrison, Roy M.

    2014-01-01

    Use of the Chemical Mass Balance (CMB) model for aerosol source apportionment requires the input of source profiles of chemical constituents. Such profiles derived from studies in North America are relatively abundant, but are very scarce from European studies. In particular, there is a lack of data from European road vehicles. This study reports results from a comparison of road traffic source profiles derived from (1) US dynamometer studies of individual vehicles with (2) a traffic profile derived from measurements in a road tunnel in France and (3) new data derived from a twin-site study in London in which concentrations at an urban background site are subtracted from those measured at a busy roadside to derive a traffic increment profile. The dynamometer data are input as a diesel exhaust, gasoline exhaust and smoking engine profile, or alternatively as just a diesel exhaust and gasoline exhaust profile. Running the CMB model with the various traffic profiles together with profiles for other sources of organic carbon gives variable estimates of the contribution of traffic to organic carbon and to PM2.5 concentrations. These are tested in two ways. Firstly, unassigned organic carbon in the output from the CMB model, assumed to be secondary organic carbon, is compared to secondary organic carbon estimated independently using the elemental carbon tracer method. Secondly, the estimated traffic contribution to organic carbon and PM2.5 is compared with an estimate derived simply from the measured elemental carbon concentrations, and the effect on aerosol mass closure is investigated. In both cases the CMB model results correlate well with the independent measures, but there are marked differences according to the traffic source profile employed. As a general observation, it appears that the use of dynamometer data with inclusion of a smoking engine profile has a tendency to over-estimate traffic emissions at some sites whereas the tunnel profile shows a tendency to

  16. Determination of acrylamide in coffee and chocolate by pressurised fluid extraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Pardo, O; Yusà, V; Coscollà, C; León, N; Pastor, A

    2007-07-01

    A selective and sensitive procedure has been developed and validated for the determination of acrylamide in difficult matrices, such as coffee and chocolate. The proposed method includes pressurised fluid extraction (PFE) with acetonitrile, florisil clean-up purification inside the PFE extraction cell and detection by liquid chromatography (LC) coupled to atmospheric pressure ionisation in positive mode tandem mass spectrometry (APCI-MS-MS). Comparison of ionisation sources (atmospheric pressure chemical ionisation (APCI), atmospheric pressure photoionization (APPI) and the combined APCI/APPI) and clean-up procedures were carried out to improve the analytical signal. The main parameters affecting the performance of the different ionisation sources were previously optimised using statistical design of experiments (DOE). PFE parameters were also optimised by DOE. For quantitation, an isotope dilution approach was used. The limit of quantification (LOQ) of the method was 1 microg kg(-1) for coffee and 0.6 microg kg(-1) for chocolate. Recoveries ranged between 81-105% in coffee and 87-102% in chocolate. The accuracy was evaluated using a coffee reference test material FAPAS T3008. Using the optimised method, 20 coffee and 15 chocolate samples collected from Valencian (Spain) supermarkets, were investigated for acrylamide, yielding median levels of 146 microg kg(-1) in coffee and 102 microg kg(-1) in chocolate. PMID:17613050

  17. 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. PMID:24633585

  18. 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

  19. 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.

  20. Occupational Exposure to Natural Sources of Ionising Radiation in Ireland

    NASA Astrophysics Data System (ADS)

    Organo, Catherine; Colgan, Tony; Fenton, David; Synnott, Hugh; Currivan, Lorraine

    2008-08-01

    The Radiological Protection Institute of Ireland (RPII) has recently completed a detailed evaluation of all radiation exposure pathways from sources of both natural and artificial radiation in the Irish environment. This paper presents a compilation of the occupational doses received by Irish workers exposed to natural sources of ionising radiation.

  1. Occupational Exposure to Natural Sources of Ionising Radiation in Ireland

    SciTech Connect

    Organo, Catherine; Colgan, Tony; Fenton, David; Synnott, Hugh; Currivan, Lorraine

    2008-08-07

    The Radiological Protection Institute of Ireland (RPII) has recently completed a detailed evaluation of all radiation exposure pathways from sources of both natural and artificial radiation in the Irish environment. This paper presents a compilation of the occupational doses received by Irish workers exposed to natural sources of ionising radiation.

  2. 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.

  3. Mass

    SciTech Connect

    Chris Quigg

    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.

  4. 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

  5. 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.

  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. PMID:11414024

  9. Capillary liquid chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Ostman, Pekka; Jäntti, Sirkku; Grigoras, Kestas; Saarela, Ville; Ketola, Raimo A; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto

    2006-07-01

    A miniaturized nebulizer chip for capillary liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (capillary LC-microchip APCI-MS) is presented. The APCI chip consists of two wafers, a silicon wafer and a Pyrex glass wafer. The silicon wafer has a DRIE etched through-wafer nebulizer gas inlet, an edge capillary insertion channel, a stopper, a vaporizer channel and a nozzle. The platinum heater electrode and pads for electrical connection were patterned on to the Pyrex glass wafer. The two wafers were joined by anodic bonding, creating a microchip version of an APCI-source. The sample inlet capillary from an LC column is directly connected to the vaporizer channel of the APCI chip. The etched nozzle in the microchip forms a narrow sample plume, which is ionized by an external corona needle, and the formed ions are analyzed by a mass spectrometer. The nebulizer chip enables for the first time the use of low flow rate separation techniques with APCI-MS. The performance of capillary LC-microchip APCI-MS was tested with selected neurosteroids. The capillary LC-microchip APCI-MS provides quantitative repeatability and good linearity. The limits of detection (LOD) with a signal-to-noise ratio (S/N) of 3 in MS/MS mode for the selected neurosteroids were 20-1000 fmol (10-500 nmol l(-1)). LODs (S/N = 3) with commercial macro APCI with the same compounds using the same MS were about 10 times higher. Fast heat transfer allows the use of the optimized temperature for each compound during an LC run. The microchip APCI-source provides a convenient and easy method to combine capillary LC to any API-MS equipped with an APCI source. The advantages and potentials of the microchip APCI also make it a very attractive interface in microfluidic APCI-MS. PMID:16804601

  10. CHEMICAL EVOLUTION IN HIGH-MASS STAR-FORMING REGIONS: RESULTS FROM THE MALT90 SURVEY

    SciTech Connect

    Hoq, Sadia; Jackson, James M.; Foster, Jonathan B.; Sanhueza, Patricio; Claysmith, Christopher; Guzmán, Andrés; Whitaker, J. Scott; Rathborne, Jill M.; Vasyunina, Tatiana; Vasyunin, Anton E-mail: jackson@bu.edu E-mail: claysmit@bu.edu E-mail: aguzmanf@cfa.harvard.edu E-mail: rathborne@csiro.au E-mail: aiv3f@virginia.edu

    2013-11-10

    The chemical changes of high-mass star-forming regions provide a potential method for classifying their evolutionary stages and, ultimately, ages. In this study, we search for correlations between molecular abundances and the evolutionary stages of dense molecular clumps associated with high-mass star formation. We use the molecular line maps from Year 1 of the Millimetre Astronomy Legacy Team 90 GHz (MALT90) Survey. The survey mapped several hundred individual star-forming clumps chosen from the ATLASGAL survey to span the complete range of evolution, from prestellar to protostellar to H II regions. The evolutionary stage of each clump is classified using the Spitzer GLIMPSE/MIPSGAL mid-IR surveys. Where possible, we determine the dust temperatures and H{sub 2} column densities for each clump from Herschel/Hi-GAL continuum data. From MALT90 data, we measure the integrated intensities of the N{sub 2}H{sup +}, HCO{sup +}, HCN and HNC (1-0) lines, and derive the column densities and abundances of N{sub 2}H{sup +} and HCO{sup +}. The Herschel dust temperatures increase as a function of the IR-based Spitzer evolutionary classification scheme, with the youngest clumps being the coldest, which gives confidence that this classification method provides a reliable way to assign evolutionary stages to clumps. Both N{sub 2}H{sup +} and HCO{sup +} abundances increase as a function of evolutionary stage, whereas the N{sub 2}H{sup +} (1-0) to HCO{sup +} (1-0) integrated intensity ratios show no discernable trend. The HCN (1-0) to HNC(1-0) integrated intensity ratios show marginal evidence of an increase as the clumps evolve.

  11. 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.

  12. Resonance laser-induced ionisation of sodium vapour taking radiative transfer into account

    SciTech Connect

    Kosarev, N I; Shaparev, N Ya

    2006-04-30

    The problem of ionisation of atomic sodium in the field of resonance laser radiation is numerically solved taking radiative transfer into account. Seed electrons are produced due to the mechanism of associative ionisation, then they gain energy in superelastic processes (collisions of the second kind) and initiate the avalanche ionisation of the medium by electron impact. We studied the effect of secondary radiation on the laser pulse propagation upon competition between the ionising and quenching electron collisions with excited atoms, on the kinetics of ionisation-induced vapour bleaching, and the plasma channel expansion in the form of a halo. (interaction of laser radiation with matter)

  13. Fragmentation energy index for universalization of fragmentation energy in ion trap mass spectrometers for the analysis of chemical weapon convention related chemicals by atmospheric pressure ionization-tandem mass spectrometry analysis.

    PubMed

    Palit, Meehir; Mallard, Gary

    2009-04-01

    The use of mass spectra generated at 70 eV in electron ionization (EI) as a universal standard for EI has helped in the generation of searchable library databases and had a profound influence on the analytical applications of gas chromatography/mass spectrometry (GC/MS), similarly for liquid chromatography tandem mass spectrometry (LC-MS/MS), suggesting a novel method to normalize the collisional energy for the universalization of fragmentation energy for the analysis of Chemical Weapon Convention (CWC)-related chemicals by atmospheric pressure ionization-tandem mass spectrometry (API-MS(n)) using three-dimensional (3D) ion trap instruments. For normalizing fragmentation energy a "fragmentation energy index" (FEI) is proposed which is an arbitrary scale based on the fact of specific MS/MS fragmentation obtained at different collisional energies for the reference chemicals which are not CWC scheduled compounds. FEI 6 for the generation of an MS(n) library-searchable mass spectral database is recommended. PMID:19331429

  14. 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

  15. 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

  16. Sensitivity effects in Uk'37 paleotemperature estimation by chemical ionization mass spectrometry.

    PubMed

    Chaler, R; Grimalt, J O; Pelejero, C; Calvo, E

    2000-12-15

    Analysis of C37 alkenone mixtures by gas chromatography (GC) with flame ionization detection (FID) and GC coupled to mass spectrometry (GC/MS) in the chemical ionization mode (CI) shows that the later is useful for paleotemperature estimation when ammonia is used as reagent gas. Conversely, the use of isobutane gives rise to Uk'37 readings that are dependent on the amount of C37 alkenones introduced in the system, being unreliable for paleoclimatic studies. However, ammonia CI GC/MS may produce Uk'37 measurements that deviate from those obtained by GC-FID, the method calibrated for temperature estimation from algal cultures and marine sedimentary data. The differences result from changes in relative sensitivity between the di- and triunsaturated alkenones and depend on the instrument used and operational conditions. This problem is solved in the present study by determination of the response factor linear equations for each alkenone and their average relative sensitivity (R) using mixtures of known composition. These parameters allow the transformation of the GC/MS readings into the GC-FID equivalents using the following equation: UG = R x UM/(1 - UM(1 - R)). Examples of the suitability of this approach are given. PMID:11140754

  17. Probing the protein interaction network of Pseudomonas aeruginosa cells by chemical cross-linking mass spectrometry

    PubMed Central

    Navare, Arti T.; Chavez, Juan D.; Zheng, Chunxiang; Weisbrod, Chad R.; Eng, Jimmy K.; Siehnel, Richard; Singh, Pradeep K.; Manoil, Colin; Bruce, James E.

