MEMS SoC: observer-based coplanar gyro-free inertial measurement unit

NASA Astrophysics Data System (ADS)

Chen, Tsung-Lin; Park, Sungsu

2005-09-01

This paper presents a novel design of a coplanar gyro-free inertial measurement unit (IMU) that consists of seven to nine single-axis linear accelerometers, and it can be utilized to perform the six DOF measurements for an object in motion. Unlike other gyro-fee IMUs, this design uses redundant accelerometers and state estimation techniques to facilitate the in situ and mass fabrication for the employed accelerometers. The alignment error from positioning accelerometers onto a measurement unit and the fabrication cost of an IMU can greatly be reduced. The outputs of the proposed design are three linear accelerations and three angular velocities. As compared to other gyro-free IMUs, the proposed design uses less integral operation and thus improves its sensing resolution and drifting problem. The sensing resolution of a gyro-free IMU depends on the sensing resolution of the employed accelerometers as well as the size of the measurement unit. Simulation results indicate that the sensing resolution of the proposed design is 2° s-1 for the angular velocity and 10 μg for the linear acceleration when nine single-axis accelerometers, each with 10 μg sensing resolution, are deployed on a 4 inch diameter disc. Also, thanks to the iterative EKF algorithm, the angle estimation error is within 10-3 deg at 2 s.

A resolution recognizing 20 years since the genocide in Rwanda, and affirming it is in the national interest of the United States to work in close coordination with international partners to help prevent and mitigate acts of genocide and mass atrocities.

THOMAS, 113th Congress

Sen. Coons, Christopher A. [D-DE

2014-04-07

Senate - 12/09/2014 Resolution agreed to in Senate with an amendment and an amended preamble by Voice. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

Characterization of primary organic aerosol emissions from meat cooking, trash burning, and motor vehicles with high-resolution aerosol mass spectrometry and comparison with ambient and chamber observations.

PubMed

Mohr, Claudia; Huffman, Alex; Cubison, Michael J; Aiken, Allison C; Docherty, Kenneth S; Kimmel, Joel R; Ulbrich, Ingrid M; Hannigan, Michael; Jimenez, Jose L

2009-04-01

Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS). High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning emissions contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to those from ambient hydrocarbon-like OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from these sources is unlikelyto be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/zs that may be useful for differentiating some of these sources. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, whereas motor vehicle emissions have very low signal at this m/z.

Diagnosis and Management of Adnexal Masses in Pregnancy

PubMed Central

Yakasai, Ibrahim Adamu; Bappa, Lawal Abdullahi

2012-01-01

Widespread use of ultrasound in early pregnancy has led to the detection of incidental adnexal masses more frequently. This article reviews the diagnosis and management options for adnexal masses in pregnancy. The availability of high-resolution ultrasound has made observation to be a viable option in some cases. However, for those masses suspicious of malignancy, at risk of torsion, rupture, or clinically symptomatic, surgical treatment is warranted. Laparoscopy has been successfully used in pregnancy and is safe in experienced and trained hands in properly equipped units. PMID:23741580

Characterization of polyesters by matrix-assisted laser desorption/ionization and Fourier transform mass spectrometry.

PubMed

Mize, Todd H; Simonsick, William J; Amster, I Jonathan

2003-01-01

Two homopolyesters, poly(neopentyl glycol-alt-isophthalic acid) and poly(hexanediol-alt-azelaic acid), and two copolyesters, poly(dipropoxylated bisphenol-A-alt-(isophthalic acid-co-adipic acid)) and poly(neopentyl glycol-alt-(adipic acid-co-isophthalic acid)) were analyzed by internal source matrix assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS). The high resolution and high mass accuracy provided by FTMS greatly facilitate the characterization of the polyester and copolyester samples. Isobaric resolution allows the ion abundances of overlapping isotopic envelopes to be assessed. Repeat units were confirmed and end functionality assigned. Single shot mass spectra of the entire polymeric distribution demonstrate that the dynamic range of this internal MALDI source instrument and the analyzer cell exceeds performance of those previously reported for higher field instruments. Corrections of space charge mass shift effects are demonstrated for the analytes using an external calibrant and (subsequent to confirmation of structure) via internal calibration which removes ambiguity due to space charge differences in calibrant and analyte spectra. Capillary gel permeation chromatography was used to prepare low polydispersity samples from a high polydispersity polyester, improving the measurement of molecular weight distribution two-fold while retaining the benefits of high resolution mass spectrometry for elucidation of oligomer identity.

Grazing Incidence Nickel Replicated Optics for Hard X-ray Telescopes

NASA Technical Reports Server (NTRS)

Peturzzo, J. J., III; Elsner, R. F.; Joy, M. K.; ODell, S. L.; Weisskopf, M. C.

1997-01-01

The requirements for future hard x-ray (up to 50 keV) telescopes are lightweight, high angular resolution optics with large collecting areas. Grazing incidence replicated optics are an excellent candidate for this, type of mission, providing better angular resolution, comparable area/unit mass, and simpler fabrication than multilayer-coated foils. Most importantly, the technology to fabricate the required optics currently exists. A comparison of several hard x-ray telescope designs will be presented.

Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers

NASA Astrophysics Data System (ADS)

Snyder, Dalton T.; Pulliam, Christopher J.; Wiley, Joshua S.; Duncan, Jason; Cooks, R. Graham

2016-07-01

Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection.

Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers.

PubMed

Snyder, Dalton T; Pulliam, Christopher J; Wiley, Joshua S; Duncan, Jason; Cooks, R Graham

2016-07-01

Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection. Graphical Abstract ᅟ.

NOMINAL VALUES FOR SELECTED SOLAR AND PLANETARY QUANTITIES: IAU 2015 RESOLUTION B3

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

Prša, Andrej; Harmanec, Petr; Torres, Guillermo

In this brief communication we provide the rationale for and the outcome of the International Astronomical Union (IAU) resolution vote at the XXIXth General Assembly in Honolulu, Hawaii, in 2015, on recommended nominal conversion constants for selected solar and planetary properties. The problem addressed by the resolution is a lack of established conversion constants between solar and planetary values and SI units: a missing standard has caused a proliferation of solar values (e.g., solar radius, solar irradiance, solar luminosity, solar effective temperature, and solar mass parameter) in the literature, with cited solar values typically based on best estimates at the timemore » of paper writing. As precision of observations increases, a set of consistent values becomes increasingly important. To address this, an IAU Working Group on Nominal Units for Stellar and Planetary Astronomy formed in 2011, uniting experts from the solar, stellar, planetary, exoplanetary, and fundamental astronomy, as well as from general standards fields to converge on optimal values for nominal conversion constants. The effort resulted in the IAU 2015 Resolution B3, passed at the IAU General Assembly by a large majority. The resolution recommends the use of nominal solar and planetary values, which are by definition exact and are expressed in SI units. These nominal values should be understood as conversion factors only, not as the true solar/planetary properties or current best estimates. Authors and journal editors are urged to join in using the standard values set forth by this resolution in future work and publications to help minimize further confusion.« less

Nominal Values for Selected Solar and Planetary Quantities: IAU 2015 Resolution B3

NASA Astrophysics Data System (ADS)

Prša, Andrej; Harmanec, Petr; Torres, Guillermo; Mamajek, Eric; Asplund, Martin; Capitaine, Nicole; Christensen-Dalsgaard, Jørgen; Depagne, Éric; Haberreiter, Margit; Hekker, Saskia; Hilton, James; Kopp, Greg; Kostov, Veselin; Kurtz, Donald W.; Laskar, Jacques; Mason, Brian D.; Milone, Eugene F.; Montgomery, Michele; Richards, Mercedes; Schmutz, Werner; Schou, Jesper; Stewart, Susan G.

2016-08-01

In this brief communication we provide the rationale for and the outcome of the International Astronomical Union (IAU) resolution vote at the XXIXth General Assembly in Honolulu, Hawaii, in 2015, on recommended nominal conversion constants for selected solar and planetary properties. The problem addressed by the resolution is a lack of established conversion constants between solar and planetary values and SI units: a missing standard has caused a proliferation of solar values (e.g., solar radius, solar irradiance, solar luminosity, solar effective temperature, and solar mass parameter) in the literature, with cited solar values typically based on best estimates at the time of paper writing. As precision of observations increases, a set of consistent values becomes increasingly important. To address this, an IAU Working Group on Nominal Units for Stellar and Planetary Astronomy formed in 2011, uniting experts from the solar, stellar, planetary, exoplanetary, and fundamental astronomy, as well as from general standards fields to converge on optimal values for nominal conversion constants. The effort resulted in the IAU 2015 Resolution B3, passed at the IAU General Assembly by a large majority. The resolution recommends the use of nominal solar and planetary values, which are by definition exact and are expressed in SI units. These nominal values should be understood as conversion factors only, not as the true solar/planetary properties or current best estimates. Authors and journal editors are urged to join in using the standard values set forth by this resolution in future work and publications to help minimize further confusion.

Super-resolution imaging by resonant tunneling in anisotropic acoustic metamaterials.

PubMed

Liu, Aiping; Zhou, Xiaoming; Huang, Guoliang; Hu, Gengkai

2012-10-01

The resonant tunneling effects that could result in complete transmission of evanescent waves are examined in acoustic metamaterials of anisotropic effective mass. The tunneling conditions are first derived for the metamaterials composed of classical mass-in-mass structures. It is found that the tunneling transmission occurs when the total length of metamaterials is an integral number of half-wavelengths of the periodic Bloch wave. Due to the local resonance of building units of metamaterials, the Bloch waves are spatially modulated within the periodic structures, leading to the resonant tunneling occurring in the low-frequency region. The metamaterial slab lens with anisotropic effective mass is designed by which the physics of resonant tunneling and the features for evanescent field manipulations are examined. The designed lens interacts with evanescent waves in the way of the propagating wavenumber weakly dependent on the spatial frequency of evanescent waves. Full-wave simulations validate the imaging performance of the proposed lens with the spatial resolution beyond the diffraction limit.

Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

USGS Publications Warehouse

Wershaw, R. L.; Rutherford, D.W.; Rostad, C.E.; Garbarino, J.R.; Ferrer, I.; Kennedy, K.R.; Momplaisir, G.-M.; Grange, A.

2003-01-01

The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound. Published by Elsevier Science B.V.

Determination of 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and -furans at the part per trillion level in United States beef fat using high-resolution gas chromatography/high-resolution mass spectrometry

NASA Technical Reports Server (NTRS)

Ferrario, J.; Byrne, C.; McDaniel, D.; Dupuy, A. Jr; Harless, R.

1996-01-01

As part of the U.S. EPA Dioxin Reassessment Program, the 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and furans were measured at part per trillion (ppt) levels in beef fat collected from slaughter facilities in the United States. This is the first statistically designed national survey of these compounds in the U.S. beef supply. Analyte concentrations were determined by high-resolution gas chromatography/high-resolution mass spectrometry, using isotope dilution methodology. Method limits of detection on a whole weight basis were 0.05 ppt for TCDD and 0.10 ppt for TCDF, 0.50 ppt for the pentas (PeCDDs/PeCDFs)/hexas (HxCDDs/HxCDFs)/heptas (HpCDDs/HpCDFs), and 3.00 ppt for the octas (OCDD/OCDF). Method detection and quantitation limits were established on the basis of demonstrated performance criteria utilizing fortified samples rather than by conventional signal-to-noise or variability of response methods. The background subtraction procedures developed for this study minimized the likelihood of false positives and increased the confidence associated with reported values near the detection limits. Mean and median values for each of the 2,3,7,8-Cl-substituted dioxins and furans are reported, along with the supporting information required for their interpretation. The mean toxic equivalence values for the samples are 0.35 ppt (nondetects = 0) and 0.89 ppt (nondetects = 1/2 LOD).

Small Business Innovations (Mass Microbalance)

NASA Technical Reports Server (NTRS)

1991-01-01

Femtometrics of Costa Mesa, CA, developed the Model 200-1 SAW Mass Microbalance under a NASA Small Business Innovation Research (SBIR) contract with Langley Research Center. The product is described as "the next generation of aerosol mass microbalance technology," because a new type of sensor, the Surface Acoustic Wave (SAW) piezoelectric crystal, offers mass resolution two orders of magnitude greater than the Quartz Crystal Microbalance cascade impactor (QCM) (used at Langley since 1979 for collection and measurement of aerosol particles in the upper atmosphere). The Model 200-1 SAW Mass Microbalance, which provides a 400-fold increase in mass sensitivity per unit area over the QCM, can be used for real-time particle monitoring in clean rooms, measuring chemical vapors in very low concentrations, measuring target chemicals in the stratosphere and in industry as a toxic vapor monitor.

Onboard data processing and compression for a four-sensor suite: the SERENA experiment.

NASA Astrophysics Data System (ADS)

Mura, A.; Orsini, S.; Di Lellis, A.; Lazzarotto, F.; Barabash, S.; Livi, S.; Torkar, K.; Milillo, A.; De Angelis, E.

2013-09-01

SERENA (Search for Exospheric Refilling and Emitted Natural Abundances) is an instrument package that will fly on board the BepiColombo/Mercury Planetary Orbiter (MPO). SERENA instrument includes four units: ELENA (Emitted Low Energy Neutral Atoms), a neutral particle analyzer/imager to detect ion sputtering and backscattering from Mercury's surface; STROFIO (Start from a Rotating FIeld mass spectrometer), a mass spectrometer to identify atomic masses released from the surface; MIPA (Miniature Ion Precipitation Analyzer) and PICAM (Planetary Ion Camera), two ion spectrometers to monitor the precipitating solar wind and measure the plasma environment around Mercury. The System Control Unit architecture is such that all four sensors are connected to a high resolution FPGA, which dialogs with a dedicated high-performance data processing unit. The unpredictability of the data rate, due to the peculiarities of these investigations, leads to several possible scenarios for the data compression and handling. In this study we first discuss about the predicted data volume that comes from the optimized operation strategy, and then we report on the instrument data processing and compression.

On the Kendrick Mass Defect Plots of Multiply Charged Polymer Ions: Splits, Misalignments, and How to Correct Them

NASA Astrophysics Data System (ADS)

Fouquet, Thierry N. J.; Cody, Robert B.; Ozeki, Yuka; Kitagawa, Shinya; Ohtani, Hajime; Sato, Hiroaki

2018-05-01

The Kendrick mass defect (KMD) analysis of multiply charged polymeric distributions has recently revealed a surprising isotopic split in their KMD plots—namely a 1/z difference between KMDs of isotopes of an oligomer at charge state z. Relying on the KMD analysis of actual and simulated distributions of poly(ethylene oxide) (PEO), the isotopic split is mathematically accounted for and found to go with an isotopic misalignment in certain cases. It is demonstrated that the divisibility (resp. indivisibility) of the nominal mass of the repeating unit (R) by z is the condition for homolog ions to line up horizontally (resp. misaligned obliquely) in a KMD plot. Computing KMDs using a fractional base unit R/z eventually corrects the misalignments for the associated charge state while using the least common multiple of all the charge states as the divisor realigns all the points at once. The isotopic split itself can be removed by using either a new charge-dependent KMD plot compatible with any fractional base unit or the remainders of KM (RKM) recently developed for low-resolution data all found to be linked in a unified theory. These original applications of the fractional base units and the RKM plots are of importance theoretically to satisfy the basics of a mass defect analysis and practically for a correct data handling of single stage and tandem mass spectra of multiply charged homo- and copolymers.

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

Niemi, Merja, E-mail: merja.niemi@joensuu.fi; Jänis, Janne; Jylhä, Sirpa

The high-resolution mass-spectrometric characterization, crystallization and X-ray diffraction studies of a recombinant IgE Fab fragment in complex with bovine β-lactoglobulin are reported. A D1 Fab fragment containing the allergen-binding variable domains of the IgE antibody was characterized by ESI FT–ICR mass spectrometry and crystallized with bovine β-lactoglobulin (BLG) using the hanging-drop vapour-diffusion method at 293 K. X-ray data suitable for structure determination were collected to 2.8 Å resolution using synchrotron radiation. The crystal belonged to the orthorhombic space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 67.0, b = 100.6, c = 168.1 Å. The three-dimensional structure ofmore » the D1 Fab fragment–BLG complex will provide the first insight into IgE antibody–allergen interactions at the molecular level.« less

A wide deep infrared look at the Pleiades with UKIDSS: new constraints on the substellar binary fraction and the low-mass initial mass function

NASA Astrophysics Data System (ADS)

Lodieu, N.; Dobbie, P. D.; Deacon, N. R.; Hodgkin, S. T.; Hambly, N. C.; Jameson, R. F.