    2015-01-01

    SUMMARY In pathogenic Gram-negative bacteria, interactions among membrane proteins are key mediators of host cell attachment, invasion, pathogenesis, and antibiotic resistance. Membrane protein interactions are highly dependent upon local properties and environment, warranting direct measurements on native protein complex structures as they exist in cells. Here we apply in vivo chemical cross-linking mass spectrometry, to reveal the first large-scale protein interaction network in the Pseudomonas aeruginosa, an opportunistic human pathogen, by covalently linking interacting protein partners, thereby fixing protein complexes in vivo. A total of 626 cross-linked peptide pairs, including previously unknown interactions of many membrane proteins are reported. These pairs not only define the existence of these interactions in cells, but also provide linkage constraints for complex structure predictions. Structures of three membrane proteins, namely, SecD-SecF, OprF, and OprI are predicted using in vivo cross-linked sites. These findings improve understanding of membrane protein interactions and structures in cells. PMID:25800553

  18. 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

  19. 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

  20. Performance of the chemical mass balance model with simulated local-scale aerosols

    NASA Astrophysics Data System (ADS)

    Javitz, H. S.; Watson, J. G.; Robinson, N.

    A general methodology for performing simulations of the Chemical Mass Balance (CMB) model is developed and applied to simple and complex local scale scenarios. The simple scenario consists of crustal, coal-fired power plant, motor vehicle and vegetative burning sources; the complex scenario adds oil-fired power plant, ocean, steel mill, lead smelter, municipal incinerator and background aerosol sources. Daily receptor filter concentrations of the most commonly measured elements in the primary emissions are simulated. These simulations incorporate daily fluctuations in source strengths, daily fluctuations in source profiles (as parameterized by a coefficient of variation, or CV, of temporal source profiles) and measurement error at the receptor (as parameterized by a CV of measurement error). The CMB is applied to each daily measurement using a source library containing all sources and their long-term profiles (which, though correct on average, are incorrect on any particular day). The extent of agreement of the actual and CMBestimated primary emission source strengths is measured as an average absolute error (AAE, the absolute difference between the daily actual and estimated primary emission source strengths averaged over 100 simulated days). These moderately realistic simulations provide an encouraging picture of CMB accuracy and precision. The CMB yields acceptable accuracy and precision (an AAE of 50% or less) even when the CV of temporal source profiles is 25% and the CV of measurement error is 10%.

  1. Laser-Induced Acoustic Desorption/Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Gao, Jinshan; Borton, David J.; Owen, Benjamin C.; Jin, Zhicheng; Hurt, Matt; Amundson, Lucas M.; Madden, Jeremy T.; Qian, Kuangnan; Kenttämaa, Hilkka I.

    2011-03-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a commercial 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. From the four APCI reagent systems tested, neat carbon disulfide provided the best results. 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 but minor amount of fragmentation was observed for these two 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 predominantly form stable molecular ions.

  2. [Determination of cyflufenamid residue in carrots by gas chromatography-negative chemical ionization mass spectrometry].

    PubMed

    Yang, Wenquan; Shen, Weijian; Zhao, Zengyun; Xu, Jinzhong; Shen, Chongyu; Wu, Bin

    2008-07-01

    A method was developed for the determination of cyflufenamid residue in carrots by solid phase extraction-gas chromatography-negative chemical ionization mass spectrometry (SPE-GC-NCI/MS). Cyflufenamid residue was extracted with ethyl acetate from carrots. The extract was cleaned-up by an active carbon SPE column connected to a neutral alumina SPE column. The analysis was carried out by the GC-NCI/MS with selected ion monitoring mode. The recoveries of cyflufenamid in carrot samples were in the range from 74.9% to 94.6% at four spiked levels, 0.005, 0.01, 0.02, 0.04 mg/kg, and the relative standard deviations (RSD) were less than 9.7% for inter-days. The linearity of the method was good in the range from 10 to 1000 ng/mL, and the limit of detection (LOD) was 0.001 mg/kg, and the limit of quantitation (LOQ) was 0.005 mg/kg. The method is selective without interference and is suitable for the determination and confirmation of cyflufenamid residue in carrots. PMID:18959256

  3. Evaluation of organic markers for chemical mass balance source apportionment at the Fresno Supersite

    NASA Astrophysics Data System (ADS)

    Chow, J. C.; Watson, J. G.; Lowenthal, D. H.; Chen, L. W. A.; Zielinska, B.; Mazzoleni, L. R.; Magliano, K. L.

    2007-04-01

    Sources of PM2.5 at the Fresno Supersite during high PM2.5 episodes occurring from 15 December 2000-3 February 2001 were estimated with the Chemical Mass Balance (CMB) receptor model. The ability of source profiles with organic markers to distinguish motor vehicle, residential wood combustion (RWC), and cooking emissions was evaluated with simulated data. Organics improved the distinction between gasoline and diesel vehicle emissions and allowed a more precise estimate of the cooking source contribution. Sensitivity tests using average ambient concentrations showed that the gasoline vehicle contribution was not resolved without organics. Organics were not required to estimate hardwood contributions. The most important RWC marker was the water-soluble potassium ion. The estimated cooking contribution did not depend on cholesterol because its concentrations were below the detection limit in most samples. Winter time source contributions were estimated by applying the CMB model to individual and average sample concentrations. RWC was the largest source, contributing 29-31% of measured PM2.5. Hardwood and softwood combustion accounted for 16-17% and 12-15%, respectively. Secondary ammonium nitrate and motor vehicle emissions accounted for 31-33% and 9-15%, respectively. The gasoline vehicle contribution (3-10%) was comparable to the diesel vehicle contribution (5-6%). The cooking contribution was 5-19% of PM2.5. Fresno source apportionment results were consistent with those estimated in previous studies.

  4. Interdomain conformational changes in Akt activation revealed by chemical cross-linking and tandem mass spectrometry.

    PubMed

    Huang, Bill X; Kim, Hee-Yong

    2006-06-01

    Akt, a serine/threonine kinase, plays a critical role in cell survival. Upon growth factor receptor stimulation, cytosolic Akt is recruited to the plasma membrane by phospholipid binding and activated through phosphorylation at Thr(308) and Ser(473). Although crystal structures for the parts of Akt have been reported, neither the three-dimensional structure of the whole molecule nor sequential conformational changes during activation have been demonstrated. In this study, we demonstrated that Akt undergoes dramatic interdomain conformational changes during activation processes by probing the three-dimensional structure of full-length Akt in solution using chemical cross-linking and tandem mass spectrometry. The cross-linking results not only provided new structural information but also revealed distinctive spatial arrangements of individual domains in the Akt molecule in resting, membrane-interacted, phosphorylated, and substrate-bound states. Our data allowed a new model for stepwise interdomain conformational changes in Akt activation sequence, setting a stage for the further investigation on Akt-membrane, Akt-protein, and/or Akt-drug interactions in solution to understand molecular mechanisms involved in physiological and pathophysiological processes of cell survival. PMID:16531397

  5. 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. PMID:25969527

  6. Molecular inventories and chemical evolution of low-mass protostellar envelopes

    NASA Astrophysics Data System (ADS)

    Jørgensen, J. K.; Schöier, F. L.; van Dishoeck, E. F.

    2004-03-01

    This paper presents the first substantial study of the chemistry of the envelopes around a sample of 18 low-mass pre- and protostellar objects for which physical properties have previously been derived from radiative transfer modeling of their dust continuum emission. Single-dish line observations of 24 transitions of 9 molecular species (not counting isotopes) including HCO+, N2H+, CS, SO, SO2, HCN, HNC, HC3N and CN are reported. The line intensities are used to constrain the molecular abundances by comparison to Monte Carlo radiative transfer modeling of the line strengths. In general the nitrogen-bearing species together with HCO+ and CO cannot be fitted by a constant fractional abundance when the lowest excitation transitions are included, but require radial dependences of their chemistry since the intensity of the lowest excitation lines are systematically underestimated in such models. A scenario is suggested in which these species are depleted in a specific region of the envelope where the density is high enough that the freeze-out timescale is shorter than the dynamical timescale and the temperature low enough that the molecule is not evaporated from the icy grain mantles. This can be simulated by a ``drop'' abundance profile with standard (undepleted) abundances in the inner- and outermost regions and a drop in abundance in between where the molecule freezes out. An empirical chemical network is constructed on the basis of correlations between the abundances of various species. For example, it is seen that the HCO+ and CO abundances are linearly correlated, both increasing with decreasing envelope mass. This is shown to be the case if the main formation route of HCO+ is through reactions between CO and H3+, and if the CO abundance still is low enough that reactions between H3+ and N2 are the main mechanism responsible for the removal of H3+. Species such as CS, SO and HCN show no trend with envelope mass. In particular no trend is seen between

  7. 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...

  8. DETERMINATION OF CHEMICAL CLASSES FROM MASS SPECTRA OF TOXIC ORGANIC COMPOUNDS BY SIMCA PATTERN RECOGNITION AND INFORMATION THEORY

    EPA Science Inventory

    The low resolution mass spectra of a set of 78 toxic volatile organic compounds were examined for information concerning chemical classes. These compounds were predominately chloro- and/or bromoaromatics, -alkanes, or -alkenes, which are routinely sought at trace levels in ambien...

  9. 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

  10. The Chemical Composition and Gas-to-Dust Mass Ratio of Nearby Interstellar Matter

    NASA Technical Reports Server (NTRS)

    Frisch, Priscilla C.; Slavin, Jonathan D.

    2003-01-01

    We use recent results on interstellar gas toward nearby stars and interstellar by-products within the solar system to select among the equilibrium radiative transfer models of the nearest interstellar material presented in Slavin & Frisch. For the assumption that O/H - 400 parts per million, models 2 and 8 are found to yield good fits to available data on interstellar material inside and outside of the heliosphere, with the exception of the Ne abundance in the pickup ion and anomalous cosmic-ray populations. For these models, the interstellar medium (ISM) at the entry point to the heliosphere has n(H(sup 0)) = 0.202-0.208/cu cm, n(He(sup 0) = 0.0137-0.0152/cu cm, and ionizations X(H) = 0.29-0.30, X(He) = 0.47-0.51. These best models suggest that the chemical composition of the nearby ISM is approx.60%-70% subsolar if S is undepleted. Both H(0) and H(+) need to be included when evaluating abundances of ions found in warm diffuse clouds. Models 2 and 8 yield an H filtration factor of approx.0.46. Gas-to-dust mass ratios for the ISM toward epsilon CMa are R(sub gd) = 178-183 for solar abundances of Holweger or R(sub gd) = 611-657 for an interstellar abundance standard 70% solar. Direct observations of dust grains in the solar system by Ulysses and Galileo yield R(sub gd) appr0x. 115 for models 2 and 8, supporting earlier results (Frisch and coworkers). If the local ISM abundances are subsolar, then gas and dust are decoupled over small spatial scales. The inferred variation in R(sub gd) over parsec length scales is consistent with the fact that the ISM near the Sun is part of a dynamically active cluster of cloudlets flowing away from the Sco-Cen association. Observations toward stars within approx.500 pc show that R(sub gd) correlates with the percentage of the dust mass that is carried by iron, suggesting that an Fe-rich grain core (by mass) remains after grain destruction. Evidently large dust grains (>10(exp -13) g) and small dust grains (<10(exp -13) g) are not

  11. 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

  12. 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

  13. 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

  14. 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

  15. 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

  16. Ionisation of a quantum dot by electric fields

    SciTech Connect

    Eminov, P A; Gordeeva, S V

    2012-08-31

    We have derived analytical formulas for differential and total ionisation probabilities of a two-dimensional quantum dot by a constant electric field. In the adiabatic approximation, we have calculated the probability of this process in the field of a plane electromagnetic wave and in a superposition of constant and alternating electric fields. The imaginary-time method is used to obtain the momentum distribution of the ionisation probability of a bound system by an intense field generated by a superposition of parallel constant and alternating electric fields. The total probability of the process per unit time is calculated with exponential accuracy. The dependence of the results obtained on the characteristic parameters of the problem is investigated. (laser applications and other topics in quantum electronics)

  17. Wedge Absorber Design for the Muon Ionisation Cooling Experiment

    SciTech Connect

    Rogers, C.; Snopok, P.; Coney, L.; Jansson, A.; /Fermilab

    2010-05-01

    In the Muon Ionisation Cooling Experiment (MICE), muons are cooled by ionisation cooling. Muons are passed through material, reducing the total momentum of the beam. This results in a decrease in transverse emittance and a slight increase in longitudinal emittance, but overall reduction of 6d beam emittance. In emittance exchange, a dispersive beam is passed through wedge-shaped absorbers. Muons with higher energy pass through more material, resulting in a reduction in longitudinal emittance as well as transverse emittance. We consider the cooling performance of different wedge materials and geometries and propose a set of measurements that would be made in MICE.We outline the resources these measurements would require and detail some constraints that guide the choice of wedge parameters.

  18. Physical and bio-chemical mass-balance model around seafloor cold seepages

    NASA Astrophysics Data System (ADS)

    Yamazaki, T.; Takeuchi, R.; Monoe, D.; Oomi, T.; Nakata, K.; Fukushima, T.

    2007-12-01

    Natural cold seepages are characterized as rapid upward transports of methane from deeper part of geological structures to the seafloors. Prior to reach the seafloors, when methane meets downwards diffusing seawater sulfate, it is oxidized anaerobically by a consortium of microorganisms that use sulfate as an oxidant, producing sulfide. The anaerobic oxidation of methane and anaerobic sulfate reduction are clarified as a coupled biological activity. A significant portion of the bicarbonate produced after the sulfate reduction as authigenic carbonate, mainly aragonite and high-Mg calcite, near the seafloor. Where the methane fluxes are much, these anaerobic reactions occur just beneath the seafloor. There, usually sulfur oxidizing microorganisms are visible on the seafloor just above the coupled consortium of microorganisms. They are called bacterial mats. When the fluxes too much, direct methane bubbling occurs and chemosynthesis-immobilization communities such as tubeworms and clams distribute around the bubbling locations with the bacterial mats. The physical and bio-chemical mass-balance model around cold seepages on seafloor and in water column has been studied by the authors and some preliminary results were reported (Yamazaki et al., 2005 and 2006; Takeuchi et al., 2007). The approach is to analyze the existing field observation and numerical modeling studies of cold seepages and to create a new physical and bio-chemical mass-balance model in the environment. The model is separated into three parts. They are methane supply, seafloor ecosystem, and water column units. The seafloor ecosystem unit has been improved to analyze the unsteady formation processes of the ecosystem. The time dependencies of formations of the consortium of microorganisms (AOM), the chemosynthetic community, and bicarbonates examined with the improved model are introduced. After the bubbling from seafloor, the methane bubble jet blows up in the water column due to the buoyancy. Then the

  19. IEC STANDARDS FOR INDIVIDUAL MONITORING OF IONISING RADIATION

    SciTech Connect

    Voytchev, Miroslav; Ambrosi, P.; Behrens, R.; Chiaro Jr, Peter John

    2011-01-01

    This paper presents IEC/SC 45B Radiation protection instrumentation and its standards for individual monitoring of ionising radiation: IEC 61526 Ed. 3 for active personal dosemeters and IEC 62387-1 for passive integrating dosimetry systems. The transposition of these standards as CENELEC (European) standards is also discussed together with the collaboration between IEC/SC 45B and ISO/TC 85/SC 2.

  20. Atmospheric amines and ammonia measured with a Chemical Ionization Mass Spectrometer (CIMS)

    NASA Astrophysics Data System (ADS)

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, A. B.; Madronich, S.; Sierra-Hernández, M. R.; Lawler, M.; Smith, J. N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, E. S.; Porcelli, L.; Brune, W. H.; Goldstein, A. H.; Lee, S.-H.

    2014-06-01

    We report ambient measurements of amines and ammonia with a~fast response chemical ionization mass spectrometer (CIMS) in a southeastern US 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 US. 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.

  1. A multivariate/chemical mass balance model for air pollution in China: A hybrid methodology

    SciTech Connect

    Zelenka, M.P.

    1992-01-01

    This research explores the possibility of using a two step method of identifying and quantifying air pollution emissions in an urban environment. The procedure uses a mathematical model called Target Transformation Factor Analysis (TTFA) to estimate source profiles using ambient trace element air concentration data. A source profile is analogous to a fingerprint since it is unique to each source of air pollution. It is important to use source profiles that are measured or estimated for the specific location under study. The profiles estimated by TTFA are then employed in a Chemical Mass Balance (CMB) source apportionment analysis for the airshed. Other known sources are estimated using source signatures from the literature. Applying the TTFA and CMB models in this fashion is called receptor modeling. Generically, a receptor model is the combination of measured air pollution concentration data with a numerical technique which apportions the measured air pollution among distinct source types. The results show that TTFA can be used to provide quantitative estimates of air pollution source profiles for an urban center in China. The number of profiles for unique source types was limited for this data set since emissions from certain types of sources co-varied during each sampling day. Consequently, the CMB analyses that applied the TTFA source profiles needed to be supplemented with standard US EPA source profiles. The application of TTFA for estimating source profiles from ambient data and the subsequent use of those profiles in CMB analyses with source profiles obtained from the EPA's source library can improve the statistical quality of the source apportionment analysis. TTFA can identify source categories of airborne pollution for specific cities, as well as give quantitative data on the composition of the emissions from those source types.

  2. 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.

  3. Erich Regener and the ionisation maximum of the atmosphere

    NASA Astrophysics Data System (ADS)

    Carlson, P.; Watson, A. A.

    2014-12-01

    In the 1930s the German physicist Erich Regener (1881-1955) did important work on the measurement of the rate of production of ionisation deep under water and in the atmosphere. Along with one of his students, Georg Pfotzer, he discovered the altitude at which the production of ionisation in the atmosphere reaches a maximum, often, but misleadingly, called the Pfotzer maximum. Regener was one of the first to estimate the energy density of cosmic rays, an estimate that was used by Baade and Zwicky to bolster their postulate that supernovae might be their source. Yet Regener's name is less recognised by present-day cosmic ray physicists than it should be, largely because in 1937 he was forced to take early retirement by the National Socialists as his wife had Jewish ancestors. In this paper we briefly review his work on cosmic rays and recommend an alternative naming of the ionisation maximum. The influence that Regener had on the field through his son, his son-in-law, his grandsons and his students, and through his links with Rutherford's group in Cambridge, is discussed in an appendix. Regener was nominated for the Nobel Prize in Physics by Schrödinger in 1938. He died in 1955 at the age of 73.

  4. 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

  5. Mass analysis of trifluoro-iodo-methane in a Surface Barrier Discharge

    NASA Astrophysics Data System (ADS)

    Rees, J. A.; Greenwood, C. L.; Lundie, D. T.; Seymour, D. L.; Hiden Analytical Team

    2011-10-01

    Surface barrier discharges operated at atmospheric pressure are effective chemical reactors. Mass analysis of the reaction products is possible using suitable high pressure mass spectrometer systems. As an example of the behaviour of simple surface barrier reactor (SBDs), experiments on the decomposition of CF3I are described in which the output from the reactor is admitted via a capillary inlet system into a Hiden HPR20 mass spectrometer. The discharge was operated using helium as the carrier gas. The observed mass spectra are discussed in terms of the plasma dissociation and the subsequent ionisation of the dissociated products in the electron impact ionisation source of the mass spectrometer. When oxygen was added to the gas mixture in the SBD, CFxO species were generated in the plasma. Their influence on the observed mass spectra is shown. The results demonstrate aspects of the capabilities of SBDs for dissociating halocarbon gases at atmospheric pressure and the possibilities of direct mass spectrometric monitoring of such processes.

  6. 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

  7. Investigation of the Reactivity of Oligodeoxynucleotides with Glyoxal and KMnO4 Chemical Probes by Electrospray Ionization Mass Spectrometry

    PubMed Central

    Parr, Carol; Pierce, Sarah E.; Smith, Suncerae I.; Brodbelt, Jennifer S.