2007-09-01

We present the results of a deep wide-field near-infrared survey of 12 deg2 of the Pleiades conducted as part of the United Kingdom Infrared Telescope (UKIRT) Infrared Deep Sky Survey (UKIDSS) Galactic Cluster Survey (GCS). We have extracted over 340 high-probability proper motion (PM) members down to 0.03 Msolar using a combination of UKIDSS photometry and PM measurements obtained by cross-correlating the GCS with data from the Two Micron All Sky Survey, the Isaac Newton Telescope and the Canada-France-Hawaii Telescope. Additionally, we have unearthed 73 new candidate brown dwarf (BD) members on the basis of five-band UKIDSS photometry alone. We have identified 23 substellar multiple system candidates out of 63 candidate BDs from the (Y - K, Y) and (J - K, J) colour-magnitude diagrams, yielding a binary frequency of 28-44 per cent in the 0.075-0.030 Msolar mass range. Our estimate is three times larger than the binary fractions reported from high-resolution imaging surveys of field ultracool dwarfs and Pleiades BDs. However, it is marginally consistent with our earlier `peculiar' photometric binary fraction of 50 +/- 10 per cent presented by Pinfield et al., in good agreement with the 32-45 per cent binary fraction derived from the recent Monte Carlo simulations of Maxted & Jeffries and compatible with the 26 +/- 10 per cent frequency recently estimated by Basri & Reiners. A tentative estimate of the mass ratios from photometry alone seems to support the hypothesis that binary BDs tend to reside in near equal-mass ratio systems. In addition, the recovery of four Pleiades members targeted by high-resolution imaging surveys for multiplicity studies suggests that half of the binary candidates may have separations below the resolution limit of the Hubble Space Telescope or current adaptive optics facilities at the distance of the Pleiades (a ~7 au). Finally, we have derived luminosity and mass functions from the sample of photometric candidates with membership probabilities. The mass function is well modelled by a lognormal peaking at 0.24Msolar and is in agreement with previous studies in the Pleiades. Based on observations made with the United Kingdom Infrared Telescope, operated by the Joint Astronomy Centre on behalf of the UK Particle Physics and Astronomy Research Council. E-mail: nlodieu@iac.es

Portable gas chromatograph-mass spectrometer

DOEpatents

Andresen, Brian D.; Eckels, Joel D.; Kimmons, James F.; Myers, David W.

1996-01-01

A gas chromatograph-mass spectrometer (GC-MS) for use as a field portable organic chemical analysis instrument. The GC-MS is designed to be contained in a standard size suitcase, weighs less than 70 pounds, and requires less than 600 watts of electrical power at peak power (all systems on). The GC-MS includes: a conduction heated, forced air cooled small bore capillary gas chromatograph, a small injector assembly, a self-contained ion/sorption pump vacuum system, a hydrogen supply, a dual computer system used to control the hardware and acquire spectrum data, and operational software used to control the pumping system and the gas chromatograph. This instrument incorporates a modified commercial quadrupole mass spectrometer to achieve the instrument sensitivity and mass resolution characteristic of laboratory bench top units.

A novel double-focusing time-of-flight mass spectrometer for absolute recoil ion cross sections measurements

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

Sigaud, L., E-mail: lsigaud@if.uff.br; Jesus, V. L. B. de; Ferreira, Natalia

In this work, the inclusion of an Einzel-like lens inside the time-of-flight drift tube of a standard mass spectrometer coupled to a gas cell—to study ionization of atoms and molecules by electron impact—is described. Both this lens and a conical collimator are responsible for further focalization of the ions and charged molecular fragments inside the spectrometer, allowing a much better resolution at the time-of-flight spectra, leading to a separation of a single mass-to-charge unit up to 100 a.m.u. The procedure to obtain the overall absolute efficiency of the spectrometer and micro-channel plate detector is also discussed.

A novel double-focusing time-of-flight mass spectrometer for absolute recoil ion cross sections measurements.

PubMed

Sigaud, L; de Jesus, V L B; Ferreira, Natalia; Montenegro, E C

2016-08-01

In this work, the inclusion of an Einzel-like lens inside the time-of-flight drift tube of a standard mass spectrometer coupled to a gas cell-to study ionization of atoms and molecules by electron impact-is described. Both this lens and a conical collimator are responsible for further focalization of the ions and charged molecular fragments inside the spectrometer, allowing a much better resolution at the time-of-flight spectra, leading to a separation of a single mass-to-charge unit up to 100 a.m.u. The procedure to obtain the overall absolute efficiency of the spectrometer and micro-channel plate detector is also discussed.

Tem Observation of Precipitates in Ag-Added Al-Mg-Si Alloys

NASA Astrophysics Data System (ADS)

Nagai, Takeshi; Matsuda, Kenji; Nakamura, Junya; Kawabata, Tokimasa; Marioara, Calin; Andersen, Sigmund J.; Holmestad, Randi; Hirosawa, Shoichi; Horita, Zenji; Terada, Daisuke; Ikeno, Susumu

The influence of addition of the small amount of transition metals to Al-Mg-Si alloy had reported by many researchers. In the previous our work, β' phase in alloys Al — 1.0 mass% Mg2Si -0.5 mass% Ag (Ag-addition) and Al -1.0 mass% Mg2Si (base) were investigated by high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED), in order to understand the effect of Ag. In addition, the distribution of Ag was investigated by energy filtered mapping and high annular angular dark field scanning transmission electron microscopy (HAADF-STEM). One Ag-containing atomic column was observed per β' unit cell, and the unit cell symmetry is slightly changed as compared with the Ag-free β'. In this work, the microstructure of G.P. zone and β'' phase was investigated by TEM observation, which were formed before β' phase. The deformed sample by high pressure torsion (HPT) technique before aging was also investigated to understand its effect for aging in this alloy.

Portable gas chromatograph-mass spectrometer

DOEpatents

Andresen, B.D.; Eckels, J.D.; Kimmons, J.F.; Myers, D.W.

1996-06-11

A gas chromatograph-mass spectrometer (GC-MS) is described for use as a field portable organic chemical analysis instrument. The GC-MS is designed to be contained in a standard size suitcase, weighs less than 70 pounds, and requires less than 600 watts of electrical power at peak power (all systems on). The GC-MS includes: a conduction heated, forced air cooled small bore capillary gas chromatograph, a small injector assembly, a self-contained ion/sorption pump vacuum system, a hydrogen supply, a dual computer system used to control the hardware and acquire spectrum data, and operational software used to control the pumping system and the gas chromatograph. This instrument incorporates a modified commercial quadrupole mass spectrometer to achieve the instrument sensitivity and mass resolution characteristic of laboratory bench top units. 4 figs.

Ultra performance liquid chromatography atmospheric pressure photoionization high resolution mass spectrometric method for determination of multiclass pesticide residues in grape and mango juices.

PubMed

Deme, Pragney; Upadhyayula, Vijayasarathi V R

2015-04-15

A novel analytical method was developed for determination of organochlorine, synthetic pyrethroid, organophosphate and carbamate pesticide residues in fruit juices using ultra performance liquid chromatography-atmospheric pressure photoionization-high resolution mass spectrometry (UPLC-APPI-HRMS). The analytes were extracted from fruit juices by dispersive solid-phase extraction using multi-walled carbon nanotubes (MWCNTs). The analysis was carried out in full scan mode using dual ionization mode of APPI in the mass range of 100-650 units. The limit of detection and limit of quantification values for the pesticides were in the range of 0.025-0.15 ng mL(-1) and 0.1-0.5 ng mL(-1) respectively. The matrix effect of the method was found to be low and extraction recoveries were in the range of 60-110%. Some of the real fruits juice samples showed the presence of some pesticides in the range of 6.5-24.8 ng L(-1). Copyright © 2014 Elsevier Ltd. All rights reserved.

Development of a High-Resolution H3O+ Chemical Ionization Mass Spectrometer for Gas-phase Hydrocarbons and its Application During the 2015 SONGNEX Aircraft Campaign

NASA Astrophysics Data System (ADS)

Koss, A.; Yuan, B.; De Gouw, J. A.; Warneke, C.; Stark, H.

2015-12-01

In-situ time-of-flight chemical ionization mass spectrometers (ToF-CIMS) using H3O+ reagent ion chemistry (PTR-MS) are a relatively new technique in detection of gas-phase hydrocarbons, and recent improvements in instrument sensitivity, mass resolution, and ease of field deployment have expanded their use in atmospheric chemistry. The comparatively low-energy H3O+ ionization technique is ideal for measuring complex mixtures of hydrocarbons, and, compared to conventional quadrupole PTRMS, the newest generation of ToF-CIMS measure many more species simultaneously and with a sensitivity that is as high as a quadrupole PTR-MS. We describe here the development of a commercially available ToF CIMS into an H3O+CIMS suitable for deployment on aircraft, and its application during an aircraft campaign studying emissions from oil and natural gas extraction industry. We provide an overview of instrument development and specifications, including design, characterization, and field operation. We then discuss data processing and interpretation. First, we investigate determination of intensities of poorly resolved peaks. The mass resolution of the present instrument (m/Δm ~4500) enables separate analysis of many isobaric peaks, but peaks are also frequently not fully resolved. Using results from laboratory tests, we quantify how the accuracy can be limited by the overlap in neighboring peaks, and compare to theoretical predictions from literature. We then briefly describe our method for quality assurance of reported compounds, and correction for background and humidity effects. Finally, we present preliminary results from the first field deployment of this instrument during the Spring 2015 SONGNEX aircraft campaign. This campaign sampled emissions from oil and natural gas extraction regions and associated infrastructure in the Western and Central United States. We will highlight results that illustrate (1) new scientific capability from improved mass resolution, which dramatically increased the number of species measured, and (2) new capability from improved time resolution, which provides better spatial coverage during flights, leads to a more thorough and accurate measure of emissions composition, and potentially could enable emission rate estimates using eddy covariance analysis.

The Use of Red Green Blue Air Mass Imagery to Investigate the Role of Stratospheric Air in a Non-Convective Wind Event

NASA Technical Reports Server (NTRS)

Berndt, E. B.; Zavodsky, B. T.; Moltham, A. L.; Folmer, M. J.; Jedlovec, G. J.

2014-01-01

The investigation of non-convective winds associated with passing extratropical cyclones and the formation of the sting jet in North Atlantic cyclones that impact Europe has been gaining interest. Sting jet research has been limited to North Atlantic cyclones that impact Europe because it is known to occur in Shapiro-Keyser cyclones and theory suggests it does not occur in Norwegian type cyclones. The global distribution of sting jet cyclones is unknown and questions remain as to whether cyclones with Shapiro-Keyser characteristics that impact the United States develop features similar to the sting jet. Therefore unique National Aeronautics and Space Administration (NASA) products were used to analyze an event that impacted the Northeast United States on 09 February 2013. Moderate Resolution Imaging Spectroradiometer (MODIS) Red Green Blue (RGB) Air Mass imagery and Atmospheric Infrared Sounder (AIRS) ozone data were used in conjunction with NASA's global Modern Era-Retrospective Analysis for Research and Applications (MERRA) reanalysis and higher-resolution regional 13-km Rapid Refresh (RAP) data to analyze the role of stratospheric air in producing high winds. The RGB Air Mass imagery and a new AIRS ozone anomaly product were used to confirm the presence of stratospheric air. Plan view and cross sectional plots of wind, potential vorticity, relative humidity, omega, and frontogenesis were used to analyze the relationship between stratospheric air and high surface winds during the event. Additionally, the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model was used to plot trajectories to determine the role of the conveyor belts in producing the high winds. Analyses of new satellite products, such as the RGB Air Mass imagery, show the utility of future GOES-R products in forecasting non-convective wind events.

Nano-LC FTICR tandem mass spectrometry for top-down proteomics: routine baseline unit mass resolution of whole cell lysate proteins up to 72 kDa.

PubMed

Tipton, Jeremiah D; Tran, John C; Catherman, Adam D; Ahlf, Dorothy R; Durbin, Kenneth R; Lee, Ji Eun; Kellie, John F; Kelleher, Neil L; Hendrickson, Christopher L; Marshall, Alan G

2012-03-06

Current high-throughput top-down proteomic platforms provide routine identification of proteins less than 25 kDa with 4-D separations. This short communication reports the application of technological developments over the past few years that improve protein identification and characterization for masses greater than 25 kDa. Advances in separation science have allowed increased numbers of proteins to be identified, especially by nanoliquid chromatography (nLC) prior to mass spectrometry (MS) analysis. Further, a goal of high-throughput top-down proteomics is to extend the mass range for routine nLC MS analysis up to 80 kDa because gene sequence analysis predicts that ~70% of the human proteome is transcribed to be less than 80 kDa. Normally, large proteins greater than 50 kDa are identified and characterized by top-down proteomics through fraction collection and direct infusion at relatively low throughput. Further, other MS-based techniques provide top-down protein characterization, however at low resolution for intact mass measurement. Here, we present analysis of standard (up to 78 kDa) and whole cell lysate proteins by Fourier transform ion cyclotron resonance mass spectrometry (nLC electrospray ionization (ESI) FTICR MS). The separation platform reduced the complexity of the protein matrix so that, at 14.5 T, proteins from whole cell lysate up to 72 kDa are baseline mass resolved on a nano-LC chromatographic time scale. Further, the results document routine identification of proteins at improved throughput based on accurate mass measurement (less than 10 ppm mass error) of precursor and fragment ions for proteins up to 50 kDa.

Evaluation of Mass Filtered, Time Dilated, Time-of-Flight Mass Spectrometry

DTIC Science & Technology

2010-01-01

Figure 4.4: Mass resolution dependence on field for selected actinides and surrogates...45 Figure 4.7: Mass resolution dependence on field for selected actinides and actinide surrogates, modeled with no initial...system. A somewhat better mass resolution would need to be achieved in order to separate hydride molecules in the actinide region. However, the

Recent applications of gas chromatography with high-resolution mass spectrometry.

PubMed

Špánik, Ivan; Machyňáková, Andrea

2018-01-01

Gas chromatography coupled to high-resolution mass spectrometry is a powerful analytical method that combines excellent separation power of gas chromatography with improved identification based on an accurate mass measurement. These features designate gas chromatography with high-resolution mass spectrometry as the first choice for identification and structure elucidation of unknown volatile and semi-volatile organic compounds. Gas chromatography with high-resolution mass spectrometry quantitative analyses was previously focused on the determination of dioxins and related compounds using magnetic sector type analyzers, a standing requirement of many international standards. The introduction of a quadrupole high-resolution time-of-flight mass analyzer broadened interest in this method and novel applications were developed, especially for multi-target screening purposes. This review is focused on the development and the most interesting applications of gas chromatography coupled to high-resolution mass spectrometry towards analysis of environmental matrices, biological fluids, and food safety since 2010. The main attention is paid to various approaches and applications of gas chromatography coupled to high-resolution mass spectrometry for non-target screening to identify contaminants and to characterize the chemical composition of environmental, food, and biological samples. The most interesting quantitative applications, where a significant contribution of gas chromatography with high-resolution mass spectrometry over the currently used methods is expected, will be discussed as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Spatial and High-Mass Resolution Imaging of Surface Metabolites of Arabidopsis thaliana by Laser Desorption-Ionization Mass Spectrometry Using Colloidal Silver

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

Jun, Ji Hyun; Song, Zhihong; Liu, Zhenjiu

High-spatial resolution and high-mass resolution techniques are developed and adopted for the mass spectrometric imaging of epicuticular lipids on the surface of Arabidopsis thaliana. Single cell level spatial resolution of {approx}12 {micro}m was achieved by reducing the laser beam size by using an optical fiber with 25 {micro}m core diameter in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer and improved matrix application using an oscillating capillary nebulizer. Fine chemical images of a whole flower were visualized in this high spatial resolution showing substructure of an anther and single pollen grains at the stigma and anthers. Themore » LTQ-Orbitrap with a MALDI ion source was adopted to achieve MS imaging in high mass resolution. Specifically, isobaric silver ion adducts of C29 alkane (m/z 515.3741) and C28 aldehyde (m/z 515.3377), indistinguishable in low-resolution LTQ, can now be clearly distinguished and their chemical images could be separately constructed. In the application to roots, the high spatial resolution allowed molecular MS imaging of secondary roots and the high mass resolution allowed direct identification of lipid metabolites on root surfaces.« less

Measuring atmospheric aerosols of organic origin on multirotor Unmanned Aerial Vehicles (UAVs).