    2010-01-01

    The reactions of two well-known chemical probes, glyoxal and potassium permanganate (KMnO4), with oligodeoxynucleotides were monitored by electrospray ionization (ESI) mass spectrometry to evaluate the influence of the sequence of DNA, its secondary structure, and interactions with associated ligands on the reactivity of the two probes. Glyoxal, a guanine-reactive probe, incorporated a mass shift of 58 Da, and potassium permanganate (KMnO4) is a thymine-reactive probe that resulted in a mass shift of 34 Da. The reactions depended on the accessibility of the nucleobases, and the peak abundances of the adducts in the ESI-mass spectra were used to quantify the extent of the chemical probe reactions. In this study, both mixed-base sequences were studied as well as control sequences in which one reactive site was located at the terminus or center of the oligodeoxynucleotide while the surrounding bases were a second, different nucleobase. In addition, the reactions of the chemical probes with non-covalent complexes formed between DNA and either actinomycin D or ethidium bromide, both known to interact with single strand DNA, were evaluated. PMID:21743793

  8. Isotopic Signature Transfer and Mass Pattern Prediction (IsoStamp): An Enabling Technique for Chemically-Directed Proteomics

    PubMed Central

    2011-01-01

    Directed proteomics applies mass spectrometry analysis to a subset of information-rich proteins. Here we describe a method for targeting select proteins by chemical modification with a tag that imparts a distinct isotopic signature detectable in a full-scan mass spectrum. Termed isotopic signature transfer and mass pattern prediction (IsoStamp), the technique exploits the perturbing effects of a dibrominated chemical tag on a peptide’s mass envelope, which can be detected with high sensitivity and fidelity using a computational method. Applying IsoStamp, we were able to detect femtomole quantities of a single tagged protein from total mammalian cell lysates at signal-to-noise ratios as low as 2.5:1. To identify a tagged-peptide’s sequence, we performed an inclusion list-driven shotgun proteomics experiment where peptides bearing a recoded mass envelope were targeted for fragmentation, allowing for direct site mapping. Using this approach, femtomole quantities of several targeted peptides were identified in total mammalian cell lysate, while traditional data-dependent methods were unable to identify as many peptides. Additionally, the isotopic signature imparted by the dibromide tag was detectable on a 12-kDa protein, suggesting applications in identifying large peptide fragments, such as those containing multiple or large posttranslational modifications (e.g., glycosylation). IsoStamp has the potential to enhance any proteomics platform that employs chemical labeling for targeted protein identification, including isotope coded affinity tagging, isobaric tagging for relative and absolute quantitation, and chemical tagging strategies for posttranslational modification. PMID:21604797

  9. Mass Spectrometry Applications for the Identification and Quantitation of Biomarkers Resulting from Human Exposure to Chemical Warfare Agents

    NASA Astrophysics Data System (ADS)

    Smith, J. Richard; Capacio, Benedict R.

    In recent years, a number of analytical methods using biomedical samples such as blood and urine have been developed for the verification of exposure to chemical warfare agents. The majority of methods utilize gas or liquid chromatography in conjunction with mass spectrometry. In a small number of cases of suspected human exposure to chemical warfare agents, biomedical specimens have been made available for testing. This chapter provides an overview of biomarkers that have been verified in human biomedical samples, details of the exposure incidents, the methods utilized for analysis, and the biomarker concentration levels determined in the blood and/or urine.

  10. Detection of trace levels of triclopyr using capillary gas chromatography-electron-capture negative-ion chemical ionization mass spectrometry.

    PubMed

    Begley, P; Foulger, B E

    1988-04-01

    Triclopyr, after esterification, is shown to be a suitable candidate for detection by gas chromatography-electron-capture negative-ion chemical ionization mass spectrometry forming a characteristic carboxylate anion which offers a high detection sensitivity. A detection limit of 70 fg reaching the ionizer is indicated. Low backgrounds and an absence of chemical interferences are shown for vegetation extracts, using a simple method of extraction and derivatisation. A similar behaviour is demonstrated for 2,4-D and 2,4,5-T. PMID:3379116

  11. Unexpected observation of ion suppression in a liquid chromatography/atmospheric pressure chemical ionization mass spectrometric bioanalytical method.

    PubMed

    Sangster, Tim; Spence, Mike; Sinclair, Peta; Payne, Richard; Smith, Christopher

    2004-01-01

    Ion suppression is a well-known phenomenon in electrospray ionization (ESI) mass spectrometry. These suppression effects have been shown to adversely affect the accuracy and precision of quantitative bioanalytical methods using ion spray. Such suppression effects have not been as well defined in atmospheric pressure chemical ionization (APCI) and there is some debate whether these effects actually occur in the ionization process using APCI. Here an example is described where clear ion suppression was observed during studies on a model compound and three metabolites using APCI liquid chromatography/tandem mass spectrometry (LC/MS/MS). PMID:15174192

  12. Imaging chemical differentiation around the low-mass protostar L483-mm

    NASA Astrophysics Data System (ADS)

    Jørgensen, J. K.

    2004-09-01

    This paper presents a millimeter wavelength aperture-synthesis study of the spatial variations of the chemistry in the envelope around the deeply embedded low-mass protostar L483-mm on ˜1000 AU (5 arcsec) scales. Lines of 8 molecular species including CN, C18O, CS, C34S, HCN, H13CN, HCO+ and N2H+ have been observed using the Owens Valley Radio Observatory Millimeter Array. Continuum emission at 2.7-3.4 mm is well-fit by an envelope model based on previously reported submillimeter continuum images down to the sensitivity of the interferometer without introducing a disk/compact source, in contrast to what is seen for other protostellar objects. A velocity gradient in dense material close to the central protostar is traced by HCN, CS and N2H+, and is perpendicular to the large-scale CO outflow, with a pattern consistent with rotation around a ˜1 M⊙ central object. Velocity gradients in the propagation direction of the outflow suggest a clear interaction between the outflowing material and ``quiescent'' core. Significant differences are observed between the emission morphologies of various molecular species. The C18O interferometer observations are fit with a ``drop'' abundance profile where CO is frozen-out in a region of the envelope with temperatures lower than 40 K and densities higher than 1.5 × 105 cm-3, which is also required to reproduce previously reported single-dish observations. The N2H+ emission strongly resembles that of NH3 and is found to be absent toward the central continuum source. This is a direct consequence of the high CO abundances in the inner region as illustrated by a chemical model for the L483 envelope. The observed CN emission forms a spatial borderline between the outflowing and quiescent material probed by, respectively, HCO+ and N2H+, and also shows intermediate velocities compared to these two species. A scenario is suggested in which CN is enhanced in the walls of an outflow cavity due to the impact of UV irradiation either from

  13. 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.

  14. 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.

  15. 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.

  16. Rapid detection of hazardous chemicals in textiles by direct analysis in real-time mass spectrometry (DART-MS).

    PubMed

    Antal, Borbála; Kuki, Ákos; Nagy, Lajos; Nagy, Tibor; Zsuga, Miklós; Kéki, Sándor

    2016-07-01

    Residues of chemicals on clothing products were examined by direct analysis in real-time (DART) mass spectrometry. Our experiments have revealed the presence of more than 40 chemicals in 15 different clothing items. The identification was confirmed by DART tandem mass spectrometry (MS/MS) experiments for 14 compounds. The most commonly detected hazardous substances were nonylphenol ethoxylates (NPEs), phthalic acid esters (phthalates), amines released by azo dyes, and quinoline derivates. DART-MS was able to detect NPEs on the skin of the person wearing the clothing item contaminated by NPE residuals. Automated data acquisition and processing method was developed and tested for the recognition of NPE residues thereby reducing the analysis time. PMID:27236310

  17. Differentiation of regioisomeric aromatic ketocarboxylic acids by atmospheric pressure chemical ionization CAD tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer

    SciTech Connect

    Amundson, Lucas M.; Owen, Ben C.; Gallardo, Vanessa A.; Habicht, S. C.; Fu, M.; Shea, R. C.; Mossman, A. B.; Kenttämaa, Hilkka I.

    2011-01-01

    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.

  18. 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

    NASA Astrophysics Data System (ADS)

    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.

  19. 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.

  20. Influence of ionisation zone motion in high power impulse magnetron sputtering on angular ion flux and NbO x film growth

    NASA Astrophysics Data System (ADS)

    Franz, Robert; Clavero, César; Kolbeck, Jonathan; Anders, André

    2016-02-01

    The ion energies and fluxes in the high power impulse magnetron sputtering plasma from a Nb target were analysed angularly resolved along the tangential direction of the racetrack. A reactive oxygen-containing atmosphere was used as such discharge conditions are typically employed for the synthesis of thin films. Asymmetries in the flux distribution of the recorded ions as well as their energies and charge states were noticed when varying the angle between mass-energy analyser and target surface. More positively charged ions with higher count rates in the medium energy range of their distributions were detected in +\\mathbf{E}× \\mathbf{B} than in -\\mathbf{E}× \\mathbf{B} direction, thus confirming the notion that ionisation zones (also known as spokes or plasma bunches) are associated with moving potential humps. The motion of the recorded negatively charged high-energy oxygen ions was unaffected. Nb{{\\text{O}}x} thin films at different angles and positions were synthesised and analysed as to their structure and properties in order to correlate the observed plasma properties to the film growth conditions. The chemical composition and the film thickness varied with changing deposition angle, where the latter, similar to the ion fluxes, was higher in +\\mathbf{E}× \\mathbf{B} than in -\\mathbf{E}× \\mathbf{B} direction.

  1. Chemical weathering, mass loss, and dust inputs across a climate by time matrix in the Hawaiian Islands

    NASA Astrophysics Data System (ADS)

    Porder, Stephen; Hilley, George E.; Chadwick, Oliver A.

    2007-06-01

    We determined the total mass loss and rate of chemical weathering from three minimally eroded, Hawaiian lava flows that are ˜ 10, 170, and 350 ka old. Using a backhoe, we sampled the entire weathering zone at 28 sites and measured the depletion or enrichment of each major element in each soil horizon relative to parent material. We were able to assess the influence of both climate and substrate age on chemical weathering because each flow crosses a precipitation gradient from ˜ 600 to ˜ 2500 mm yr - 1 . Mass loss rates were highest for the 0-10 ka interval under the wettest climatic conditions (54 t km - 2 yr - 1 ), and decreased to near zero in the wet sites during the 10-170 and 170-350 ka intervals. Not surprisingly, weathering rates were lower in drier sites; ˜ 24 t km - 2 yr - 1 from 0-10 ka to < 2 t km - 2 yr - 1 thereafter. However the effects of precipitation were non-linear. There was a precipitation threshold below which mass loss was relatively small, and above which mass loss was substantial but insensitive to increased rainfall. Chemical weathering rates depend on tectonic uplift, erosion, climate, rock type or some combination thereof. By working on stable, uneroded surfaces of a single rock type across a well-constrained precipitation gradient, we were able to identify another potential driver: the rate of dust deposition. Although Hawaíi is one of the least dusty places in the northern hemisphere, dust inputs reached 82% of the total mass loss from the weathering zone at some sites, and averaged 30% on the 170 ka flow. This highlights the potential importance of dust as a component of observed weathering fluxes from catchments worldwide.

  2. 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. PMID:25642789

  3. 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}⊙ 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.

  4. Atmospheric mass loss from Hot Jupiters: chemical reactions and a new hypothesis for the origin of water in habitable planets

    NASA Astrophysics Data System (ADS)

    Pinotti, Rafael; Boechat-Roberty, Heloisa M.