NASA Astrophysics Data System (ADS)

Crazzolara, Claudio; Platis, Andreas; Bange, Jens

2017-04-01

In-situ measurements of the spatial distribution and transportation of atmospheric organic particles such as pollen and spores are of great interdisciplinary interest such as: - In agriculture to investigate the spread of transgenetic material, - In paleoclimatology to improve the accuracy of paleoclimate models derived from pollen grains retrieved from sediments, and - In meteorology/climate research to determine the role of spores and pollen acting as nuclei in cloud formation processes. The few known state of the art in-situ measurement systems are using passive sampling units carried by fixed wing UAVs, thus providing only limited spatial resolution of aerosol concentration. Also the passively sampled air volume is determined with low accuracy as it is only calculated by the length of the flight path. We will present a new approach, which is based on the use of a multirotor UAV providing a versatile platform. On this UAV an optical particle counter in addition to a particle collecting unit, e.g. a conventional filter element and/or a inertial mass separator were installed. Both sampling units were driven by a mass flow controlled blower. This allows not only an accurate determination of the number and size concentration, but also an exact classification of the type of collected aerosol particles as well as an accurate determination of the sampled air volume. In addition, due to the application of a multirotor UAV with its automated position stabilisation system, the aerosol concentration can be measured with a very high spatial resolution of less than 1 m in all three dimensions. The combination of comprehensive determination of number, type and classification of aerosol particles in combination with the very high spatial resolution provides not only valuable progress in agriculture, paleoclimatology and meteorology, but also opens up the application of multirotor UAVs in new fields, for example for precise determination of the mechanisms of generation and distribution of fine particulate matter as the result of road traffic.

Fourier Transfrom Ion Cyclotron Resonance Mass Spectrometry at High Magnetic Field

NASA Astrophysics Data System (ADS)

Marshall, Alan G.

1998-03-01

At high magnetic field (9.4 tesla at NHMFL), Fourier transform ion cyclotron resonance mass spectrometry performance improves dramatically: mass resolving power, axialization efficiency, and scan speed (each proportional to B), maximum ion mass, dynamic range, ion trapping period, kinetic energy, and electron self-cooling rate for sympathetic cooling (each proportional to B^2), and ion coalescence tendency (proportional 1/B^2). These advantages may apply singly (e.g., unit mass resolution for proteins of >100,000 Da), or compound (e.g., 10-fold improvement in S/N ratio for 9.4 T vs. 6 T at the same resolving power). Examples range from direct determination of molecular formulas of diesel fuel components by accurate mass measurement (=B10.1 ppm) to protein structure and dynamics probed by H/D exchange. This work was supported by N.S.F. (CHE-93-22824; CHE-94-13008), N.I.H. (GM-31683), Florida State University, and the National High Magnetic Field Laboratory in Tallahassee, FL.

Rim Fire and its Radiative impact Simulated in CESM/CARMA

NASA Astrophysics Data System (ADS)

Yu, P.; Toon, O. B.; Bardeen, C.; Bucholtz, A.; Rosenlof, K. H.; Saide, P. E.; da Silva, A. M., Jr.; Ziemba, L. D.; Jimenez, J. L.; Schwarz, J. P.; Wagner, N. L.; Lack, D. A.; Mills, M. J.; Reid, J. S.

2015-12-01

The Rim Fire of 2013, the third largest area burned by fire recorded in California history, is simulated by CESM1/CARMA. Modeled aerosol mass, number, effective radius, and extinction coefficient are within variability of data obtained from multiple airborne measurements and satellite measurements. Simulations suggest Rim Fire smoke may block 4-6% of sunlight reaching the surface, with a cooling efficiency around 120-150 W m-2 per unit aerosol optical depth. This study shows that exceptional events like the 2013 Rim Fire can be simulated by a climate model with one-degree resolution, though that resolution is still not sufficient to resolve the smoke peak near the source region.

FDR-controlled metabolite annotation for high-resolution imaging mass spectrometry.

PubMed

Palmer, Andrew; Phapale, Prasad; Chernyavsky, Ilya; Lavigne, Regis; Fay, Dominik; Tarasov, Artem; Kovalev, Vitaly; Fuchser, Jens; Nikolenko, Sergey; Pineau, Charles; Becker, Michael; Alexandrov, Theodore

2017-01-01

High-mass-resolution imaging mass spectrometry promises to localize hundreds of metabolites in tissues, cell cultures, and agar plates with cellular resolution, but it is hampered by the lack of bioinformatics tools for automated metabolite identification. We report pySM, a framework for false discovery rate (FDR)-controlled metabolite annotation at the level of the molecular sum formula, for high-mass-resolution imaging mass spectrometry (https://github.com/alexandrovteam/pySM). We introduce a metabolite-signal match score and a target-decoy FDR estimate for spatial metabolomics.

The new high-resolution IRMS MAT253 ULTRA at Utrecht University

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Hofmann, Magdalena; Paul, Dipayan; Popa, Elena; Adnew, Getachew

2017-04-01

In 2016, the new high-resolution, multi-collector isotope ratio mass spectrometer MAT253 ULTRA [1] was installed at Utrecht University. This instrument is designed to reach a mass resolving power of 20,000 to 40,000 (M/ΔM). The ion currents are detected with a variable multi-collector unit that allows to register up to 9 ion currents simultaneously with Faraday cups and ion counters. The width of the entrance slit can be varied between 5 and 250μm so that the instrument can be operated under low, medium and high mass resolution, and an optimum balance between resolution and sensitivity can be selected for the respective applications. The central field of application of the new IRMS at Utrecht University is the measurement of multiply substituted isotopologues (clumped isotopes) in atmospheric trace compounds (e.g. 13CDH3, 13C18O16O, 18O18O, 15N14N18O) [1-7]. It is known from thermodynamics that the zero point energy of a chemical bond usually decreases when multiple heavy isotopes clump together in a molecule, and this effect depends on temperature [7]. Therefore, the abundance of clumped isotopes can be used as temperature indicator under thermodynamical equilibrium conditions. However, in the atmosphere, many reactions are controlled kinetically. It has been shown recently for a few examples that negative clumping signatures (anti-clumping) can be produced under non-equilibrium conditions [3,4]. In addition, based on purely statistical reasons, anti-clumping signatures will be produced in any molecule that contains indistinguishable atoms, which originate from isotopically distinct reservoir [5,6]. Thus, the investigation of multiply substituted isotopologues is expected to generate novel isotope signatures that can complement conventional stable isotope analysis in atmospheric science. We will present data on the performance of the MAT 253 ULTRA instrument and first scientific applications to atmospheric research. 1. Eiler, J.M., et al., A high-resolution gas-source isotope ratio mass spectrometer, Int. J. Mass Spect., 2013. 335: 45- 56. 2. Young, E.D., et al., A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases, Int. J. Mass Spect., 2016. 401: 1-10. 3. Wang, D.T., et al., Nonequilibrium clumped isotope signals in microbial methane, Science, 2015. 348: 428-431. 4. Yeung, L.Y., et al., Biological signatures in clumped isotopes of O2, Science, 2015. 348: 431-434. 5. Yeung, L.Y., Combinatorial effects on clumped isotopes and their significance in biogeochemistry, Geochim. Cosmochim. Act., 2016: doi:10.1016/j.gca.2015.09.020. 6. Röckmann, T., et al., Statistical clumped isotope signatures Scientific reports, 2016. 6: 31947; doi: 10.1038/srep31947. 7. Wang, Z.G., et al., Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases, Geochim. Cosmochim. Act., 2004. 68: 4779-4797.

Utility of Higher Harmonics in Electrospray Ionization Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometry.

PubMed

Dziekonski, Eric T; Johnson, Joshua T; McLuckey, Scott A

2017-04-18

Mass resolution (M/ΔM fwhm) is observed to linearly increase with harmonic order in a Fourier transform electrostatic linear ion trap (ELIT) mass spectrometer. This behavior was predicted by Grosshans and Marshall for frequency-multiple detection in a Fourier transform ion cyclotron resonance mass spectrometer only for situations when the prominent mechanism for signal decay is ion ejection from the trap. As the analyzer pressure in our ELIT chamber is relatively high, such that collisional scattering and collision-induced dissociation are expected to underlie much of the ion loss, we sought to explore the relationship between harmonic order and mass resolution. Mass resolutions of 36 900 (fundamental), 75 850 (2nd harmonic), and 108 200 (3rd harmonic) were obtained for GdO + (avg. m/z 173.919) with a transient length of 300 ms. To demonstrate that the mass resolution was truly increasing with harmonic order, the unresolved isotopes at the fundamental distribution of cytochrome c +8 (m/z ∼ 1549) were nearly baseline, resolved at the third harmonic (mass resolution ≈ 23 000) with a transient length of only 200 ms. This experiment demonstrates that, when the ion density is sufficiently low, ions with frequency differences of less than 4 Hz remain uncoalesced. Higher harmonics can be used to increase the effective mass resolution for a fixed transient length and thereby may enable the resolution of closely spaced masses, determination of a protein ion's charge state, and study of the onset of peak coalescence when the resolution at the fundamental frequency is insufficient.

Improved mass resolution and mass accuracy in TOF-SIMS spectra and images using argon gas cluster ion beams.

PubMed

Shon, Hyun Kyong; Yoon, Sohee; Moon, Jeong Hee; Lee, Tae Geol

2016-06-09

The popularity of argon gas cluster ion beams (Ar-GCIB) as primary ion beams in time-of-flight secondary ion mass spectrometry (TOF-SIMS) has increased because the molecular ions of large organic- and biomolecules can be detected with less damage to the sample surfaces. However, Ar-GCIB is limited by poor mass resolution as well as poor mass accuracy. The inferior quality of the mass resolution in a TOF-SIMS spectrum obtained by using Ar-GCIB compared to the one obtained by a bismuth liquid metal cluster ion beam and others makes it difficult to identify unknown peaks because of the mass interference from the neighboring peaks. However, in this study, the authors demonstrate improved mass resolution in TOF-SIMS using Ar-GCIB through the delayed extraction of secondary ions, a method typically used in TOF mass spectrometry to increase mass resolution. As for poor mass accuracy, although mass calibration using internal peaks with low mass such as hydrogen and carbon is a common approach in TOF-SIMS, it is unsuited to the present study because of the disappearance of the low-mass peaks in the delayed extraction mode. To resolve this issue, external mass calibration, another regularly used method in TOF-MS, was adapted to enhance mass accuracy in the spectrum and image generated by TOF-SIMS using Ar-GCIB in the delayed extraction mode. By producing spectra analyses of a peptide mixture and bovine serum albumin protein digested with trypsin, along with image analyses of rat brain samples, the authors demonstrate for the first time the enhancement of mass resolution and mass accuracy for the purpose of analyzing large biomolecules in TOF-SIMS using Ar-GCIB through the use of delayed extraction and external mass calibration.

System and Mass Storage Study for Defense Mapping Agency Topographic Center (DMATC/HC)

DTIC Science & Technology

1977-04-01

34•»-—•—■»■—- view. The assessment should be based on carefully designed control condi- tions—data volume, resolution, function, etc...egories: hardware control and library management support. This software is designed to interface with IBM 360/370 OS and OS/VS. No interface with a...laser re- cording unit includes a programmable recorder control subsystem which can be designed to provide a hardware and software interface compatible

A micropixelated ion-imaging detector for mass resolution enhancement of a QMS instrument.

PubMed

Syed, Sarfaraz U A H; Eijkel, Gert B; Maher, Simon; Kistemaker, Piet; Taylor, Stephen; Heeren, Ron M A

2015-03-01

An in-vacuum position-sensitive micropixelated detector (Timepix) is used to investigate the time-dependent spatial distribution of different charge state (and hence different mass-to-charge (m/z)) ions exiting an electrospray ionization (ESI)-based quadrupole mass spectrometer (QMS) instrument. Ion images obtained from the Timepix detector provide a detailed insight into the positions of stable and unstable ions of the mass peak as they exit the QMS. With the help of image processing algorithms and by selecting areas on the ion images where more stable ions impact the detector, an improvement in mass resolution by a factor of 5 was obtained for certain operating conditions. Moreover, our experimental approach of mass resolution enhancement was confirmed by in-house-developed novel QMS instrument simulation software. Utilizing the imaging-based mass resolution enhancement approach, the software predicts instrument mass resolution of ∼1,0000 for a single-filter QMS instrument with a 210-mm long mass filter and a low operating frequency (880 kHz) of the radio frequency (RF) voltage.

High-resolution Kendrick Mass Defect Analysis of Poly(ethylene oxide)-based Non-ionic Surfactants and Their Degradation Products.

PubMed

Fouquet, Thierry; Shimada, Haruo; Maeno, Katsuyuki; Ito, Kanako; Ozeki, Yuka; Kitagawa, Shinya; Ohtani, Hajime; Sato, Hiroaki

2017-09-01

Matrix assisted laser desorption ionization (MALDI) high-resolution mass spectrometry (HRMS) and the recently introduced high-resolution Kendrick mass defect (HRKMD) analysis are combined to thoroughly characterize non-ionic surfactants made of a poly(ethylene oxide) (PEO) core capped by esters of fatty acids. A PEO monostearate surfactant is first analyzed as a proof of principle of the HRKMD analysis conducted with a fraction of EO as the base unit (EO/X with X being an integer) in lieu of EO for a regular KMD analysis. Data visualization is greatly enhanced and the distributions detected in the MALDI mass spectrum are assigned to a pristine (H, OH)-PEO as well as mono- and di-esterified PEO chains with palmitate and stearate end-groups in HRKMD plots computed with EO/45. The MALDI-HRMS/HRKMD analysis is then successfully applied to the more complex case of ethoxylated hydrogenated castor oil (EHCO) found to contain a large number of hydrogenated ricinoleate moieties (up to 14) in its HRKMD plot computed with EO/43, departing from the expected triglyceride structure. The exhaustiveness of the MALDI-HRMS/HRKMD strategy is validated by comparing the so-obtained fingerprints with results from alternative techniques (electrospray ionization MS, size exclusion and liquid adsorption chromatography, ion mobility spectrometry). Finally, aged non-ionic surfactants formed upon hydrolytic degradation are analyzed by MALDI-HRMS/HRKMD to easily assign the degradation products and infer the associated degradation routes. In addition to the hydrolysis of the ester groups observed for EHCO, chain scissions and new polar end-groups are observed in the HRKMD plot of PEO monostearate arising from a competitive oxidative ageing.

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

Smith, Donald F.; Schulz, Carl; Konijnenburg, Marco

High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry imaging enables the spatial mapping and identification of biomolecules from complex surfaces. The need for long time-domain transients, and thus large raw file sizes, results in a large amount of raw data (“big data”) that must be processed efficiently and rapidly. This can be compounded by largearea imaging and/or high spatial resolution imaging. For FT-ICR, data processing and data reduction must not compromise the high mass resolution afforded by the mass spectrometer. The continuous mode “Mosaic Datacube” approach allows high mass resolution visualization (0.001 Da) of mass spectrometry imaging data, butmore » requires additional processing as compared to featurebased processing. We describe the use of distributed computing for processing of FT-ICR MS imaging datasets with generation of continuous mode Mosaic Datacubes for high mass resolution visualization. An eight-fold improvement in processing time is demonstrated using a Dutch nationally available cloud service.« less

An investigation of the oxidation behaviour of zirconium alloys using isotopic tracers and high resolution SIMS

NASA Astrophysics Data System (ADS)

Yardley, Sean S.; Moore, Katie L.; Ni, Na; Wei, Jang Fei; Lyon, Stuart; Preuss, Michael; Lozano-Perez, Sergio; Grovenor, Chris R. M.