    2015-08-01

    The chemistry along the mass loss of Hot Jupiters is generally considered to be simple, consisting mainly of atoms, prevented from forming more complex species by the intense radiation field from their host stars. However, the results of our chemical reaction simulations, involving 56 species and 566 reactions, indicate that many simple molecules, including H2O+ and OH+, are formed along the mass loss of HD 209458 b and analogs, in a region farther away from the planet, where the temperature is lower (T < 2000 K). Our simulations included benzene formation reactions; the results indicate that carbon chain species are not formed in the mass loss of HD 209458 b. We also formulate a new hypothesis for the origin of water on the surface of habitable planets in general: chemical interaction of their primordial atmospheres with hydrogen and oxygen ions from the atmospheric mass loss of primordial, low density Hot Jupiters. This mechanism could have possibly operated in the Solar System and accounted for the formation of the oceans of the Earth.

  5. Direct Analysis of Nonvolatile Chemical Compounds on Surfaces Using a Hand-Held Mass Spectrometer with Synchronized Discharge Ionization Function.

    PubMed

    Wang, Xiao; Zhou, Xiaoyu; Ouyang, Zheng

    2016-01-01

    Synchronized discharge ionization (SDI) was previously developed for hand-held mass spectrometers with discontinuous atmospheric pressure interfaces. The function of SDI has been demonstrated for analysis of volatile organic compounds in air at high sensitivity, which is attributed to the fact that ions were produced next to the ion trap mass analyzer inside the vacuum manifold. In this study, a simple sampling device was designed and fitted to a hand-held mass spectrometer to characterize its potential in direct analysis of low-volatility chemicals on surfaces. Nine chemicals of vapor pressures ranging from 10(-4) to 10(-8) Torr (at room temperature), including pesticides, illicit drugs, and explosives, were selected to evaluate and demonstrate the analytical capability of the designed system. Compounds of vapor pressures below 10(-7) Torr, such as tetryl, cocaine, and tetrahydrocannabinol (THC), have been successfully detected. Direct analysis of pesticides from fruit and explosives from a large surface area has also been demonstrated. Tandem mass analysis was performed, which helped to confirm the analyte identity as well as to improve the signal-to-noise ratio (S/N). PMID:26618852

  6. 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

  7. Comprehensive Two Dimensional Gas Chromatography Fast Quadrupole Mass Spectrometry (GC×GC-qMS) for Urinary Steroid Profiling. Mass Spectral Characteristics with Chemical Ionization

    PubMed Central

    Zhang, Ying; Tobias, Herbert J.; Auchus, Richard J.; Brenna, J. Thomas

    2013-01-01

    Comprehensive two dimensional GC (GC×GC), coupled to either a time of flight MS (TOF-MS) or a fast scanning quadrupole MS (qMS) has greatly increased the peak capacity and separation space compared to conventional GC-MS. However, commercial GC×GC-TOFMS systems are not equipped with chemical ionization (CI) and do not provide dominant molecular ions or enable single ion monitoring for maximal sensitivity. A GC×GC-qMS in mass scanning mode was investigated with EI and positive CI (PCI), using CH4 and NH3 as reagent gases. Compared to EI, PCI-NH3 produced more abundant molecular ions and high mass structure specific ions for steroid acetates. Chromatography in two dimensions was optimized with a mixture of 12 endogenous and 3 standard acetylated steroids (SM15-AC) relevant to doping control. Eleven endogenous target steroid acetates were identified in normal urine based on their two retention times, and EI and PCI-NH3 mass spectra; nine of these endogenous target steroid acetates were identified in congenital adrenal hyperplasia (CAH) patients. The difference between the urinary steroids profiles of normal individuals and from a CAH patient can easily be visually distinguished by their GC×GC-qMS chromatograms. We focus here on the comparison and interpretation of the various mass spectra of the targeted endogenous steroids. PCI-NH3 mass spectra were most useful for unambiguous molecular weight determination and for establishing the number of -OH by the losses of 1 or more acetate groups. We conclude that PCI-NH3 with GC×GC-qMS provides improved peak capacity and pseudomolecular ions with structural specificity. PMID:22147458

  8. 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. PMID:22573054

  9. Characterization of Nonpolar Lipids and Selected Steroids by Using Laser-Induced Acoustic Desorption/Chemical Ionization, Atmospheric Pressure Chemical Ionization, and Electrospray Ionization Mass Spectrometry†

    PubMed Central

    Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

    2011-01-01

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H2O) with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids. PMID:21528012

  10. 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.

  11. Threshold law for positron-atom impact ionisation

    NASA Technical Reports Server (NTRS)

    Temkin, A.

    1982-01-01

    The threshold law for ionisation of atoms by positron impact is adduced in analogy with our approach to the electron-atom ionization. It is concluded the Coulomb-dipole region of the potential gives the essential part of the interaction in both cases and leads to the same kind of result: a modulated linear law. An additional process which enters positron ionization is positronium formation in the continuum, but that will not dominate the threshold yield. The result is in sharp contrast to the positron threshold law as recently derived by Klar on the basis of a Wannier-type analysis.

  12. 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.

  13. Imaging of Cells and Tissues with Mass Spectrometry: Adding Chemical Information to Imaging

    PubMed Central

    Zimmerman, Tyler A.; Monroe, Eric B.; Tucker, Kevin R.; Rubakhin, Stanislav S.; Sweedler, Jonathan V.

    2009-01-01

    Techniques that map the distribution of compounds in biological tissues can be invaluable in addressing a number of critical questions in biology and medicine. One of the newest methods, mass spectrometric imaging, has enabled investigation of spatial localization for a variety of compounds ranging from atomics to proteins. The ability of mass spectrometry to detect and differentiate a large number of unlabeled compounds makes the approach amenable to the study of complex biological tissues. This chapter focuses on recent advances in the instrumentation and sample preparation protocols that make mass spectrometric imaging of biological samples possible, including strategies for both tissue and single cell imaging using the following mass spectrometric ionization methods: matrix-assisted laser desorption/ionization, secondary ion, electrospray and desorption electrospray. PMID:19118682

  14. 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.

  15. 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

  16. Mass distributions and morphological and chemical characterization of urban aerosols in the continental Balkan area (Belgrade).

    PubMed

    Đorđević, D; Buha, J; Stortini, A M; Mihajlidi-Zelić, A; Relić, D; Barbante, C; Gambaro, A

    2016-01-01

    This work presents characteristics of atmospheric aerosols of urban central Balkans area, using a size-segregated aerosol sampling method, calculation of mass distributions, SEM/EDX characterization, and ICP/MS analysis. Three types of mass distributions were observed: distribution with a pronounced domination of coarse mode, bimodal distribution, and distribution with minimum at 1 μm describing the urban aerosol. SEM/EDX analyses have shown morphological difference and variation in the content of elements in samples. EDX spectra demonstrate that particles generally contain the following elements: Al, Ca, K, Fe, Mg, Ni, K, Si, S. Additionally, the presence of As, Br, Sn, and Zn found in air masses from southeast segment points out the anthropogenic activities most probably from mining activities in southeastern part of Serbia. The ratio Al/Si equivalent to the ratio of desert dust was associated with air masses coming from southeastern and southwestern segments, pointing to influences from North Africa and Middle East desert areas whereas the Al/Si ratio in other samples is significantly lower. In several samples, we found high values of aluminum in the nucleation mode. Samples with low share of crustal elements in the coarse mode are collected when Mediterranean air masses prevailed, while high share in the coarse mode was associated with continental air masses that could be one of the approaches for identification of the aerosol origin. Graphical abstract ᅟ. PMID:26347417

  17. 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. PMID:26237339

  18. 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

  19. Chemical compositions and radiative properties of dust and anthropogenic air masses study in Taipei Basin, Taiwan, during spring of 2004

    NASA Astrophysics Data System (ADS)

    Chang, Shih-Yu; Fang, Guor-Cheng; Chou, Charles C.-K.; Chen, Wei-Nai

    Asia is one of the major sources of not only mineral dust but also anthropogenic aerosols. Continental air masses associated with the East Asian winter monsoon always contain high contents of mineral dust and anthropogenic species and transported southeastward to Taiwan, which have significant influences on global atmospheric radiation transfer directly by scattering and absorbing solar radiation in each spring. However, few measurements for the long-range transported aerosol and its optical properties were announced in this area, between the Western Pacific and the southeastern coast of Mainland China. The overall objective of this work is to quantify the optical characteristics of different aerosol types in the Eastern Asian. In order to achieve this objective, meteorological parameters, concentrations of PM 10 and its soluble species, and optical property of atmospheric scattering coefficients were measured continuously with 1 h time-resolved from 11 February to 7 April 2004 in Taipei Basin (25°00'N, 121°32'E). In this work, the dramatic changes of meteorological parameters such as temperature and winds were used to determine the influenced period of each air mass. Continental, strong continental, marine, and stagnant air masses defined by the back-trajectory analysis and local meteorology were further characterized as long-range transport pollution, dust, clean marine, and local pollution aerosols, respectively, according to the diagnostic ratios. The aerosol mass scattering efficiency of continental pollution, dust, clean marine, and local pollution aerosols were ranged from 1.3 to 1.6, 0.7 to 1.0, 1.4 and 1.4 to 2.3 m 2 g -1, respectively. Overall, there are two distinct populations of aerosol mass scattering efficiencies, one for an aerosol chemical composition dominated by dust (<1.0 m 2 g -1) and the other for an aerosol chemical composition dominated by anthropogenic pollutants (1.3-2.3 m 2 g -1), which were similar to the previous measurements with

  20. 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.

  1. Application of electrospray and fast atom bombardment mass spectrometry to the identification of post-translational and other chemical modifications of proteins and peptides.

    PubMed

    Kouach, M; Belaïche, D; Jaquinod, M; Couppez, M; Kmiecik, D; Ricart, G; Van Dorsselaer, A; Sautière, P; Briand, G

    1994-05-01

    Mass spectrometry is a very powerful tool in the identification of chemical modifications of proteins and peptides. Often these modifications cannot be determined by conventional techniques. This report describes the combined use of electrospray ionization mass spectrometry and fast atom bombardment mass spectrometry to complete the primary structure of proteins and peptides. Examples illustrate how mass spectrometry is used to locate sites of phosphorylation, methylation and acetylation, and identify blocking groups and unexpected side reactions such as deamidation or alkylation. PMID:8204685

  2. Method for quantification of chemicals in a pollution plume using a moving membrane-based sensor exemplified by mass spectrometry.

    PubMed

    Janfelt, Christian; Lauritsen, Frants R; Toler, Strawn K; Bell, Ryan J; Short, R Timothy

    2007-07-15

    Quantification of a chemical concentration in a pollution plume using a moving membrane-based sensor can be problematic. In many cases, the sensor passes through the plume faster than the time necessary to reach a steady-state signal, which is often used for quantification. Since the exposure time is typically not known, quantification based upon the flow injection analysis principle is also impractical. In this paper, we present a two-dimensional calibration model, exemplified by membrane inlet mass spectrometry, in which the concentration of a chemical can be determined using a simple algorithm. The concentration is given by a calibration factor, which is multiplied by the peak height and divided by the value of a polynomial, calculated at a normalized peak width. The model is demonstrated to give good quantitative estimates of concentrations for exposure times down to approximately 1/10 of the time it takes to reach steady-state diffusion through the membrane. Although the model is demonstrated using membrane inlet mass spectrometry and detection of volatile organic chemicals, it should be generally applicable to many membrane-covered sensors. PMID:17563118

  3. Chemical mass balance source apportionment of TSP in a lignite-burning area of Western Macedonia, Greece

    NASA Astrophysics Data System (ADS)

    Samara, Constantini

    Total suspended particle mass concentrations (TSP) were determined in the Kozani-Ptolemais-Florina basin (western Macedonia, Greece), an area with intensive lignite burning for power generation. The study was conducted over a 1-year period (November 2000-November 2001) at 10 receptor sites located at variable distances from the power plants. Ambient TSP samples were analyzed for 27 major, minor and trace elements. Particulate emissions were also collected from a variety of sources including fly ash, lignite dust, automobile traffic, domestic heating, and open-air burning of agricultural biomass and refuse, and analyzed for the same chemical components. Ambient and source chemical profiles were used for source identification and apportionment of TSP by employing a chemical mass balance (CMB) receptor model. Diesel burning in vehicular traffic and in the power plants for generator start up was found to be the major contributor to ambient TSP levels at all 10 sites. Other sources with significant contributions were domestic coal burning, vegetative burning (wood combustion and agricultural burns) and refuse open-air burning. Fly ash escaping the electrostatic precipitators of the power plants was a minor contributor to ambient TSP.

  4. 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+.

  5. 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

  6. SHAMS: Combining chemical modification of RNA with mass spectrometry to examine polypurine tract-containing RNA/DNA hybrids

    PubMed Central

    Turner, Kevin B.; Yi-Brunozzi, Hye Young; Brinson, Robert G.; Marino, John P.; Fabris, Daniele; Le Grice, Stuart F.J.

    2009-01-01

    Selective 2′-hydroxyl acylation analyzed by primer extension (SHAPE) has gained popularity as a facile method of examining RNA structure both in vitro and in vivo, exploiting accessibility of the ribose 2′-OH to acylation by N-methylisatoic anhydride (NMIA) in unpaired or flexible configurations. Subsequent primer extension terminates at the site of chemical modification, and these products are fractionated by high-resolution gel electrophoresis. When applying SHAPE to investigate structural features associated with the wild-type and analog-substituted polypurine tract (PPT)–containing RNA/DNA hybrids, their size (20–25 base pairs) rendered primer extension impractical. As an alternative method of detection, we reasoned that chemical modification could be combined with tandem mass spectrometry, relying on the mass increment of RNA fragments containing the NMIA adduct (Mr = 133 Da). Using this approach, we demonstrate both specific modification of the HIV-1 PPT RNA primer and variations in its acylation pattern induced by replacing template nucleotides with a non-hydrogen-bonding thymine isostere. Our selective 2′-hydroxyl acylation analyzed by mass spectrometry strategy (SHAMS) should find utility when examining the structure of small RNA fragments or RNA/DNA hybrids where primer extension cannot be performed. PMID:19535461

  7. 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

    2016-04-01

    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+.

  8. 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

  9. Romanian medical exposure to ionising radiation in 2012.

    PubMed

    Girjoaba, O; Cucu, A

    2015-07-01

    Medical exposure, the main source of artificial exposure, shows an increasing trend in the last years, manifested both by increasing the number of examinations with ionising radiation and by increasing the patient dose level. Annual results obtained for medical exposure to ionising radiation based on the data collected from Romanian hospitals are useful for the update of the national database and optimisation of diagnostic procedures in radiology and nuclear medicine. Medical exposure level is expressed in terms of annual collective dose and is evaluated from annual frequencies and the average effective dose per procedure for different types of radiological and nuclear medicine procedures. The Romanian hospitals reported during 2012 a number of 5,505,792 radiological examinations and 17,088 diagnostic procedures of nuclear medicine. Based on the data reported, the average effective doses and their contributions to the collective dose were evaluated. The main contributions to the collective dose of the radiological procedures are registered for CT abdomen and pelvis region, followed by thorax CT and head CT examinations. The next positions are fluoroscopic examination of the thorax and gastrointestinal disease and radiographic examination of the lumbar spine and thorax, which in spite of their low effective dose have an important contribution to the collective dose due to the large number of examinations. For nuclear medicine procedures, major contributions to collective dose are given by bone scintigraphy, followed by PET-CT and thyroid scintigraphy. PMID:25848102

  10. 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.

  11. 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...

  12. 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...

  13. FAST ANALYSIS OF BEVERAGES USING A MASS SPECTRAL BASED CHEMICAL SENSOR

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Detection of adulteration, contamination or inconsistencies in food and flavor samples should be accurate and fast. Chemical sensors are ideal for these types of applications because they provide fast measurement times (2-6 minutes). While analysis times are crucial, accuracy and precision of the ...

  14. Real-time Detection of Particulate Chemical Composition Near Agricultural Facilities Using Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Agricultural facilities are the source of many types of particles and gases that can exhibit an influence on air quality. Emissions potentially impacting air quality from agricultural sources have become a concern for various state and federal regulatory agencies. Particle mass concentration influe...

  15. 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...

  16. 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

  17. The temperature, mass and chemical composition of the bare ONe white dwarf SDSS1102+4054

    NASA Astrophysics Data System (ADS)

    Gaensicke, Boris

    2010-09-01

    SDSS1102+2054 is a cool white dwarf with a helium-dominated atmosphere that exhibits strong oxygen and carbon lines in its optical spectrum. The oxygen-to-carbon {O/C} abundance ratio implied by the line strengths is much larger than unity, which rules out out a carbon-oxygen core composition and provides strong evidence that SDSS1102+2054 is a naked oxygen-neon {ONe} core. Stellar evolution models predict that such extreme O/C abundance ratios are achieved only in the most massive stars that just avoid core-collapse, and we hence believe that SDSS1102+2054 descends from an intermediate mass star close to the 8-10Msun boundary between stars leaving behind either white dwarfs, or neutron stars. As such, this white dwarf has the potential to provide important constraints on our understanding of the evolution of intermediate mass stars, in particular testing predictions of mass loss, the efficiency of convective core mixing, and the relevant nuclear reaction rates. We propose to obtain intermediate-resolution HST/COS spectroscopy of SDSS1102+2054 to overcome the limitations of the available ground-based data and accurately measure its effective temperature, mass, and Mg abundance, and stringently test the current models of stellar evolution.

  18. Simultaneous Measurement of Serum Chemical Castration Agents and Testosterone Levels Using Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry.

    PubMed

    Ko, Dae-Hyun; Lee, Kyunghoon; Jeon, Sun-Hee; Song, Sang Hoon; Yun, Yeo-Min; Chun, Sail; Kim, Hee Seung; Kim, Jin Young; In, Moon Kyo; Song, Junghan

    2016-05-01

    Chemical castration involves administration of drugs to prevent pathological sexual behavior, reduce abnormal sexual drive and treat hormone-dependent cancers. Various drugs have been used for chemical castration; however, substantial interindividual variability and side effects are often observed. In this study, we proposed a useful monitoring method for the application of chemical castration agents using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS-MS). Testosterone, cyproterone acetate, medroxyprogesterone, goserelin acetate, leuprolide acetate and triptorelin acetate were analyzed by UPLC-MS-MS. The target drugs were extracted from serum samples by double protein precipitation using methanol. Testosterone-1,2-d2 and buserelin acetate were used as internal standards. Parameters of analytical performance were evaluated, including imprecision, linearity, ion suppression and detection capabilities. Testosterone measurements were compared with the results of immunoassays. Serum specimens from 51 subjects who underwent chemical castration were analyzed. All drugs and testosterone were well extracted and separated using our method. The method was essentially free from potential interferences and ion suppression. Within-run and between-run imprecision values were <15%. The lower limits of quantification were 0.125 and 0.5-1.0 ng/mL for testosterone and other drugs, respectively. Good correlations with pre-existing immunoassays for testosterone measurement were observed. Sera from subjects who underwent androgen deprivation therapy showed variable levels of drugs. We successfully developed a UPLC-MS-MS-based monitoring method for chemical castration. The performance of our method was generally acceptable. This method may provide a novel monitoring strategy for chemical castration to enhance expected effects while reducing unwanted side effects. PMID:26989223

  19. 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

  20. Ion chemistry of VX surrogates and ion energetics properties of VX: new suggestions for VX chemical ionization mass spectrometry detection.

    PubMed

    Midey, Anthony J; Miller, Thomas M; Viggiano, A A; Bera, Narayan C; Maeda, Satoshi; Morokuma, Keiji

    2010-05-01

    Room temperature rate constants and product ion branching ratios have been measured for the reactions of numerous positive and negative ions with VX chemical warfare agent surrogates representing the amine (triethylamine) and organophosphonate (diethyl methythiomethylphosphonate (DEMTMP)) portions of VX. The measurements have been supplemented by theoretical calculations of the proton affinity, fluoride affinity, and ionization potential of VX and the simulants. The results show that many proton transfer reactions are rapid and that the proton affinity of VX is near the top of the scale. Many proton transfer agents should detect VX selectively and sensitively in chemical ionization mass spectrometers. Charge transfer with NO(+) should also be sensitive and selective since the ionization potential of VX is small. The surrogate studies confirm these trends. Limits of detection for commercial and research grade CIMS instruments are estimated at 80 pptv and 5 ppqv, respectively. PMID:20384284

  1. 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.

  2. 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

  3. 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

  4. [A study on the chemical components of essential oil of oak moss concrete by gas chromatography/mass spectrometry].

    PubMed

    Gao, Y; Liu, B Z; Zhu, X L; Shi, L; Chen, J L; Gong, M; Zhang, L G

    2000-05-01

    The essential oil of oak moss concrete was extracted by volatile oil content equipment. The chemical compositions and their relative contents were analyzed by GC and GC/MS. A Supelco-5 fused silica capillary column (30 m x 0.32 mm i.d.; 0.25 micron thickness) and a flame ionization detector (FID) were employed in GC analysis. The temperature program included temperature increase of 4 degrees C/min from 50 degrees C to 250 degrees C, and a 10 min isothermal period at 250 degrees C. Mass spectra were obtained by electron impact at 70 eV and a source temperature of 170 degrees C. Twenty-four volatile compounds of oak mass concrete were identified, which comprised more than 83% of volatile fraction. The major components were diethyl phthalate, alpha-terpineol, cedrane and linalool. PMID:12541566

  5. Characterization of a novel diclofenac metabolite in human urine by capillary gas chromatography-negative chemical ionization mass spectrometry.