2013-11-01

High resolution secondary ion mass spectrometry (SIMS) analysis has been used to study the oxidation mechanisms when commercial low tin ZIRLO™Low tin ZIRLO™ is a trademark of Westinghouse Electric Company LLC in the United States and may be registered in other countries throughout the world. Unauthorized use is strictly prohibited.1 and Zircaloy 4 materials are exposed to corroding environments containing both 18O and 2H isotopes. Clear evidence has been shown for different characteristic distributions of 18O before and after the kinetic transitions, and this behaviour has been correlated with the development of porosity in the oxide which allows the corroding medium to penetrate locally to the metal/oxide interface.

The Oklahoma City bombing: the roles of the dental teams ... and the lessons learned.

PubMed

Glass, R T

1998-01-01

The Oklahoma City bombing is considered by most historians the worst act of domestic terrorism ever to have occurred in the United States. The response to the disaster, however, is considered by most experts in the field as being the best; creating what is known as the "Oklahoma Standard". The roles of the dental teams in the resolution were pivotal and until now, the recognition of these roles have not been described, due to this being considered a case of mass murder. The purpose of this paper is to give an overview of the preparations, the initial responses, the roles of the dental teams in the resolution, the preparations for the criminal trials, and some of the lessons that were learned.

Polymeric spatial resolution test patterns for mass spectrometry imaging using nano-thermal analysis with atomic force microscopy

DOE PAGES

Tai, Tamin; Kertesz, Vilmos; Lin, Ming -Wei; ...

2017-05-11

As the spatial resolution of mass spectrometry imaging technologies has begun to reach into the nanometer regime, finding readily available or easily made resolution reference materials has become particularly challenging for molecular imaging purposes. This study describes the fabrication, characterization and use of vertical line array polymeric spatial resolution test patterns for nano-thermal analysis/atomic force microscopy/mass spectrometry chemical imaging.

Polymeric spatial resolution test patterns for mass spectrometry imaging using nano-thermal analysis with atomic force microscopy

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

Tai, Tamin; Kertesz, Vilmos; Lin, Ming -Wei

As the spatial resolution of mass spectrometry imaging technologies has begun to reach into the nanometer regime, finding readily available or easily made resolution reference materials has become particularly challenging for molecular imaging purposes. This study describes the fabrication, characterization and use of vertical line array polymeric spatial resolution test patterns for nano-thermal analysis/atomic force microscopy/mass spectrometry chemical imaging.

Laser Ablation Mass Spectrometer (LAMS) as a Standoff Analyzer in Space Missions for Airless Bodies

NASA Technical Reports Server (NTRS)

Li, X.; Brinckerhoff, W. B.; Managadze, G. G.; Pugel, D. E.; Corrigan, C. M.; Doty, J. H.

2012-01-01

A laser ablation mass spectrometer (LAMS) based on a time-of-flight (TOF) analyzer with adjustable drift length is proposed as a standoff elemental composition sensor for space missions to airless bodies. It is found that the use of a retarding potential analyzer in combination with a two-stage reflectron enables LAMS to be operated at variable drift length. For field-free drift lengths between 33 cm to 100 cm, at least unit mass resolution can be maintained solely by adjustment of internal voltages, and without resorting to drastic reductions in sensitivity. Therefore, LAMS should be able to be mounted on a robotic arm and analyze samples at standoff distances of up to several tens of cm, permitting high operational flexibility and wide area coverage of heterogeneous regolith on airless bodies.

[Preparation and certification of mussel reference material for organochlorine pesticides and polychlorinated biphenyls using isotope dilution-high resolution mass spectrometry].

PubMed

Lu, Xianbo; Chen, Jiping; Wang, Shuqiu; Zou, Lili; Tian, Yuzeng; Ni, Yuwen; Su, Fan

2012-09-01

A method for the preparation and certification of the reference material of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in mussel tissue is described. The mussel tissue from Dalian Bay was frozen-dried, comminuted, sieved, homogenized, packaged, and sterilized by 60Co radiation sterilization in turn. The certified values for 18 OCPs and 16 PCBs were determined by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) using isotope dilution and internal standard quantitation techniques. The certified values were validated and given based on seven accredited laboratories, and these values are traceable to the SI (international system of units) through gravimetrically prepared standards of established purity and measurement intercomparisons. The certified values of PCBs and OCPs in mussel span 4 orders of magnitude with a relative uncertainty of about 10%. This material is a natural biological material with confirmed good homogeneity and stability, and it was approved as the grade "primary reference material" (GBW10069) in June 2012 in China. This reference material provided necessary quality control products for our country to implement the Stockholm Treaty on the monitoring of persistent organic pollutants (POPs). The material is intended to be used for the method validation and quality control in the determination of OCPs and PCBs in biota samples.

Iterative and function-continuation Fourier deconvolution methods for enhancing mass spectrometer resolution

NASA Technical Reports Server (NTRS)

Ioup, J. W.; Ioup, G. E.; Rayborn, G. H., Jr.; Wood, G. M., Jr.; Upchurch, B. T.

1984-01-01

Mass spectrometer data in the form of ion current versus mass-to-charge ratio often include overlapping mass peaks, especially in low- and medium-resolution instruments. Numerical deconvolution of such data effectively enhances the resolution by decreasing the overlap of mass peaks. In this paper two approaches to deconvolution are presented: a function-domain iterative technique and a Fourier transform method which uses transform-domain function-continuation. Both techniques include data smoothing to reduce the sensitivity of the deconvolution to noise. The efficacy of these methods is demonstrated through application to representative mass spectrometer data and the deconvolved results are discussed and compared to data obtained from a spectrometer with sufficient resolution to achieve separation of the mass peaks studied. A case for which the deconvolution is seriously affected by Gibbs oscillations is analyzed.

The Infrared Automatic Mass Screening (IRAMS) System For Printed Circuit Board Fault Detection

NASA Astrophysics Data System (ADS)

Hugo, Perry W.

1987-05-01

Office of the Program Manager for TMDE (OPM TMDE) has initiated a program to develop techniques for evaluating the performance of printed circuit boards (PCB's) using infrared thermal imaging. It is OPM TMDE's expectation that the standard thermal profile (STP) will become the basis for the future rapid automatic detection and isolation of gross failure mechanisms on units under test (UUT's). To accomplish this OPM TMDE has purchased two Infrared Automatic Mass Screening ( I RAMS) systems which are scheduled for delivery in 1987. The IRAMS system combines a high resolution infrared thermal imager with a test bench and diagnostic computer hardware and software. Its purpose is to rapidly and automatically compare the thermal profiles of a UUT with the STP of that unit, recalled from memory, in order to detect thermally responsive failure mechanisms in PCB's. This paper will review the IRAMS performance requirements, outline the plan for implementing the two systems and report on progress to date.

Introducing Graduate Students to High-Resolution Mass Spectrometry (HRMS) Using a Hands-On Approach

ERIC Educational Resources Information Center

Stock, Naomi L.

2017-01-01

High-resolution mass spectrometry (HRMS) features both high resolution and high mass accuracy and is a powerful tool for the analysis and quantitation of compounds, determination of elemental compositions, and identification of unknowns. A hands-on laboratory experiment for upper-level undergraduate and graduate students to investigate HRMS is…

The Evolution of the Indian Ocean Triple Junction and the Finite Rotation Problem.

DTIC Science & Technology

1980-09-01

AD-AG&9 103 ~S HOLE OCEANOGRAPHIC INSTITUTION MASS F/6 6/7 THE EVOLUTION OF THE INDIAN OCEAN TRIPLE JUNCTION AND THE FINIT-ETC(U1 SEP 80 C R TAPSCOTT...1111flfl 1.4 111116 MICROCOPY RESOLUTION TEST CHART WHOI-80-37 THE EVOLUTION OF THE INDIAN OCEAN TRIPLE JUNCTION AND THE FINITE ROTATION PROBLEM by...purpose of the United States Government. This thesis should be cited as: Christopher R. Tapscott, 1979. The Evolution of the Indian Ocean Triple Junction

Laser Time-of-Flight Mass Spectrometry for Space

NASA Technical Reports Server (NTRS)

Brinckerhoff, W. B.; Managadze, G. G.; McEntire, R. W.; Cheng, A. F.; Green, W. J.

2000-01-01

A miniature reflection time-of-flight mass spectrometer for in situ planetary surface analysis is described. The laser ablation mass spectrometer (LAMS) measures the regolith's elemental and isotopic composition without high-voltage source extraction or sample preparation. The compact size (< 2 x 10(exp 3) cubic cm) and low mass (approximately 2 kg) of LAMS, due to its fully coaxial design and two-stage reflectron, fall within the strict resource limitations of landed science missions to solar system bodies. A short-pulse laser focused to a spot with a diameter approximately 30-50 micrometers is used to obtain microscopic surface samples. Assisted by a microimager, LAMS can interactively select and analyze a range of compositional regions (with lateral motion) and with repeated pulses can access unweathered, subsurface materials. The mass resolution is calibrated to distinguish isotopic peaks at unit masses, and detection limits are on resolved to a few ppm. The design and calibration method of a prototype LAMS device is described, which include the development of preliminary relative sensitivity coefficients for major element bulk abundance measurements.

Static Time-of-Flight Secondary Ion Mass Spectrometry (SIMS) | Materials

Science.gov Websites

-Flight Secondary Ion Mass Spectrometry (SIMS) Image of high mass resolution and mass accuracy provided by TOF SIMS We used the high mass resolution and mass accuracy of TOF SIMS to study surface cleanliness acidic wash resulted in contamination by Fe and other metals. Without high mass accuracy, the CaO signal

Enhanced Mass Defect Filtering To Simplify and Classify Complex Mixtures of Lignin Degradation Products.

PubMed

Dier, Tobias K F; Egele, Kerstin; Fossog, Verlaine; Hempelmann, Rolf; Volmer, Dietrich A

2016-01-19

High resolution mass spectrometry was utilized to study the highly complex product mixtures resulting from electrochemical breakdown of lignin. As most of the chemical structures of the degradation products were unknown, enhanced mass defect filtering techniques were implemented to simplify the characterization of the mixtures. It was shown that the implemented ionization techniques had a major impact on the range of detectable breakdown products, with atmospheric pressure photoionization in negative ionization mode providing the widest coverage in our experiments. Different modified Kendrick mass plots were used as a basis for mass defect filtering, where Kendrick mass defect and the mass defect of the lignin-specific guaiacol (C7H7O2) monomeric unit were utilized, readily allowing class assignments independent of the oligomeric state of the product. The enhanced mass defect filtering strategy therefore provided rapid characterization of the sample composition. In addition, the structural similarities between the compounds within a degradation sequence were determined by comparison to a tentatively identified product of this compound series. In general, our analyses revealed that primarily breakdown products with low oxygen content were formed under electrochemical conditions using protic ionic liquids as solvent for lignin.

DETERMINATION OF ELEMENTAL COMPOSITIONS BY HIGH RESOLUTION MASS SPECTROMETRY WITHOUT MASS CALIBRANTS

EPA Science Inventory

Widely applicable mass calibrants, including perfluorokerosene, are available for gas-phase introduction of analytes ionized by electron impact (EI) prior to analysis using high resolution mass spectrometry. Unfortunately, no all-purpose calibrants are available for recently dev...

Short-period variability in terrestrial water storage from GNSS observations of Earth surface deformation

NASA Astrophysics Data System (ADS)

Borsa, A. A.; Adusumilli, S.; Agnew, D. C.; Silverii, F.; Small, E. E.

2017-12-01

Modern geodetic observations of Earth surface deformation, initially targeted at processes such as tectonics and volcanism, also record the subtle signature of mass movements within Earth's atmosphere and hydrosphere. These observations, which track the elastic response of the solid earth to changing surface mass loads, are clearly evident in position time series from permanent Global Navigation Satellite System (GNSS) stations, which recent work has used to recover changes in terrestrial water storage (TWS) over seasonal and multi-annual time scales. Earth's elastic reponse is nearly instantaneous, which suggests the possibility of observing TWS changes at much shorter periods, limited only by the 24 hour resolution of standard GNSS data products and noise in the GNSS position estimates. We present results showing that TWS increases from individual storms can be recovered using the GNSS network in the United States, and that the water mass changes are similar to gridded precipitation estimates from the National Centers for Environmental Prediction (NCEP). The gradual decline we observe in TWS following each storm is diagnostic of runoff and local evapotranspiration, and varies by location. By greatly increasing the temporal resolution of GNSS-derived estimates of TWS, we hope to provide constraints on integrated water fluxes from hydrological models on all relevant timescales.

Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

PubMed

Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

2016-11-01

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH 4 and CO 2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH 4 as the source of carbon and treat CO 2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH 4 /CO 2 /N 2 atmosphere. UMR results suggest that CH 4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO 2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

Nitrogen Containing Organic Compounds and Oligomers in Secondary Organic Aerosol Formed by Photooxidation of Isoprene

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

Nguyen, Tran B.; Laskin, Julia; Laskin, Alexander

2011-07-06

Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NOx conditions. Up to 80-90% of the observed products are oligomers and up to 33% are nitrogen-containing organic compounds (NOC). We observe oligomers with up to 8 monomer units in length. Tandem mass spectrometry (MSn) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C2-C5 monomer units are identified including methylglyoxal,more » hydroxyacetone, hydroxyacetic acid, glycolaldehyde, and 2-methyltetrols. The majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NOx conditions and 0.83 under the high-NOx conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.« less

A New ɛNd Record Covering Termination II

NASA Astrophysics Data System (ADS)

Deaney, E. L.; Thornalley, D. J.; van de Flierdt, T.; Kreissig, K.; Barker, S.

2014-12-01

The 143Nd/144Nd ratio (ɛNd) of seawater is used as a quasi-conservative tracer to examine past changes in water mass composition of the deep ocean. Records of ɛNd across the last deglaciation (Termination 1, T1) provide valuable information about water mass mixing that has improved our understanding of the ocean dynamics relevant to the process of deglaciation. However, questions remain concerning end-member source characteristics and regional hydrographic processes. Here we present a high resolution record of ɛNd derived from fish debris from ODP site 1063 across Termination 2. The different external and internal forcing (e.g. insolation versus freshwater) applicable to T2 make this a useful comparator for studies focused on T1. Accordingly we find large (up to 4 ɛNd units) fluctuations across T2 that can be related to high latitude climate changes as recorded by ice cores and other high resolution climate archives. We also identify periods of extremely negative values that require new explanations for changing end-member compositions. Our results have important implications for understanding North Atlantic deep water formation processes during critical climate transitions.

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

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

Andersen, T.; Jensen, R.; Christensen, M. K.

2012-07-15

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/{Delta}m > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detectionmore » by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH{sub 3}.« less

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

NASA Astrophysics Data System (ADS)

Andersen, T.; Jensen, R.; Christensen, M. K.; Pedersen, T.; Hansen, O.; Chorkendorff, I.

2012-07-01

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH3.

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors.

PubMed

Andersen, T; Jensen, R; Christensen, M K; Pedersen, T; Hansen, O; Chorkendorff, I

2012-07-01

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH(3).

Current position of high-resolution MS for drug quantification in clinical & forensic toxicology.

PubMed

Meyer, Markus R; Helfer, Andreas G; Maurer, Hans H

2014-08-01

This paper reviews high-resolution MS approaches published from January 2011 until March 2014 for the quantification of drugs (of abuse) and/or their metabolites in biosamples using LC-MS with time-of-flight or Orbitrap™ mass analyzers. Corresponding approaches are discussed including sample preparation and mass spectral settings. The advantages and limitations of high-resolution MS for drug quantification, as well as the demand for a certain resolution or a specific mass accuracy are also explored.