    PubMed

    Blum, W; Faigle, J W; Pfaar, U; Sallmann, A

    1996-10-25

    A sensitive analytical method was developed to characterize diclofenac metabolites in small amounts of body fluids. Desalted and lyophilized urine samples were extracted with supercritical carbon dioxide directly or after acidic hydrolysis. The extracts were derivatized with N-tert.-butyldimethylsilyl-N-methyltrifluoroacetamide. The derivatives were separated by capillary gas chromatography and identified by negative chemical ionization mass spectrometry. Full mass spectra were obtained at a level of 1.10(-9) g/ml. With direct extraction, the metabolites could be analysed in one step as open-chained acids and as (cyclic) oxindoles. By acidic hydrolysis the conjugates were transformed to the oxindoles. With both methods, a new main metabolite, [2-[2,6-dichloro-4-hydroxy-3-methoxyphenyl)amino]phenyl]acetic acid, was identified The mechanism of its formation is discussed. PMID:8953166

  6. 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

  7. Collection method for chemical particulates on surfaces with detection using thermal desorption-ion trap mass spectrometry.

    PubMed

    Ewing, K J; Gibson, D; Sanghera, J; Miklos, F

    2013-05-01

    Successful analysis of particulate/low vapor pressure analytes such as explosives and toxic chemicals, and commercial pesticides require new sampling tools that enable detection of these analytes using current vapor phase detection instruments. We describe a sampling approach that uses stainless steel screens coated with a sticky polydimethyl siloxane (PDMS) coating to capture particulates from surfaces. Preliminary results for the collection of dimethyl methylphosphonate (DMMP) sorbed onto silica gel (SG) particulates (DMMP/SG) from a surface with subsequent analysis by thermal desorption-cylindrical ion trap mass spectrometry (TD-CITMS) are reported. PMID:23601282

  8. 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.

  9. Characteristics of low-temperature plasma ionization for ambient mass spectrometry compared to electrospray ionization and atmospheric pressure chemical ionization.

    PubMed

    Albert, Anastasia; Engelhard, Carsten

    2012-12-18

    Ambient desorption/ionization mass spectrometry (ADI-MS) is an attractive method for direct analysis with applications in homeland security, forensics, and human health. For example, low-temperature plasma probe (LTP) ionization was successfully used to detect, e.g., explosives, drugs, and pesticides directly on the target. Despite the fact that the field is gaining significant attention, few attempts have been made to classify ambient ionization techniques based on their ionization characteristics and performance compared to conventional ionization sources used in mass spectrometry. In the present study, relative ionization efficiencies (RIEs) for a large group of compound families were determined with LTP-Orbitrap-MS and compared to those obtained with electrospray ionization mass spectrometry (ESI-MS) and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). RIEs were normalized against one reference compound used across all methods to ensure comparability of the results. Typically, LTP analyte ionization through protonation/deprotonation (e.g., 4-acetamidophenol) was observed; in some cases (e.g., acenaphthene) radicals were formed. Amines, amides, and aldehydes were ionized successfully with LTP. A benefit of LTP over conventional methods is the possibility to successfully ionize PAHs and imides. Here, the studied model compounds could be detected by neither APCI nor ESI. LTP is a relatively soft ionization method because little fragmentation of model compounds was observed. It is considered to be an attractive method for the ionization of low molecular weight compounds over a relatively wide polarity range. PMID:23134531

  10. 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.

  11. Facility monitoring of chemical warfare agent simulants in air using an automated, field-deployable, miniature mass spectrometer.

    PubMed

    Smith, Jonell N; Noll, Robert J; Cooks, R Graham

    2011-05-30

    Vapors of four chemical warfare agent (CWA) stimulants, 2-chloroethyl ethyl sulfide (CEES), diethyl malonate (DEM), dimethyl methylphosphonate (DMMP), and methyl salicylate (MeS), were detected, identified, and quantitated using a fully automated, field-deployable, miniature mass spectrometer. Samples were ionized using a glow discharge electron ionization (GDEI) source, and ions were mass analyzed with a cylindrical ion trap (CIT) mass analyzer. A dual-tube thermal desorption system was used to trap compounds on 50:50 Tenax TA/Carboxen 569 sorbent before their thermal release. The sample concentrations ranged from low parts per billion [ppb] to two parts per million [ppm]. Limits of detection (LODs) ranged from 0.26 to 5.0 ppb. Receiver operating characteristic (ROC) curves are presented for each analyte. A sample of CEES at low ppb concentration was combined separately with two interferents, bleach (saturated vapor) and diesel fuel exhaust (1%), as a way to explore the capability of detecting the simulant in an environmental matrix. Also investigated was a mixture of the four CWA simulants (at concentrations in air ranging from 270 to 380 ppb). Tandem mass (MS/MS) spectral data were used to identify and quantify the individual components. PMID:21504010

  12. 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

  13. Chemical modification of deoxyribonucleic acids: Quantitation of 3-methylthymidine and O4-methylthymidine by tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wood, Joe M.; Hoke, Steven H., II; Graham Cooks, R.; Chae, Whi-Gun; Chang, Ching-Jer

    1991-12-01

    Quantitation of 3-methylthymidine and O4-methylthymidine generated in the reaction of calf thymus DNA with methyl methanesulfonate (MeMS) and 1-methyl-1nitrosourea (MeNU) by mass spectrometry is reported. Quantitative precision of 7% or better is achieved on samples of 10-12 -10-13 mole in the HPLC and a final stage of separation before quantification by tandem mass spectrometry using desorption chemical ionization. Synthetic CD3-labeled nucleosides were used as internal standards for mass spectral quantification. A unique mass spectrometric scanning procedure, which allowed simultaneous MS--MS product ion analysis of both the analyte and the internal standard, was utilized to enchance precision and accuracy in these low level determinations. MeNU (a potent carcinogen) resulted in 18&%; 3-methylation and 0.17% O4-methylation of deoxythymidine whereas MeMS (a weak carcinogen) produced only 6.8% 3-methylation and 0.005% of deoxythymidine. These results demonstrate that the sensitivity and accuracy of this method should be adequate for the detection and quantification of methyl-nucleosides at the sub-picomole level at which mutation is induced in cell cultures.

  14. 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

  15. 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.

  16. Plasma flame for mass purification of contaminated air with chemical and biological warfare agents

    NASA Astrophysics Data System (ADS)

    Uhm, Han S.; Shin, Dong H.; Hong, Yong C.

    2006-09-01

    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 22cm diameter and 30cm length, purifies an airflow rate of 5000lpm 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.

  17. 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

  18. 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

  19. 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.

  20. CHEMICAL RESIDUES IN DOLPHINS FROM THE U.S. ATLANTIC COAST INCLUDING ATLANTIC BOTTLENOSE OBTAINED DURING THE 1987/88 MASS MORTALITY

    EPA Science Inventory

    Bottlenose dolphins (Tursiops truncatus) collected during the 1987/88 mass mortality event along the Atlantic coast ot the United States have been analyzed for anthropogenic chemical contaminants. Average contaminant concentrations in adult males were higher than the average conc...

  1. 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

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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

    2015-01-01

    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

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. 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

  12. Identification of the chemical constituents of Chinese medicine Yi-Xin-Shu capsule by molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation.

    PubMed

    Wang, Hong-ping; Chen, Chang; Liu, Yan; Yang, Hong-Jun; Wu, Hong-Wei; Xiao, Hong-Bin

    2015-11-01

    The incomplete identification of the chemical components of traditional Chinese medicinal formula has been one of the bottlenecks in the modernization of traditional Chinese medicine. Tandem mass spectrometry has been widely used for the identification of chemical substances. Current automatic tandem mass spectrometry acquisition, where precursor ions were selected according to their signal intensity, encounters a drawback in chemical substances identification when samples contain many overlapping signals. Compounds in minor or trace amounts could not be identified because most tandem mass spectrometry information was lost. Herein, a molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation method for complex Chinese medicine chemical constituent analysis was developed. The precursor ions were selected according to their two-dimensional characteristics of retention times and mass-to-charge ratio ranges from herbal compounds, so that all precursor ions from herbal compounds were included and more minor chemical constituents in Chinese medicine were identified. Compared to the conventional automatic tandem mass spectrometry setups, the approach is novel and can overcome the drawback for chemical substances identification. As an example, 276 compounds from the Chinese Medicine of Yi-Xin-Shu capsule were identified. PMID:26311399

  13. 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. PMID:26890087

  14. 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.

  15. 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.

  16. On-line characterization of organic aerosols formed from biogenic precursors using atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Kückelmann, U; Warscheid, B; Hoffmann, T

    2000-04-15

    A method to investigate the chemical composition of organic aerosols formed from biogenic hydrocarbon oxidation using atmospheric pressure chemical ionization mass spectrometry (APCI/MS) is described. The method involves the direct introduction of aerosol particles into the ion source of the mass spectrometer. Using this technique, reaction monitoring experiments of alpha-pinene ozonolysis show the formation of hetero- and homomolecular cluster anions (dimers) of the primary oxidation products (multifunctional carboxylic acids). Since the formation of dimers plays a profound role in new particle formation processes by homogeneous nucleation in the atmosphere and, at the same time, is an intrinsic feature of APCI, it is essential to differentiate between both processes when on-line APCI/MS is applied. In this paper, we compare the results from the investigations of organic aerosols and artificially generated dimer cluster ions of the same compounds using identical ionization conditions. The clusters and their formation processes are characterized by varying the analyte concentration, investigating the thermal stability of dimers, and studying collisional activation properties of both ion species. The investigations show a significant difference in ion stability: dimer anions measured on-line have an estimated stability that is 20 kJ mol(-1) higher than that of the corresponding artificially generated cluster ions. Hence, the technique provides the possibility to accurately characterize dimers as ionized reaction products from biogenic hydrocarbon oxidation and allows an insight into the process of new-particle formation by homogeneous nucleation. PMID:10784160

  17. An Ultra-Trace Analysis Technique for SF6 Using Gas Chromatography with Negative Ion Chemical Ionization Mass Spectrometry.

    PubMed

    Jong, Edmund C; Macek, Paul V; Perera, Inoka E; Luxbacher, Kray D; McNair, Harold M

    2015-07-01

    Sulfur hexafluoride (SF6) is widely used as a tracer gas because of its detectability at low concentrations. This attribute of SF6 allows the quantification of both small-scale flows, such as leakage, and large-scale flows, such as atmospheric currents. SF6's high detection sensitivity also facilitates greater usage efficiency and lower operating cost for tracer deployments by reducing quantity requirements. The detectability of SF6 is produced by its high molecular electronegativity. This property provides a high potential for negative ion formation through electron capture thus naturally translating to selective detection using negative ion chemical ionization mass spectrometry (NCI-MS). This paper investigates the potential of using gas chromatography (GC) with NCI-MS for the detection of SF6. The experimental parameters for an ultra-trace SF6 detection method utilizing minimal customizations of the analytical instrument are detailed. A method for the detection of parts per trillion (ppt) level concentrations of SF6 for the purpose of underground ventilation tracer gas analysis was successfully developed in this study. The method utilized a Shimadzu gas chromatography with negative ion chemical ionization mass spectrometry system equipped with an Agilent J&W HP-porous layer open tubular column coated with an alumina oxide (Al2O3) S column. The method detection limit (MDL) analysis as defined by the Environmental Protection Agency of the tracer data showed the method MDL to be 5.2 ppt. PMID:25452581

  18. Real time in situ chemical characterization of submicrometer organic particles using direct analysis in real time-mass spectrometry.