Mars Exospheric studies with MENCA on a Mars Orbiter

NASA Astrophysics Data System (ADS)

Bhardwaj, Anil; Menca Team

2012-07-01

The study of Martian exosphere is important for understanding the escape rate of Martian atmosphere and its impact on Mars' climate change. The neutral density distribution and the composition of Martian exosphere still remain largely unexplored. There are no in-situ measurements of the Martian exosphere; only a few remote sensing measurements have been made and some modelling studies are carried out. We proposed to fly a neutral mass spectrometer, namely "MENCA" (Mars Exospheric Neutral Composition Analyser) to explore the Martian exospheric neutral density and composition at an altitude of ~500 km and above from the surface of Mars, and to study its radial and diurnal variations. MENCA is based on the technique of quadrupole mass spectrometry and has the mass range of 1-300 amu with unit mass resolution. (*) MENCA Team includes: S.V. Mohankumar, T. P. Das, P. Sreelatha, P. Pradeepkumar, B. Sunder, Amarnath Nandi, Neha Naik, G. Supriya, Vipin K. Yadav, M. B. Dhanya, R. Satheesh Thampi, G. P. Padmanabhan

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS.

PubMed

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-11-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation. Graphical Abstract ᅟ.

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS

NASA Astrophysics Data System (ADS)

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-07-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation.

Direct sampling of sub-µm atmospheric particulate organic matter in sub-ng m-3 mass concentrations by proton-transfer-reaction mass spectrometry

NASA Astrophysics Data System (ADS)

Armin, W.; Mueller, M.; Klinger, A.; Striednig, M.

2017-12-01

A quantitative characterization of the organic fraction of atmospheric particulate matter is still challenging. Herein we present the novel modular "Chemical Analysis of Aerosol Online" (CHARON) particle inlet system coupled to a new-generation proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF 6000 X2, Ionicon Analytik, Austria) that quantitatively detects organic analytes in real-time and sub-pptV levels by chemical ionization with hydronium reagent ions. CHARON consists of a gas-phase denuder for stripping off gas-phase analytes (efficiency > 99.999%), an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. With typical particle enrichment factors of around 30 for particle diameters (DP) between 120 nm and 1000 nm (somewhat reduced enrichment for 60 nm < DP < 120 nm) we boost the already excellent limits of detection of the PTR-TOF 6000 X2 system to unprecedented levels. We demonstrate that particulate organic analytes of mass concentrations down to 100 pg m-3 can be detected on-line and in single-minute time-resolutions. In addition, PTR-MS allows for a quantitative detection of almost the full range of particulate organics of intermediate to low volatility. With the high mass resolution (R > 6000) and excellent mass accuracies (< 10 ppm) chemical compositions can be assigned and included in further analyses. In addition to a detailed characterization of the CHARON PTR-TOF 6000 X2 we will present first results on the chemical composition of sub-µm particulate organic matter in the urban atmosphere in Innsbruck (Austria).

Molecular characterization of dissolved organic matter in contrasted freshwater environments by electrospray ionization mass spectrometry and EEM-PARAFAC

NASA Astrophysics Data System (ADS)

Parot, Jérémie; Parlanti, Edith; Guéguen, Céline

2015-04-01

Dissolved organic matter (DOM) is a key parameter in the fate, transport and mobility of inorganic and organic pollutants in natural waters. Excitation emission matrix (EEM) spectra coupled to parallel factor analysis (PARAFAC) provide insights on the main fluorescent DOM constituents. However, the molecular structures associated with PARAFAC DOM remain poorly understood. In this study, DOM from rivers, marshes and algal culture was characterized by EEM-PARAFAC and electrospray ionization Fourier transform mass spectrometry (ESI-FT-MS, Orbitrap Q Exactive). The high resolution of the Orbitrap (i.e. 140,000) allowed us to separate unique molecular species from the complex DOM mixtures. The majority of chemical species were found within the mass to charge ratio (m/z) 200 to 400. Weighted averages of neutral mass were 271.254, 236.480, 213.992Da for river, marsh and algal-derived DOM, respectively, congruent with previous studies. The assigned formula were dominated by CHO in humic-rich river waters whereas N- and S-containing compounds were predominant in marsh and algal samples. Marsh consisted of N and S-containing compounds, which were presumed to be linear alkylbenzene sulfonates. And the double bond equivalent (DBE) was higher in the marsh and in comparison was lower in the algal culture. Kendrick masses, used to identify homologous compounds differing only by a number of base units in high resolution mass spectra, and Van Krevelen diagrams, plot of molar ratio of hydrogen to carbon (H/C) versus oxygen to carbon (O/C), will be discussed in relation to PARAFAC components to further discriminate freshwater systems based on the origin and maturity of DOM. Together, these results showed that ESI-FT-MS has a great potential to distinguish freshwater DOM at the molecular level without any fractionation.

3D Printing of Advanced Biocomposites on Earth and Beyond

NASA Technical Reports Server (NTRS)

Rothschild, Lynn J.; Gentry, Diana M.; Micks, Ashley

2015-01-01

Human exploration off planet is severely limited by the cost of launching materials into space and re-supply. Thus materials brought from earth must be light, stable and reliable at destination. Using traditional approaches a lunar or Mars base would require either transporting a hefty store of metals or heavy manufacturing equipment and construction materials for in situ extraction; both would severely limit any other mission objectives. Long-term human space presence requires periodic replenishment, adding a massive cost overhead. Even robotic missions often sacrifice science goals for heavy radiation and thermal protection. Biology has the potential to solve these problems because it can replicate and repair itself, and do a wide variety of chemical reactions including making food, fuel and materials. Synthetic biology can greatly enhance and expand life's evolved repertoire. Using natural and synthetically altered organisms as the feedstock for additive manufacturing could one day make possible the dream of producing bespoke tools, food, smart fabrics and even replacement organs on demand. To this end our lab has produced a proof-of-concept bioprinter with nearly one-cell resolution. Genetically engineering yeast cells to secrete bioproducts subsequent to printing allows the potential to make biomaterials with a fine microstructure. Imagine a production system that, at a few micron scale resolution, can add mollusk shell for compressive strength per unit mass, spider silk or collagen for tensile strength per unit mass, and potentially biologically-deposited wires. Now imagine what new products can be enabled by such a technology, on earth or beyond

3D Printing of Advanced Biocomposites on Earth and Beyond

NASA Technical Reports Server (NTRS)

Rothschild, Lynn J.; Gentry, Diana; Micks, Ashley

2014-01-01

Human exploration off planet is severely limited by the cost of launching materials into space and re-supply. Thus materials brought from earth must be light, stable and reliable at destination. Using traditional approaches a lunar or Mars base would require either transporting a hefty store of metals or heavy manufacturing equipment and construction materials for in situ extraction; both would severely limit any other mission objectives. Long-term human space presence requires periodic replenishment, adding a massive cost overhead. Even robotic missions often sacrifice science goals for heavy radiation and thermal protection. Biology has the potential to solve these problems because it can replicate and repair itself, and do a wide variety of chemical reactions including making food, fuel and materials. Synthetic biology can greatly enhance and expand life's evolved repertoire. Using natural and synthetically altered organisms as the feedstock for additive manufacturing could one day make possible the dream of producing bespoke tools, food, smart fabrics and even replacement organs on demand. To this end our lab has produced a proof-of-concept bioprinter with nearly one-cell resolution. Genetically engineering yeast cells to secrete bioproducts subsequent to printing allows the potential to make biomaterials with a fine microstructure. Imagine a production system that, at a few micron scale resolution, can add mollusk shell for compressive strength per unit mass, spider silk or collagen for tensile strength per unit mass, and potentially biologically-deposited wires. Now imagine what new products can be enabled by such a technology, on earth or beyond.

SWICS/Ulysses and MASS/wind observations of solar wind sulfur charge states

NASA Technical Reports Server (NTRS)

Cohen, C. M. S.; Galvin, A. B.; Hamilton, D. C.; Gloeckler, G.; Geiss, J.; Bochsler, P.

1995-01-01

As Ulysses journeys from the southern to the northern solar pole, the newly launched Wind spacecraft is monitoring the solar wind near 1 AU, slightly upstream of the Earth. Different solar wind structures pass over both spacecraft as coronal holes and other features rotate in and out of view. Ulysses and Wind are presently on opposing sides of the sun allowing us to monitor these streams for extended periods of time. Composition measurements made by instruments on both spacecraft provide information concerning the evolution and properties of these structures. We have combined data from the Solar Wind Ion Composition Spectrometer (SWICS) on Ulysses and the high mass resolution spectrometer (MASS) on Wind to determine the charge state distribution of sulfur in the solar wind. Both instruments employ electrostatic deflection with time-of-flight measurement. The high mass resolution of the MASS instrument (M/Delta-M approximately 100) allows sulfur to be isolated easily while the stepping energy/charge selection provides charge state information. SWICS measurements allow the unique identification of heavy ions by their mass and mass/charge with resolutions of M/Delta-M approximately 3 and M/q/Delta(M/q) approximately 20. The two instruments complement each other nicely in that MASS has the greater mass resolution while SWICS has the better mass/charge resolution and better statistics.

Boundaries of mass resolution in native mass spectrometry.

PubMed

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

2014-06-01

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

A novel ToF-SIMS operation mode for sub 100 nm lateral resolution: Application and performance.

PubMed

Kubicek, Markus; Holzlechner, Gerald; Opitz, Alexander K; Larisegger, Silvia; Hutter, Herbert; Fleig, Jürgen

2014-01-15

A novel operation mode for time of flight-secondary ion mass spectrometry (ToF-SIMS) is described for a TOF.SIMS 5 instrument with a Bi-ion gun. It features sub 100 nm lateral resolution, adjustable primary ion currents and the possibility to measure with high lateral resolution as well as high mass resolution. The adjustment and performance of the novel operation mode are described and compared to established ToF-SIMS operation modes. Several examples of application featuring novel scientific results show the capabilities of the operation mode in terms of lateral resolution, accuracy of isotope analysis of oxygen, and combination of high lateral and mass resolution. The relationship between high lateral resolution and operation of SIMS in static mode is discussed.

Overcoming interference with the detection of a stable isotopically labeled microtracer in the evaluation of beclabuvir absolute bioavailability using a concomitant microtracer approach.

PubMed

Jiang, Hao; Titsch, Craig; Zeng, Jianing; Jones, Barry; Joyce, Philip; Gandhi, Yash; Turley, Wesley; Burrell, Richard; Aubry, Anne F; Arnold, Mark E

2017-09-05

The oral absolute bioavailability of beclabuvir in healthy subjects was determined using a microdose (100μg) of the stable isotopically labeled tracer via intravenous (IV) infusion started after oral dosing of beclabuvir (150mg). To simultaneously analyze the concentrations of the IV microtracer ([ 13 C 6 ]beclabuvir) and beclabuvir in plasma samples, a liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) method was initially developed. Surprisingly beclabuvir significantly interfered with the IV microtracer detection when using the selected reaction monitoring (SRM) in the assay. An interfering component from the drug substance was observed using a high resolution mass spectrometer (HRMS). The mass-to-charge (m/z) of the interfering component was -32ppm different from the nominal value for the IV microtracer and thus could not be differentiated in the SRM assay by the unit mass resolution. To overcome this interference, we evaluated two approaches by either monitoring an alternative product ion using the SRM assay or isolating the interfering component using the parallel reaction monitoring (PRM) assay on the HRMS. This case study has demonstrated two practical approaches for overcoming interferences with the detection of stable isotopically labeled IV microtracers in the evaluation of absolute bioavailability, which provides users the flexibility in using either LC-MS/MS or HRMS to mitigate unpredicted interferences in the assay to support microtracer absolute bioavailability studies. Copyright © 2017 Elsevier B.V. All rights reserved.

NAOMI instrument: a product line of compact and versatile cameras designed for high resolution missions in Earth observation

NASA Astrophysics Data System (ADS)

Luquet, Ph.; Chikouche, A.; Benbouzid, A. B.; Arnoux, J. J.; Chinal, E.; Massol, C.; Rouchit, P.; De Zotti, S.

2017-11-01

EADS Astrium is currently developing a new product line of compact and versatile instruments for high resolution missions in Earth Observation. First version has been developed in the frame of the ALSAT-2 contract awarded by the Algerian Space Agency (ASAL) to EADS Astrium. The Silicon Carbide Korsch-type telescope coupled with a multilines detector array offers a 2.5 m GSD in PAN band at Nadir @ 680 km altitude (10 m GSD in the four multispectral bands) with a 17.5 km swath width. This compact camera - 340 (W) x 460 (L) x 510 (H) mm3, 13 kg - is embarked on a Myriade-type small platform. The electronics unit accommodates video, housekeeping, and thermal control functions and also a 64 Gbit mass memory. Two satellites are developed; the first one is planned to be launched on mid 2009. Several other versions of the instrument have already been defined with enhanced resolution or/and larger field of view.

Hodoscope Cineradiography Of Nuclear Fuel Destruction Experiments

NASA Astrophysics Data System (ADS)

De Volpi, A.

1983-08-01

Nuclear reactor safety studies have applied cineradiographic techniques to achieve key information regarding the durability of fuel elements that are subjected to destructive transients in test reactors. Beginning with its development in 1963, the fast-neutron hodoscope has recorded data at the TREAT reactor in the United States of America. Consisting of a collimator instrumented with several hundred parallel channels of detectors and associated instrumentation, the hodoscope measures fuel motion that takes place within thick-walled steel test containers. Fuel movement is determined by detecting the emission of fast neutrons induced in the test capsule by bursts of the test reactor that last from 0.3 to 30 s. The system has been designed so as to achieve under certain typical conditions( horizontal) spatial resolution less than lmm, time resolution close to lms, mass resolution below 0.1 g, with adequate dynamic range and recording duration. A variety of imaging forms have been developed to display the results of processing and analyzing recorded data.*

Dustbuster: a New Generation Impact-ionization Time-of-flight Mass Spectrometer for in situ Analysis of Cosmic Dust

NASA Astrophysics Data System (ADS)

Austin, D. E.; Ahrens, T. J.; Beauchamp, J. L.

2000-10-01

We have developed and tested a small impact-ionization time-of-flight mass spectrometer for analysis of cosmic dust, suitable for use on deep space missions. This mass spectrometer, named Dustbuster, incorporates a large target area and a reflectron, simultaneously optimizing mass resolution, sensitivity, and collection efficiency. Dust particles hitting the 65-cm2 target plate are partially ionized. The resulting ions are accelerated through a modified reflectron that focuses the ions in space and time to produce high-resolution spectra. The instrument, shown below, measures 10 x 10 x 20 cm, has a mass of 500 g, and consumes little power. Laser desorption ionization of metal and mineral samples (embedded in the impact plate) simulates particle impacts for instrument performance tests. Mass resolution in these experiments is near 200, permitting resolution of isotopes. The mass spectrometer can be combined with other instrument components to determine dust particle trajectories and sizes. This project was funded by NASA's Planetary Instrument Definition and Development Program.

A catastrophic event in Lake Geneva region during the Early Bronze Age?

NASA Astrophysics Data System (ADS)

Kremer, Katrina; Yrro, Blé; Marillier, François; Hilbe, Michael; Corboud, Pierre; Rachoud-Schneider, Anne-Marie; Girardclos, Stéphanie

2013-04-01

Similarly to steep oceanic continental margins, lake slopes can collapse, producing large sublacustrine landslides and tsunamis. Lake sediments are excellent natural archives of such mass movements and their study allows the reconstructions of these prehistoric events, such as the 563 AD large tsunami over Lake Geneva (Kremer et al, 2012). In Lake Geneva, more than 100 km of high-resolution seismic reflection profiles reveal the late Holocene sedimentation history. The seismic record shows a succession of five large lens-shaped seismic units (A to I), characterized by transparent/chaotic seismic facies with irregular lower boundaries, and interpreted as mass-movement deposits. These units are interbedded with parallel, continuous and strong amplitude reflections, interpreted as the 'background' lake sediments. The oldest dated mass movement (Unit D) covers a surface of 22 km2 in the deep basin, near the city of Lausanne. This deposit has an estimated minimum volume of 0.18 km3 and thus was very likely tsunamigenic (Kremer et al, 2012). A 12-m-long sediment core confirms the seismic interpretation of the mass movement unit and shows that the uppermost 3 m of Unit D are characterized by deformed hemipelagic sediments topped by a 5 cm thick turbidite. This deposit can be classified as a slump whose scar can be interpreted in the seismic data and visualized by multibeam bathymetry. This slump of Lausanne was likely triggered by an earthquake but a spontaneous slope collapse cannot be excluded (Girardclos et al, 2007). Radiocarbon dating of plant macro-remains reveals that the unit D happened during Early Bronze Age. Three other mass wasting deposits occurred during the same time period and may have been triggered during the same event, either by a single earthquake or by a tsunami generated by the slump of Lausanne. Although the exact trigger mechanism of the all these mass-wasting deposits remains unknown, a tsunami likely generated by this event may have affected the installation of palafittic villages on the shore of Lake Geneva during the Early Bronze Age. References: Girardclos S., Schmidt O.T., Sturm M., Ariztegui D., Pugin A., Anselmetti F.S., 2007, The 1996 AD delta collapse and large turbidite in Lake Brienz, Marine Geology (241), 137-154. Kremer K., Simpson G., Girardclos S., 2012, Giant Lake Geneva tsunami in 563 AD, Nature Geoscience (5), 756-757. This project is financed by the Swiss National Foundation project nr. 200021-121666/1 and the Fondation Ernest Boninchi.

Time‐of‐flight secondary ion mass spectrometry imaging of biological samples with delayed extraction for high mass and high spatial resolutions

PubMed Central

Vanbellingen, Quentin P.; Elie, Nicolas; Eller, Michael J.; Della‐Negra, Serge; Touboul, David

2015-01-01

Rationale In Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS), pulsed and focused primary ion beams enable mass spectrometry imaging, a method which is particularly useful to map various small molecules such as lipids at the surface of biological samples. When using TOF‐SIMS instruments, the focusing modes of the primary ion beam delivered by liquid metal ion guns can provide either a mass resolution of several thousand or a sub‐µm lateral resolution, but the combination of both is generally not possible. Methods With a TOF‐SIMS setup, a delayed extraction applied to secondary ions has been studied extensively on rat cerebellum sections in order to compensate for the effect of long primary ion bunches. Results The use of a delayed extraction has been proven to be an efficient solution leading to unique features, i.e. a mass resolution up to 10000 at m/z 385.4 combined with a lateral resolution of about 400 nm. Simulations of ion trajectories confirm the experimental determination of optimal delayed extraction and allow understanding of the behavior of ions as a function of their mass‐to‐charge ratio. Conclusions Although the use of a delayed extraction has been well known for many years and is very popular in MALDI, it is much less used in TOF‐SIMS. Its full characterization now enables secondary ion images to be recorded in a single run with a submicron spatial resolution and with a mass resolution of several thousand. This improvement is very useful when analyzing lipids on tissue sections, or rare, precious, or very small size samples. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26395603

First insights on the organic species from the high resolution mass spectrometer ROSINA DFMS on-board the Rosetta spacecraft

NASA Astrophysics Data System (ADS)

Le Roy, L.; Altwegg, K.; Berthelier, J. J.; Calmonte, U.; Dhooghe, F.; Fiethe, B.; Fuselier, S.; Gombosi, T. I.; Rubin, M.; Tzou, C. Y.

2014-12-01

Starting in August 2014, the ROSINA experiment will characterize the composition and dynamics of 67P/Churyumov-Gerasimenko's coma. ROSINA consists of a suite of three instruments: a pressure sensor (COPS: COmetary Pressure Sensor) and two mass spectrometers: the Reflectron Time of Flight mass spectrometer (RTOF) and the Double Focusing Mass Spectrometer (DFMS). Here we will focus on the first results obtained by DFMS, the high-resolution mass spectrometer of ROSINA. DFMS is a traditional magnetic mass spectrometer that combines an electrostatic analyzer for energy analysis with a magnet for momentum analysis. To date, DFMS is the highest mass resolution mass spectrometer in space, with resolution (m/Δm = 3000 at 1% of the peak height at 28 amu/q). It will be able to resolve CO from N2 at m/z= 28 amu/q or 12CH and 13C at m/z= 13 amu/q. We will present the first results of DFMS: the detection of organic species and their implication for the origin of cometary material.

PTR-QMS versus PTR-TOF comparison in a region with oil and natural gas extraction industry in the Uintah Basin in 2013

NASA Astrophysics Data System (ADS)

Warneke, C.; Veres, P.; Murphy, S. M.; Soltis, J.; Field, R. A.; Graus, M. G.; Koss, A.; Li, S.-M.; Li, R.; Yuan, B.; Roberts, J. M.; de Gouw, J. A.

2015-01-01

Here we compare volatile organic compound (VOC) measurements using a standard proton-transfer-reaction quadrupole mass spectrometer (PTR-QMS) with a new proton-transfer-reaction time of flight mass spectrometer (PTR-TOF) during the Uintah Basin Winter Ozone Study 2013 (UBWOS2013) field experiment in an oil and gas field in the Uintah Basin, Utah. The PTR-QMS uses a quadrupole, which is a mass filter that lets one mass to charge ratio pass at a time, whereas the PTR-TOF uses a time of flight mass spectrometer, which takes full mass spectra with typical 0.1 s-1 min integrated acquisition times. The sensitivity of the PTR-QMS in units of counts per ppbv (parts per billion by volume) is about a factor of 10-35 times larger than the PTR-TOF, when only one VOC is measured. The sensitivity of the PTR-TOF is mass dependent because of the mass discrimination caused by the sampling duty cycle in the orthogonal-acceleration region of the TOF. For example, the PTR-QMS on mass 33 (methanol) is 35 times more sensitive than the PTR-TOF and for masses above 120 amu less than 10 times more. If more than 10-35 compounds are measured with PTR-QMS, the sampling time per ion decreases and the PTR-TOF has higher signals per unit measuring time for most masses. For UBWOS2013 the PTR-QMS measured 34 masses in 37 s and on that timescale the PTR-TOF is more sensitive for all masses. The high mass resolution of the TOF allows for the measurements of compounds that cannot be separately detected with the PTR-QMS, such as oxidation products from alkanes and cycloalkanes emitted by oil and gas extraction. PTR-TOF masses do not have to be preselected, allowing for identification of unanticipated compounds. The measured mixing ratios of the two instruments agreed very well (R2 ≥ 0.92 and within 20%) for all compounds and masses monitored with the PTR-QMS.

PTR-QMS vs. PTR-TOF comparison in a region with oil and natural gas extraction industry in the Uintah Basin in 2013

NASA Astrophysics Data System (ADS)

Warneke, C.; Veres, P. R.; Murphy, S. M.; Soltis, J.; Field, R. A.; Graus, M. G.; Koss, A.; Li, S.-M.; Li, R.; Yuan, B.; Roberts, J. M.; de Gouw, J. A.

2014-07-01

Here we compare volatile organic compound (VOC) measurements using a standard Proton-Transfer-Reaction Quadrupole Mass Spectrometer (PTR-QMS) with a new Proton-Transfer-Reaction Time Of Flight Mass Spectrometer (PTR-TOF) during the Uintah Basin Winter Ozone Study 2013 (UBWOS2013) field experiment in an oil and gas field in the Uintah Basin, Utah. The PTR-QMS uses a quadrupole, which is a mass filter that lets one mass pass at a time, whereas the PTR-TOF uses a Time Of Flight mass spectrometer, which takes full mass spectra with typical 0.1 s to 1 min integrated acquisition times. The sensitivity of the PTR-QMS in units of counts per ppbv is about a factor of 10-35 times larger than the PTR-TOF, when only one VOC is measured. The sensitivity of the PTR-TOF is mass dependent because of the mass discrimination caused by the sampling duty cycle in the orthogonal-acceleration region of the TOF. For example, the PTR-QMS on mass 33 (methanol) is 35 times more sensitive than the PTR-TOF and for masses above 120 amu less than 10 times more. If more than 10-35 compounds are measured with PTR-QMS, the sampling time per ion decreases and the PTR-TOF has higher signals per unit measuring time for most masses. For UBWOS2013 the PTR-QMS measured 34 masses in 37 s and on that time-scale the PTR-TOF is more sensitive for all masses. The high mass resolution of the TOF allows for the measurements of compounds that cannot be separately detected with the PTR-QMS, such as oxidation products from alkanes and cycloalkanes emitted by oil and gas extraction. PTR-TOF masses do not have to be pre-selected allowing for identification of unanticipated compounds. The measured mixing ratios of the two instruments agreed very well (R2 ≥ 0.92 and within 20%) for all compounds and masses monitored with the PTR-QMS.

MULTISPECTRAL IDENTIFICATION OF ALKYL AND CHLOROALKYL PHOSPHATES FROM AN INDUSTRIAL EFFLUENT

EPA Science Inventory

Multispectral techniques (gas chromatography combined with low and high resolution electron-impact mass spectrometry, low and high resolution chemical ionization mass spectrometry, and Fourier transform infrared mass spectroscopy) were used to identify 13 alkyl and chloralkyl pho...

Amend the title so as to read: `Condemning Joseph Kony and the Lord's Resistance Army for committing crimes against humanity and mass atrocities, and supporting ongoing efforts by the United States Government and governments and regional organizations in central Africa to remove Joseph Kony and Lord's Resistance Army commanders from the battlefield.'.

THOMAS, 112th Congress

Sen. Coons, Christopher A. [D-DE

2012-03-21

Senate - 08/02/2012 Resolution agreed to in Senate with an amendment and an amendment to the Title and an amended preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

Reionization Simulations Powered by Graphics Processing Units. I. On the Structure of the Ultraviolet Radiation Field

NASA Astrophysics Data System (ADS)

Aubert, Dominique; Teyssier, Romain

2010-11-01

We present a set of cosmological simulations with radiative transfer in order to model the reionization history of the universe from z = 18 down to z = 6. Galaxy formation and the associated star formation are followed self-consistently with gas and dark matter dynamics using the RAMSES code, while radiative transfer is performed as a post-processing step using a moment-based method with the M1 closure relation in the ATON code. The latter has been ported to a multiple Graphics Processing Unit (GPU) architecture using the CUDA language together with the MPI library, resulting in an overall acceleration that allows us to tackle radiative transfer problems at a significantly higher resolution than previously reported: 10243 + 2 levels of refinement for the hydrodynamic adaptive grid and 10243 for the radiative transfer Cartesian grid. We reach a typical acceleration factor close to 100× when compared to the CPU version, allowing us to perform 1/4 million time steps in less than 3000 GPU hr. We observe good convergence properties between our different resolution runs for various volume- and mass-averaged quantities such as neutral fraction, UV background, and Thomson optical depth, as long as the effects of finite resolution on the star formation history are properly taken into account. We also show that the neutral fraction depends on the total mass density, in a way close to the predictions of photoionization equilibrium, as long as the effect of self-shielding are included in the background radiation model. Although our simulation suite has reached unprecedented mass and spatial resolution, we still fail in reproducing the z ~ 6 constraints on the neutral fraction of hydrogen and the intensity of the UV background. In order to account for unresolved density fluctuations, we have modified our chemistry solver with a simple clumping factor model. Using our most spatially resolved simulation (12.5 Mpc h -1 with 10243 particles) to calibrate our subgrid model, we have resimulated our largest box (100 Mpc h -1 with 10243 particles) with the modified chemistry, successfully reproducing the observed level of neutral hydrogen in the spectra of high-redshift quasars. We however did not reproduce the average photoionization rate inferred from the same observations. We argue that this discrepancy could be partly explained by the fact that the average radiation intensity and the average neutral fraction depend on different regions of the gas density distribution, so that one quantity cannot be simply deduced from the other.

Detecting kinematic boundary surfaces in phase space: particle mass measurements in SUSY-like events

NASA Astrophysics Data System (ADS)

Debnath, Dipsikha; Gainer, James S.; Kilic, Can; Kim, Doojin; Matchev, Konstantin T.; Yang, Yuan-Pao

2017-06-01

We critically examine the classic endpoint method for particle mass determination, focusing on difficult corners of parameter space, where some of the measurements are not independent, while others are adversely affected by the experimental resolution. In such scenarios, mass differences can be measured relatively well, but the overall mass scale remains poorly constrained. Using the example of the standard SUSY decay chain \\tilde{q}\\to {\\tilde{χ}}_2^0\\to \\tilde{ℓ}\\to {\\tilde{χ}}_1^0 , we demonstrate that sensitivity to the remaining mass scale parameter can be recovered by measuring the two-dimensional kinematical boundary in the relevant three-dimensional phase space of invariant masses squared. We develop an algorithm for detecting this boundary, which uses the geometric properties of the Voronoi tessellation of the data, and in particular, the relative standard deviation (RSD) of the volumes of the neighbors for each Voronoi cell in the tessellation. We propose a new observable, \\overline{Σ} , which is the average RSD per unit area, calculated over the hypothesized boundary. We show that the location of the \\overline{Σ} maximum correlates very well with the true values of the new particle masses. Our approach represents the natural extension of the one-dimensional kinematic endpoint method to the relevant three dimensions of invariant mass phase space.

Characterization and identification of a C-terminal amidated mechano growth factor (MGF) analogue in black market products.

PubMed

Esposito, Simone; Deventer, Koen; Van Eenoo, Peter

2012-03-30

Mechano growth factor (MGF) is a splice variant of insulin-like growth factor that possesses anabolic properties and has not yet been approved for therapeutic use. Nevertheless, it is readily available on the black market. Although the World Anti-Doping Agency (WADA) has banned the use of MGF in sports, no routinely performed methods have been reported for its detection. In this work, two preparations from the black market containing an unknown MGF analogue were characterized. Mass spectrometry characterizations of unknown preparations and a reference human MGF were performed on an Orbitrap and a triple quadrupole mass spectrometers after separation by liquid chromatography. High accuracy measurements allowed protein identification from full scan MS data, and low-resolution full scan MS/MS provided further information on fragmentation. HCD scans of the analytes showed the presence of common b series product ions in the black market preparations and the human MGF reference standard, but all the y series ions starting from (y(1))(+) exhibited a difference of 1 m/z unit in nominal mass. This difference was demonstrated to be due to a C-terminal amidation of MGF. High-resolution data demonstrated that the black market products were both C-terminal amidated analogues of human MGF. In addition, low-resolution MS/MS characterization revealed a potentially diagnostic transition (m/z 717.8 → 431.1) for the discrimination of C-amidated MGF from the endogenous form. Qualitative identification of a MGF C-terminal amidated analogue in two black market products was successfully achieved. This report demonstrates that illegal MGF preparations are commercially available for use as doping agent in sports. Copyright © 2012 John Wiley & Sons, Ltd.

High Resolution Tissue Imaging Using the Single-probe Mass Spectrometry under Ambient Conditions

NASA Astrophysics Data System (ADS)

Rao, Wei; Pan, Ning; Yang, Zhibo

2015-06-01

Ambient mass spectrometry imaging (MSI) is an emerging field with great potential for the detailed spatial analysis of biological samples with minimal pretreatment. We have developed a miniaturized sampling and ionization device, the Single-probe, which uses in-situ surface micro-extraction to achieve high detection sensitivity and spatial resolution during MSI experiments. The Single-probe was coupled to a Thermo LTQ Orbitrap XL mass spectrometer and was able to create high spatial and high mass resolution MS images at 8 ± 2 and 8.5 μm on flat polycarbonate microscope slides and mouse kidney sections, respectively, which are among the highest resolutions available for ambient MSI techniques. Our proof-of-principle experiments indicate that the Single-probe MSI technique has the potential to obtain ambient MS images with very high spatial resolutions with minimal sample preparation, which opens the possibility for subcellular ambient tissue MSI to be performed in the future.

Crystallization and preliminary X-ray diffraction analysis of the TetR-family transcriptional repressor YhgD from Bacillus halodurans

PubMed Central

Yeo, Hyun Ku; Park, Young Woo; Kang, Jina; Lee, Jae Young

2013-01-01

YhgD is a member of the TetR-family transcription factors, which regulate genes encoding proteins involved in multidrug resistance, virulence, osmotic stress and pathogenicity. YhgD from the alkaliphilic bacterium Bacillus halodurans was cloned and overexpressed in Escherichia coli. YhgD (Bh2145) from B. halodurans is composed of 193 amino-acid residues with a molecular mass of 21 853 Da. YhgD was crystallized at 296 K using ethylene glycol as a precipitant by the sitting-drop vapour-diffusion method. The crystal diffracted to 1.9 Å resolution and belonged to the apparent triclinic space group P1, with unit-cell parameters a = 37.22, b = 47.85, c = 54.15 Å, α = 92.75, β = 107.9, γ = 90.27°. The asymmetric unit is likely to contain two molecules of monomeric YhgD, giving a crystal volume per mass (V M) of 2.05 Å3 Da−1 and a solvent content of 40.2%. PMID:23695570

Crystallization and preliminary X-ray diffraction analysis of the TetR-family transcriptional repressor YhgD from Bacillus halodurans.