    PubMed

    Nah, Theodora; Chan, ManNin; Leone, Stephen R; Wilson, Kevin R

    2013-02-19

    Direct analysis in real time mass spectrometry (DART-MS) is used to analyze the surface chemical composition of nanometer-sized organic aerosol particles in real time at atmospheric pressure. By introducing a stream of particles in between the DART ionization source and the atmospheric pressure inlet of the mass spectrometer, the aerosol is exposed to a thermal flow of helium or nitrogen gas containing some fraction of metastable helium atoms or nitrogen molecules. In this configuration, the molecular constituents of organic particles are desorbed, ionized, and detected with reduced molecular ion fragmentation, allowing for compositional identification. Aerosol particles detected include alkanes, alkenes, acids, esters, alcohols, aldehydes, and amino acids. The ion signal produced by DART-MS scales with the aerosol surface area rather than volume, suggesting that DART-MS is a viable technique to measure the chemical composition of the particle interface. For oleic acid, particle size measurements of the aerosol stream exiting the ionization region suggest that the probing depth depends upon the desorption temperature, and the probing depth is estimated to be on the order of 5 nm for a 185 nm diameter particle at a DART heater temperature of 500 °C with nitrogen as the DART gas. The reaction of ozone with submicrometer oleic acid particles is measured to demonstrate the ability of this technique to identify products and quantify reaction rates in a heterogeneous reaction. PMID:23330910

  19. New method for comprehensive detection of chemical warfare agents using an electron-cyclotron-resonance ion-source mass spectrometer.

    PubMed

    Kidera, Masanori; Seto, Yasuo; Takahashi, Kazuya; Enomoto, Shuichi; Kishi, Shintaro; Makita, Mika; Nagamatsu, Tsuyoshi; Tanaka, Tatsuhiko; Toda, Masayoshi

    2011-03-01

    We developed a detection technology for vapor forms of chemical warfare agents (CWAs) with an element analysis system using an electron cyclotron resonance ion source. After the vapor sample was introduced directly into the ion source, the molecular material was decomposed into elements using electron cyclotron resonance plasma and ionized. The following CWAs and stimulants were examined: diisopropyl fluorophosphonate (DFP), 2-chloroethylethylsulfide (2CEES), cyanogen chloride (CNCl), and hydrogen cyanide (HCN). The type of chemical warfare agents, specifically, whether it was a nerve agent, blister agent, blood agent, or choking agent, could be determined by measuring the quantities of the monatomic ions or CN(+) using mass spectrometry. It was possible to detect gaseous CWAs that could not be detected by a conventional mass spectrometer. The distribution of electron temperature in the plasma could be closely controlled by adjusting the input power of the microwaves used to generate the electron cyclotron resonance plasma, and the target compounds could be detected as molecular ions or fragment ions, enabling identification of the target agents. PMID:21242103

  20. New method for comprehensive detection of chemical warfare agents using an electron-cyclotron-resonance ion-source mass spectrometer

    NASA Astrophysics Data System (ADS)

    Kidera, Masanori; Seto, Yasuo; Takahashi, Kazuya; Enomoto, Shuichi; Kishi, Shintaro; Makita, Mika; Nagamatsu, Tsuyoshi; Tanaka, Tatsuhiko; Toda, Masayoshi

    2011-03-01

    We developed a detection technology for vapor forms of chemical warfare agents (CWAs) with an element analysis system using an electron cyclotron resonance ion source. After the vapor sample was introduced directly into the ion source, the molecular material was decomposed into elements using electron cyclotron resonance plasma and ionized. The following CWAs and stimulants were examined: diisopropyl fluorophosphonate (DFP), 2-chloroethylethylsulfide (2CEES), cyanogen chloride (CNCl), and hydrogen cyanide (HCN). The type of chemical warfare agents, specifically, whether it was a nerve agent, blister agent, blood agent, or choking agent, could be determined by measuring the quantities of the monatomic ions or CN + using mass spectrometry. It was possible to detect gaseous CWAs that could not be detected by a conventional mass spectrometer. The distribution of electron temperature in the plasma could be closely controlled by adjusting the input power of the microwaves used to generate the electron cyclotron resonance plasma, and the target compounds could be detected as molecular ions or fragment ions, enabling identification of the target agents.

  1. 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

  2. Fast gas chromatography and negative-ion chemical ionization tandem mass spectrometry for forensic analysis of cannabinoids in whole blood.

    PubMed

    Thomas, Aurélien; Widmer, Christèle; Hopfgartner, Gérard; Staub, Christian

    2007-11-01

    The present work describes a fast gas chromatography/negative-ion chemical ionization tandem mass spectrometric assay (Fast GC/NICI-MS/MS) for analysis of tetrahydrocannabinol (THC), 11-hydroxy-tetrahydrocannabinol (THC-OH) and 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) in whole blood. The cannabinoids were extracted from 500 microL of whole blood by a simple liquid-liquid extraction (LLE) and then derivatized by using trifluoroacetic anhydride (TFAA) and hexafluoro-2-propanol (HFIP) as fluorinated agents. Mass spectrometric detection of the analytes was performed in the selected reaction-monitoring mode on a triple quadrupole instrument after negative-ion chemical ionization. The assay was found to be linear in the concentration range of 0.5-20 ng/mL for THC and THC-OH, and of 2.5-100 ng/mL for THC-COOH. Repeatability and intermediate precision were found less than 12% for all concentrations tested. Under standard chromatographic conditions, the run cycle time would have been 15 min. By using fast conditions of separation, the assay analysis time has been reduced to 5 min, without compromising the chromatographic resolution. Finally, a simple approach for estimating the uncertainty measurement is presented. PMID:17913432

  3. 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.

  4. Chemical mass-wasting of the northern Yucatan Peninsula by groundwater dissolution.

    USGS Publications Warehouse

    Hanshaw, B.B.; Back, W.

    1980-01-01

    In the interior of the peninsula, the recharging water annually dissolves about 37.5 metric tons of calcite per 1 km2. When the groundwater has become saturated with calcite, little additional water-rock interaction occurs until the active mixing (dispersion) zone is reched near the coastline. As much as 1.2 mmol/L additional calcite can be dissolved in the brackish groundwater zone of dispersion. This indicates that if the total solution potential of the amount of water discharging at Xel Ha lagoon has focused within the lagoon area, the lagoon could be chemically incised in less than 3000 yr. -after Authors

  5. 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

  6. 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%).

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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

  15. Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    SciTech Connect

    Not Available

    1981-01-01

    The standard covers analytical procedures to determine compliance of nuclear-grade uranyl nitrate solution to specifications. The following methods are described in detail: uranium by ferrous sulfate reduction-potassium dichromate titrimetry and by ignition gravimetry; specific gravity by pycnometry; free acid by oxalate complexation; thorium by the Arsenazo(III) (photometric) method; chromium by the diphenylcarbazide (photometric) method; molybdenum by the thiocyanate (photometric) method; halogens separation by steam distillation; fluorine by specific ion electrode; halogen distillate analysis: chloride, bromide and iodide by amperometric microtitrimetry; bromine by the fluorescein (photometric) method; sulfate sulfur by (photometric) turbidimetry; phosphorus by the molybdenum blue (photometric) method; silicon by the molybdenum blue (photometric) method; carbon by persulfate oxidation-acid titrimetry; nonvolatile impurities by spectrography; volatile impurities by rotating-disk spark spectrography; boron by emission spectrography; impurity elements by spark source mass spectrography; isotopic composition by multiple filament surface-ionization mass spectrometry; uranium-232 by alpha spectrometry; total alpha activity by direct alpha counting; fission product activity by beta and gamma counting; entrained organic matter by infrared spectrophotometry. (JMT)

  16. 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.

  17. 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.

  18. 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.

  19. Rapid characterization of chemical compounds in liquid and solid states using thermal desorption electrospray ionization mass spectrometry.

    PubMed

    Huang, Min-Zong; Zhou, Chi-Chang; Liu, De-Lin; Jhang, Siou-Sian; Cheng, Sy-Chyi; Shiea, Jentaie

    2013-10-01

    Rapid characterization of thermally stable chemical compounds in solid or liquid states is achieved through thermal desorption electrospray ionization mass spectrometry (TD-ESI/MS). A feature of this technique is that sampling, desorption, ionization, and mass spectrometric detection are four separate events with respect to time and location. A metal probe was used to sample analytes in their solid or liquid states. The probe was then inserted in a preheated oven to thermally desorb the analytes on the probe. The desorbed analytes were carried by a nitrogen gas stream into an ESI plume, where analyte ions were formed via interactions with charged solvent species generated in the ESI plume. The analyte ions were subsequently detected by a mass analyzer attached to the TD-ESI source. Quantification of acetaminophen in aqueous solutions using TD-ESI/MS was also performed in which a linear response for acetaminophen was obtained between 25 and 500 ppb (R(2) = 0.9978). The standard deviation for a reproducibility test for ten liquid samples was 9.6%. Since sample preparation for TD-ESI/MS is unnecessary, a typical analysis can be completed in less than 10 s. Analytes such as the active ingredients in over-the-counter drugs were rapidly characterized regardless of the different physical properties of said drugs, which included liquid eye drops, viscous cold syrup solution, ointment cream, and a drug tablet. This approach was also used to detect trace chemical compounds in illicit drugs and explosives, in which samples were obtained from the surfaces of a cell phone, piece of luggage made from hard plastic, business card, and wooden desk. PMID:24050317

  20. 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

  1. 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

  2. In planta chemical cross-linking and mass spectrometry analysis of protein structure and interaction in Arabidopsis.

    PubMed

    Zhu, Xinliang; Yu, Fengchao; Yang, Zhu; Liu, Shichang; Dai, Chen; Lu, Xiaoyun; Liu, Chenyu; Yu, Weichuan; Li, Ning

    2016-07-01

    Site-specific chemical cross-linking in combination with mass spectrometry analysis has emerged as a powerful proteomic approach for studying the three-dimensional structure of protein complexes and in mapping protein-protein interactions (PPIs). Building on the success of MS analysis of in vitro cross-linked proteins, which has been widely used to investigate specific interactions of bait proteins and their targets in various organisms, we report a workflow for in vivo chemical cross-linking and MS analysis in a multicellular eukaryote. This approach optimizes the in vivo protein cross-linking conditions in Arabidopsis thaliana, establishes a MudPIT procedure for the enrichment of cross-linked peptides, and develops an integrated software program, exhaustive cross-linked peptides identification tool (ECL), to identify the MS spectra of in planta chemical cross-linked peptides. In total, two pairs of in vivo cross-linked peptides of high confidence have been identified from two independent biological replicates. This work demarks the beginning of an alternative proteomic approach in the study of in vivo protein tertiary structure and PPIs in multicellular eukaryotes. PMID:27198063

  3. 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

  4. [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 b