PubMed

Yeo, Hyun Ku; Park, Young Woo; Kang, Jina; Lee, Jae Young

2013-05-01

YhgD is a member of the TetR-family transcription factors, which regulate genes encoding proteins involved in multidrug resistance, virulence, osmotic stress and pathogenicity. YhgD from the alkaliphilic bacterium Bacillus halodurans was cloned and overexpressed in Escherichia coli. YhgD (Bh2145) from B. halodurans is composed of 193 amino-acid residues with a molecular mass of 21 853 Da. YhgD was crystallized at 296 K using ethylene glycol as a precipitant by the sitting-drop vapour-diffusion method. The crystal diffracted to 1.9 Å resolution and belonged to the apparent triclinic space group P1, with unit-cell parameters a = 37.22, b = 47.85, c = 54.15 Å, α = 92.75, β = 107.9, γ = 90.27°. The asymmetric unit is likely to contain two molecules of monomeric YhgD, giving a crystal volume per mass (VM) of 2.05 Å(3) Da(-1) and a solvent content of 40.2%.

A New Mass Spectrometer for Upper Atmospheric Measurements in the Auroral Region

NASA Astrophysics Data System (ADS)

Everett, E. A.; Dyer, J. S.; Watson, M.; Sanderson, W.; Schicker, S.; Work, D.; Mertens, C. J.; Bailey, S. M.; Syrstad, E. A.

2011-12-01

We have previously presented a new rocket-borne time-of-flight mass spectrometer (TOF-MS) for measurements in the mesosphere / lower thermosphere (MLT). Traditionally, mass spectrometry in the MLT has been difficult, mainly due to the elevated ambient pressures of the MLT and high speeds of a sounding rocket flight, which affect the direct sampling of the ambient atmosphere and spatial resolution. The TOF-MS is a versatile, inherently adaptable, axial-sampling instrument, capable of operating in a traditional TOF mode or in a multiplexing Hadamard-transform mode where high spatial resolution is desired. To minimize bow shock effects at low altitudes (~70-110km), the ram surface of the TOF-MS can be cryogenically cooled using liquid He to adsorb impinging gas particles. The vacuum pumping system for the TOF-MS is tailored to the specific mission and instrument configuration. Depending on the instrument gas load and operating altitude, cryo, miniature turbo pump or getter-based pumping systems may be employed. Terrestrial TOF-MS instruments often employ a reflectron, essentially an ion-mirror, to improve mass resolving power and compensate for the thermal velocity distribution of particles being measured. The TOF-MS can be arranged in either a simple linear or reflectron configuration. Simulations and modeling are used to compare instrument mass resolution for linear and reflectron configurations for several variable conditions including vehicle velocity and ambient temperature, ultimately demonstrating the potential to make rocket-borne mass spectrometry measurements with unit-mass resolution up to at least 48 amu. Preliminary analyses suggest that many species of interest (including He, CO2, O2, O2+ , N2, N2+, and NO+) can be measured with an uncertainty below 10% relative standard deviation on a sounding rocket flight. We also present experimental data for a laboratory prototype linear TOF-MS. Experimental data is compared to simulation and modeling efforts to validate and confirm instrument performance and capability. Two proposed rocket campaigns for investigations of the auroral region include the TOF-MS. By making accurate composition measurements of the neutral atmosphere from 70 to 120km, Mass Spectrometry of the Turbopause Region (MSTR) aims to improve the accuracy of temperature measurements in the turbopause region, improve the MSIS model atmosphere and examine the transition from the turbulently mixed lower atmosphere to the diffusive equilibrium of the upper atmosphere. The ROCKet-borne STorm Energetics of Auroral Dosing in the E-region (ROCK-STEADE) mission will study energy transfer in the E-region during an aurora by examining auroral emissions and measuring concentrations of neutrals and ions. The instrument suite for ROCK-STEADE includes two mass spectrometers, one each to measure neutrals and ions in the altitude range of 70 - 170km. The ability of the TOF-MS instrument to make accurate measurements will greatly aid in better understanding the MLT.

MASS MEASUREMENTS BY AN ACCURATE AND SENSITIVE SELECTED ION RECORDING TECHNIQUE

EPA Science Inventory

Trace-level components of mixtures were successfully identified or confirmed by mass spectrometric accurate mass measurements, made at high resolution with selected ion recording, using GC and LC sample introduction. Measurements were made at 20 000 or 10 000 resolution, respecti...

Quantification of steroid hormones in human serum by liquid chromatography-high resolution tandem mass spectrometry.

PubMed

Matysik, Silke; Liebisch, Gerhard

2017-12-01

A limited specificity is inherent to immunoassays for steroid hormone analysis. To improve selectivity mass spectrometric analysis of steroid hormones by liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been introduced in the clinical laboratory over the past years usually with low mass resolution triple-quadrupole instruments or more recently by high resolution mass spectrometry (HR-MS). Here we introduce liquid chromatography-high resolution tandem mass spectrometry (LC-MS/HR-MS) to further increase selectivity of steroid hormone quantification. Application of HR-MS demonstrates an enhanced selectivity compared to low mass resolution. Separation of isobaric interferences reduces background noise and avoids overestimation. Samples were prepared by automated liquid-liquid extraction with MTBE. The LC-MS/HR-MS method using a quadrupole-Orbitrap analyzer includes eight steroid hormones i.e. androstenedione, corticosterone, cortisol, cortisone, 11-deoxycortisol, 17-hydroxyprogesterone, progesterone, and testosterone. It has a run-time of 5.3min and was validated according to the U.S. Food and Drug Administration (FDA) and the European Medicines Agency (EMA) guidelines. For most of the analytes coefficient of variation were 10% or lower and LOQs were determined significantly below 1ng/ml. Full product ion spectra including accurate masses substantiate compound identification by matching their masses and ratios with authentic standards. In summary, quantification of steroid hormones by LC-MS/HR-MS is applicable for clinical diagnostics and holds also promise for highly selective quantification of other small molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

Workstation-Based Real-Time Mesoscale Modeling Designed for Weather Support to Operations at the Kennedy Space Center and Cape Canaveral Air Station

NASA Technical Reports Server (NTRS)

Manobianco, John; Zack, John W.; Taylor, Gregory E.

1996-01-01

This paper describes the capabilities and operational utility of a version of the Mesoscale Atmospheric Simulation System (MASS) that has been developed to support operational weather forecasting at the Kennedy Space Center (KSC) and Cape Canaveral Air Station (CCAS). The implementation of local, mesoscale modeling systems at KSC/CCAS is designed to provide detailed short-range (less than 24 h) forecasts of winds, clouds, and hazardous weather such as thunderstorms. Short-range forecasting is a challenge for daily operations, and manned and unmanned launches since KSC/CCAS is located in central Florida where the weather during the warm season is dominated by mesoscale circulations like the sea breeze. For this application, MASS has been modified to run on a Stardent 3000 workstation. Workstation-based, real-time numerical modeling requires a compromise between the requirement to run the system fast enough so that the output can be used before expiration balanced against the desire to improve the simulations by increasing resolution and using more detailed physical parameterizations. It is now feasible to run high-resolution mesoscale models such as MASS on local workstations to provide timely forecasts at a fraction of the cost required to run these models on mainframe supercomputers. MASS has been running in the Applied Meteorology Unit (AMU) at KSC/CCAS since January 1994 for the purpose of system evaluation. In March 1995, the AMU began sending real-time MASS output to the forecasters and meteorologists at CCAS, Spaceflight Meteorology Group (Johnson Space Center, Houston, Texas), and the National Weather Service (Melbourne, Florida). However, MASS is not yet an operational system. The final decision whether to transition MASS for operational use will depend on a combination of forecaster feedback, the AMU's final evaluation results, and the life-cycle costs of the operational system.

High Resolution Mass Spectra Analysis with a Programmable Calculator.

ERIC Educational Resources Information Center

Holdsworth, David K.

1980-01-01

Highlighted are characteristics of programs written for a pocket-sized programmable calculator to analyze mass spectra data (such as displaying high resolution masses for formulas, predicting whether formulas are stable molecules or molecular ions, determining formulas by isotopic abundance measurement) in a laboratory or classroom. (CS)

Unraveling the chemical complexity of biomass burning VOC emissions via H3O+ ToF-CIMS (PTR-ToF): emissions characterization

NASA Astrophysics Data System (ADS)

Koss, A.; Sekimoto, K.; Gilman, J.; Selimovic, V.; Coggon, M.; Zarzana, K. J.; Yuan, B.; Lerner, B. M.; Brown, S. S.; Jimenez, J. L.; Krechmer, J. E.; Warneke, C.; Yokelson, R. J.; De Gouw, J. A.

2017-12-01

Gas-phase biomass burning emissions can include hundreds, if not thousands, of unique volatile and intermediate-volatility organic compounds. It is crucial to know the composition of these emissions to understand secondary organic aerosol formation, ozone formation, and human health effects resulting from fires. However, the composition can vary greatly with fuel type and fire combustion process. During the FIREX 2016 laboratory intensive at the US Forest Service Fire Sciences Laboratory in Missoula, Montana, high-resolution H3O+-CIMS (PTR-ToF) was deployed to characterize VOC emissions. More than 500 ion masses were consistently enhanced in each of 58 fires, which included a wide variety of fuel types representative of the western United States. Using a combination of extensive literature review, H3O+ and NO+ CIMS with GC preseparation, comparison to other instruments, and mass spectral context, we were able to identify the VOC contributors to 90% of the instrument signal. This provides unprecedented chemical detail in high time resolution. We present chemical characteristics of emissions, including OH reactivity and volatility, and highlight areas where better identification is needed.

Conversational high resolution mass spectrographic data reduction

NASA Technical Reports Server (NTRS)

Romiez, M. P.

1973-01-01

A FORTRAN 4 program is described which reduces the data obtained from a high resolution mass spectrograph. The program (1) calculates an accurate mass for each line on the photoplate, and (2) assigns elemental compositions to each accurate mass. The program is intended for use in a time-shared computing environment and makes use of the conversational aspects of time-sharing operating systems.

Performance evaluation of a miniature magnetic sector mass spectrometer onboard a satellite in space.

PubMed

Guo, Meiru; Li, Detian; Cheng, Yongjun; Wang, Yongjun; Sun, Wenjun; Pei, Xiaoqiang; Dong, Meng; Sheng, Xuemin; Zhao, Lan; Li, Yanwu

2018-04-01

With the rapid development of space technology in China, it is urgent to use mass spectrometer to detect the space environment. In this work, a space miniature magnetic sector mass spectrometer is evaluated, which consists of three subsystems: (1) physical unit, (2) electric control unit, (3) and high voltage power. It has 90° magnetic sector-field analyzer with double trajectory, in which a trajectory measurement range is from 1 to 12 amu, the other range is from 6 to 90 amu.The mass spectrometer has two work models, one is used to measure space neutral gas when the filament of mass spectrometer ion source turned on, the other is used to measure space charged ions when the filament turned off. The absolute resolution of this device is less than 1 amu, the minimum detectable ion current is about 10 -13  A, and the sensitivity is 10 -6  A/Pa (N 2 ). Its overall size is 170 mm × 165 mm × 170 mm, its weight is 4.5 kg, and its power consumption is 18 W. A series of environmental adaptability tests, including high and low temperature cycle, shock, vibration, thermal vacuum cycle, were carried out on the ground before launching, and sensitivity and peak position were also calibrated on the ground. In November 2012, the mass spectrometer was carried by an experimental satellite to 499 km sun synchronization and is still working right now. It successfully detected the atmosphere compositions both in the satellite orbit and gas-emitted from satellite, including O, He, 12 CO 2 , 13 CO 2 , H 2 , N 2 , O 2 , H 2 O, and so on.

Novel strategy for the determination of illegal adulterants in health foods and herbal medicines using high-performance liquid chromatography with high-resolution mass spectrometry.

PubMed

Wang, Zhe; Wu, Caisheng; Wang, Gangli; Zhang, Qingsheng; Zhang, Jinlan

2015-03-01

The detection, confirmation, and quantification of multiple illegal adulterants in health foods and herbal medicines by using a single analytical method are a challenge. This paper reports on a new strategy to meet this challenge by employing high-performance liquid chromatography coupled with high-resolution mass spectrometry and a mass spectral tree similarity filter technique. This analytical method can rapidly collect high-resolution, high-accuracy, optionally multistage mass data for compounds in samples. After a preliminary screening by retention time and high-resolution mass spectral data, known illegal adulterants can be detected. The mass spectral tree similarity filter technique has been applied to rapidly confirm these adulterants and simultaneously discover unknown ones. By using full-scan mass spectra as stem and data-dependent subsequent stage mass spectra to form branches, mass spectrometry data from detected compounds are converted into mass spectral trees. The known or unknown illegal adulterants in the samples are confirmed or discovered based on the similarity between their mass spectral trees and those of the references in a library, and they are finally quantified against standard curves. This new strategy has been tested by using 50 samples, and the illegal adulterants were rapidly and effectively detected, confirmed and quantified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detecting kinematic boundary surfaces in phase space: particle mass measurements in SUSY-like events

DOE PAGES

Debnath, Dipsikha; Gainer, James S.; Kilic, Can; ...

2017-06-19

We critically examine the classic endpoint method for particle mass determination, focusing on difficult corners of parameter space, where some of the measurements are not independent, while others are adversely affected by the experimental resolution. In such scenarios, mass differences can be measured relatively well, but the overall mass scale remains poorly constrained. Using the example of the standard SUSY decay chain q ~→χ ~ 0 2→ℓ ~→χ ~ 0 1 , we demonstrate that sensitivity to the remaining mass scale parameter can be recovered by measuring the two-dimensional kinematical boundary in the relevant three-dimensional phase space of invariant massesmore » squared. We develop an algorithm for detecting this boundary, which uses the geometric properties of the Voronoi tessellation of the data, and in particular, the relative standard deviation (RSD) of the volumes of the neighbors for each Voronoi cell in the tessellation. We propose a new observable, Σ¯ , which is the average RSD per unit area, calculated over the hypothesized boundary. We show that the location of the Σ¯ maximum correlates very well with the true values of the new particle masses. Our approach represents the natural extension of the one-dimensional kinematic endpoint method to the relevant three dimensions of invariant mass phase space.« less

Detecting kinematic boundary surfaces in phase space: particle mass measurements in SUSY-like events

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

Debnath, Dipsikha; Gainer, James S.; Kilic, Can

We critically examine the classic endpoint method for particle mass determination, focusing on difficult corners of parameter space, where some of the measurements are not independent, while others are adversely affected by the experimental resolution. In such scenarios, mass differences can be measured relatively well, but the overall mass scale remains poorly constrained. Using the example of the standard SUSY decay chain q ~→χ ~ 0 2→ℓ ~→χ ~ 0 1 , we demonstrate that sensitivity to the remaining mass scale parameter can be recovered by measuring the two-dimensional kinematical boundary in the relevant three-dimensional phase space of invariant massesmore » squared. We develop an algorithm for detecting this boundary, which uses the geometric properties of the Voronoi tessellation of the data, and in particular, the relative standard deviation (RSD) of the volumes of the neighbors for each Voronoi cell in the tessellation. We propose a new observable, Σ¯ , which is the average RSD per unit area, calculated over the hypothesized boundary. We show that the location of the Σ¯ maximum correlates very well with the true values of the new particle masses. Our approach represents the natural extension of the one-dimensional kinematic endpoint method to the relevant three dimensions of invariant mass phase space.« less

Implementation of Precursor and Neutral Loss Scans on a Miniature Ion Trap Mass Spectrometer and Performance Comparison to a Benchtop Linear Ion Trap

NASA Astrophysics Data System (ADS)

Snyder, Dalton T.; Szalwinski, Lucas J.; Hilger, Ryan; Cooks, R. Graham

2018-03-01

Implementation of orthogonal double resonance precursor and neutral loss scans on the Mini 12 miniature rectilinear ion trap mass spectrometer is described, and performance is compared to that of a commercial Thermo linear trap quadropole (LTQ) linear ion trap. The ac frequency scan version of the technique at constant rf voltage is used here because it is operationally much simpler to implement. Remarkably, the Mini 12 shows up to two orders of magnitude higher sensitivity compared to that of the LTQ. Resolution on the LTQ is better than unit at scan speeds of 400 Th/s, whereas peak widths on the Mini 12, on average, range from 0.5 to 2.0 Th full width at half maximum and depend heavily on the precursor ion Mathieu q parameter as well as the pump down time that precedes the mass scan. Both sensitivity and resolution are maximized under higher pressure conditions (short pump down time) on the Mini 12. The effective mass range of the product ion ejection waveform was found to be 5.8 Th on the Mini 12 in the precursor ion scan mode vs. that of 3.9 Th on the LTQ. In the neutral loss scan mode, the product ion selectivity was between 8 and 11 Th on the Mini 12 and between 7 and 8 Th on the LTQ. The effects of nonlinear resonance lines on the Mini 12 were also explored. [Figure not available: see fulltext.

31 CFR 560.510 - Transactions related to the resolution of disputes between the United States or United States...

Code of Federal Regulations, 2010 CFR

2010-07-01

... resolution of disputes between the United States or United States nationals and the Government of Iran. 560... between the United States or United States nationals and the Government of Iran. (a) Except as otherwise... with awards, decisions or orders of the Iran-United States Claims Tribunal in The Hague, the...

GLS-Finder: A Platform for Fast Profiling of Glucosinolates in Brassica Vegetables.

PubMed

Sun, Jianghao; Zhang, Mengliang; Chen, Pei

2016-06-01

Mass spectrometry combined with related tandem techniques has become the most popular method for plant secondary metabolite characterization. We introduce a new strategy based on in-database searching, mass fragmentation behavior study, formula predicting for fast profiling of glucosinolates, a class of important compounds in brassica vegetables. A MATLAB script-based expert system computer program, "GLS-Finder", was developed. It is capable of qualitative and semi-quantitative analyses of glucosinolates in samples using data generated by ultrahigh-performance liquid chromatography-high-resolution accurate mass with multi-stage mass fragmentation (UHPLC-HRAM/MS(n)). A suite of bioinformatic tools was integrated into the "GLS-Finder" to perform raw data deconvolution, peak alignment, glucosinolate putative assignments, semi-quantitation, and unsupervised principal component analysis (PCA). GLS-Finder was successfully applied to identify intact glucosinolates in 49 commonly consumed Brassica vegetable samples in the United States. It is believed that this work introduces a new way of fast data processing and interpretation for qualitative and quantitative analyses of glucosinolates, where great efficacy was improved in comparison to identification manually.

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

Martínez-Rodríguez, Sergio; González-Ramírez, Luis Antonio; Clemente-Jiménez, Josefa María

The dihydropyrimidinase from S. meliloti CECT4114, with activity towards both hydantoin and dihydrouracil substrates, was crystallized, and diffraction data were collected to 1.85 Å resolution. Dihydropyrimidinases are involved in the reductive pathway of pyrimidine degradation, catalysing the hydrolysis of 5,6-dihydrouracil and 5,6-dihydrothymine to the corresponding N-carbamoyl β-amino acids. This enzyme has often been referred to as hydantoinase owing to its industrial application in the production of optically pure amino acids starting from racemic mixtures of 5-monosubstituted hydantoins. Recombinant dihydropyrimidinase from Sinorhizobium meliloti CECT4114 (SmelDhp) has been expressed, purified and crystallized. Crystallization was performed using the counter-diffusion method with capillaries ofmore » 0.3 mm inner diameter. Crystals of SmelDhp suitable for data collection and structure determination were grown in the presence of agarose at 0.1%(w/v) in order to ensure mass transport controlled by diffusion. X-ray data were collected to a resolution of 1.85 Å. The crystal belongs to the orthorhombic space group C222{sub 1}, with unit-cell parameters a = 124.89, b = 126.28, c = 196.10 Å and two molecules in the asymmetric unit. A molecular-replacement solution has been determined and refinement is in progress.« less

Ultrastructural instability of paired helical filaments from corticobasal degeneration as examined by scanning transmission electron microscopy.

PubMed Central

Ksiezak-Reding, H.; Tracz, E.; Yang, L. S.; Dickson, D. W.; Simon, M.; Wall, J. S.

1996-01-01

Paired helical filaments (PHFs) accumulate in the brains of subjects affected with Alzheimer's disease (AD) and certain other neurodegenerative disorders, including corticobasal degeneration (CBD). Electron microscope studies have shown that PHFs from CBD differ from those of AD by being wider and having a longer periodicity of the helical twist. Moreover, PHFs from CBD have been shown to be primarily composed of two rather than three highly phosphorylated polypeptides of tau (PHF-tau), with these polypeptides expressing no exons 3 and 10. To further explore the relationship between the heterogeneity of PHF-tau and the appearance of abnormal filaments, the ultrastructure and physical parameters such as mass per unit length and dimensions were compared in filaments from CBD and AD using high resolution scanning transmission electron microscopy (STEM). Filament-enriched fractions were isolated as Sarcosyl-insoluble pellets and for STEM studies, samples were freeze-dried without prior fixation or staining. Ultrastructurally, PHFs from CBD were shown to be a heterogeneous population as double- and single-stranded filaments could be identified based on their width and physical mass per unit length expressed in kilodaltons (kd) per nanometer (nm). Less abundant, double-stranded filaments had a maximal width of 29 nm and a mass per unit length of 133 kd/nm, whereas three times more abundant single-stranded filaments were 15 nm wide and bad a mass per unit length of 62 kd/nm. Double-stranded filaments also displayed a distinct axial region of less dense mass, which appeared to divide the PHFs into two protofilament-like strands. Furthermore, these filaments were frequently observed to physically separate along the long axis into two single strands or to break longitudinally. In contrast, PHFs from AD were ultrastructurally stable and uniform both in their width (22 nm) and physical mass per unit length (104 kd/nm). The ultrastructural features indicate that filaments of CBD and AD differ both in stability and packing of tau and that CBD filaments, composed of two distinct protofilaments, are more labile under STEM conditions. As fixed and stained filaments from CBD have been shown to be stable and uniform in size by conventional transmission electron microscopy, STEM studies may be particularly suitable for detecting instability of unstained and unfixed filaments. The results also suggest that molecular heterogeneity and/or post-translational modifications of tau may strongly influence the morphology and stability of abnormal filaments. Images Figure 1 Figure 2 Figure 3 PMID:8702002

Ion Mass Spectroscopy for the Outer Solar System

NASA Astrophysics Data System (ADS)

Reisenfeld, D. B.; Elphic, R. C.; McComas, D. J.; Nordholt, J. E.; Steinberg, J. T.; Wiens, R. C.

2001-01-01

A proven method for determination of the exospheric and surface composition of moons and comets is ion mass spectroscopy. Ions are produced via sputtering of surface constituents by the ambient plasma (solar wind or planetary magnetospheres), and via photo- and electron impact ionization of neutral exospheric/atmospheric constituents. A promising emergent technology in the field of space-based ion mass spectrometry is the low-cost, miniaturized but high-performance ion mass spectrometer (IMS) as exhibited by the Plasma Experiment for Planetary Exploration (PEPE) on Deep Space 1 (DS-1). A technology demonstration instrument, the PEPE IMS realized a mass resolution (M/delta(M)) of approximately 10. Its energy range extends from 5 eV to 9 keV at this mass resolution, and up to 33.5 keV in a lower mass resolution mode. With minimal development, these capabilities can be greatly extended. Already, we have produced a fully functional engineering model having a M/delta(M) = 20 and an energy range extending to 18 keV in the high-mass resolution mode. Further design modifications anticipate extending the mass resolution to 30-40 while still maintaining a miniaturized design. This makes possible many more isotopic and molecular differentiations than achievable with the original PEPE design. A PEPE-class spectrometer can address a significant number of the OPP key strategic objectives. In particular, in situ cometary nucleus analysis, studies of Triton's atmospheric and surface composition, and Europa surface composition analysis, can all be performed through IMS measurements. Additional information is contained in the original extended abstract.

A homemade high-resolution orthogonal-injection time-of-flight mass spectrometer with a heated capillary inlet

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

Guo Changjuan; Huang Zhengxu; Gao Wei

2008-01-15

We describe a homemade high-resolution orthogonal-injection time-of-flight (O-TOF) mass spectrometer combing a heated capillary inlet. The O-TOF uses a heated capillary tube combined with a radio-frequency only quadrupole (rf-only quadrupole) as an interface to help the ion transmission from the atmospheric pressure to the low-pressure regions. The principle, configuration of the O-TOF, and the performance of the instrument are introduced in this paper. With electrospray ion source, the performances of the mass resolution, the sensitivity, the mass range, and the mass accuracy are described. We also include our results obtained by coupling atmospheric pressure matrix-assisted laser deporption ionization with thismore » instrument.« less

Linear Ion Traps in Space: The Mars Organic Molecule Analyzer (MOMA) Instrument and Beyond

NASA Astrophysics Data System (ADS)

Arevalo, Ricardo; Brinckerhoff, William; Mahaffy, Paul; van Amerom, Friso; Danell, Ryan; Pinnick, Veronica; Li, Xiang; Hovmand, Lars; Getty, Stephanie; Grubisic, Andrej; Goesmann, Fred; Cottin, Hervé

2015-11-01

Historically, quadrupole mass spectrometer (QMS) instruments have been used to explore a wide survey of planetary targets in our solar system, from Venus (Pioneer Venus) to Saturn (Cassini-Huygens). However, linear ion trap (LIT) mass spectrometers have found a niche as smaller, versatile alternatives to traditional quadrupole analyzers.The core astrobiological experiment of ESA’s ExoMars Program is the Mars Organic Molecule Analyzer (MOMA) onboard the ExoMars 2018 rover. The MOMA instrument is centered on a linear (or 2-D) ion trap mass spectrometer. As opposed to 3-D traps, LIT-based instruments accommodate two symmetrical ion injection pathways, enabling two complementary ion sources to be used. In the case of MOMA, these two analytical approaches are laser desorption mass spectrometry (LDMS) at Mars ambient pressures, and traditional gas chromatography mass spectrometry (GCMS). The LIT analyzer employed by MOMA also offers: higher ion capacity compared to a 3-D trap of the same volume; redundant detection subassemblies for extended lifetime; and, a link to heritage QMS designs and assembly logistics. The MOMA engineering test unit (ETU) has demonstrated the detection of organics in the presence of wt.%-levels of perchlorate, effective ion enhancement via stored waveform inverse Fourier transform (SWIFT), and derivation of structural information through tandem mass spectrometry (MS/MS).A more progressive linear ion trap mass spectrometer (LITMS), funded by the NASA ROSES MatISSE Program, is being developed at NASA GSFC and promises to augment the capabilities of the MOMA instrument by way of: an expanded mass range (i.e., 20 - 2000 Da); detection of both positive and negative ions; spatially resolved (<1 mm) characterization of individual rock core layers; and, evolved gas analysis and GCMS with pyrolysis up to 1300° C (enabling breakdown of refractory phases). The Advanced Resolution Organic Molecule Analyzer (AROMA) instrument, being developed through NASA PICASSO and ESA Research and Development Programs, combines a highly capable LIT front end (a la LITMS) with a high-resolution OrbitrapTM (a la CosmOrbitrap) mass analyzer to enable disambiguation of complex molecular signals in organic-rich targets.

Resolution of co-eluting compounds of Cannabis Sativa in comprehensive two-dimensional gas chromatography/mass spectrometry detection with Multivariate Curve Resolution-Alternating Least Squares.

PubMed

Omar, Jone; Olivares, Maitane; Amigo, José Manuel; Etxebarria, Nestor

2014-04-01

Comprehensive Two Dimensional Gas Chromatography - Mass Spectrometry (GC × GC/qMS) analysis of Cannabis sativa extracts shows a high complexity due to the large variety of terpenes and cannabinoids and to the fact that the complete resolution of the peaks is not straightforwardly achieved. In order to support the resolution of the co-eluted peaks in the sesquiterpene and the cannabinoid chromatographic region the combination of Multivariate Curve Resolution and Alternating Least Squares algorithms was satisfactorily applied. As a result, four co-eluting areas were totally resolved in the sesquiterpene region and one in the cannabinoid region in different samples of Cannabis sativa. The comparison of the mass spectral profiles obtained for each resolved peak with theoretical mass spectra allowed the identification of some of the co-eluted peaks. Finally, the classification of the studied samples was achieved based on the relative concentrations of the resolved peaks. Copyright © 2014 Elsevier B.V. All rights reserved.

First astronomical unit scale image of the GW Orionis triple system. Direct detection of a new stellar companion

NASA Astrophysics Data System (ADS)

Berger, J.-P.; Monnier, J. D.; Millan-Gabet, R.; Renard, S.; Pedretti, E.; Traub, W.; Bechet, C.; Benisty, M.; Carleton, N.; Haguenauer, P.; Kern, P.; Labeye, P.; Longa, F.; Lacasse, M.; Malbet, F.; Perraut, K.; Ragland, S.; Schloerb, P.; Schuller, P. A.; Thiébaut, E.

2011-05-01

Context. Young and close multiple systems are unique laboratories to probe the initial dynamical interactions between forming stellar systems and their dust and gas environment. Their study is a key building block to understanding the high frequency of main-sequence multiple systems. However, the number of detected spectroscopic young multiple systems that allow dynamical studies is limited. GW Orionis is one such system. It is one of the brightest young T Tauri stars and is surrounded by a massive disk. Aims: Our goal is to probe the GW Orionis multiplicity at angular scales at which we can spatially resolve the orbit. Methods: We used the IOTA/IONIC3 interferometer to probe the environment of GW Orionis with an astronomical unit resolution in 2003, 2004, and 2005. By measuring squared visibilities and closure phases with a good UV coverage we carry out the first image reconstruction of GW Ori from infrared long-baseline interferometry. Results.We obtained the first infrared image of a T Tauri multiple system with astronomical unit resolution. We show that GW Orionis is a triple system, resolve for the first time the previously known inner pair (separation ρ ~ 1.4 AU) and reveal a new more distant component (GW Ori C) with a projected separation of ~ 8 AU with direct evidence of motion. Furthermore, the nearly equal (2:1) H-band flux ratio of the inner components suggests that either GW Ori B is undergoing a preferential accretion event that increases its disk luminosity or that the estimate of the masses has to be revisited in favour of a more equal mass-ratio system that is seen at lower inclination. Conclusions: Accretion disk models of GW Ori will need to be completely reconsidered because of this outer companion C and the unexpected brightness of companion B.

ION COMPOSITION ELUCIDATION (ICE): A HIGH RESOLUTION MASS SPECTROMETRIC TECHNIQUE FOR CHARACTERIZATION AND IDENTIFICATION OF ORGANIC COMPOUNDS

EPA Science Inventory

Identifying compounds found in the environment without knowledge of their origin is a very difficult analytical problem. Comparison of the low resolution mass spectrum of a compound with those in the NIST or Wiley mass spectral libraries can provide a tentative identification whe...

Quantifying the resolution level where the GRACE satellites can separate Greenland's glacial mass balance from surface mass balance

NASA Astrophysics Data System (ADS)

Bonin, J. A.; Chambers, D. P.

2015-09-01

Mass change over Greenland can be caused by either changes in the glacial dynamic mass balance (DMB) or the surface mass balance (SMB). The GRACE satellite gravity mission cannot directly separate the two physical causes because it measures the sum of the entire mass column with limited spatial resolution. We demonstrate one theoretical way to indirectly separate cumulative SMB from DMB with GRACE, using a least squares inversion technique with knowledge of the location of the glaciers. However, we find that the limited 60 × 60 spherical harmonic representation of current GRACE data does not provide sufficient resolution to adequately accomplish the task. We determine that at a maximum degree/order of 90 × 90 or above, a noise-free gravity measurement could theoretically separate the SMB from DMB signals. However, current GRACE satellite errors are too large at present to separate the signals. A noise reduction of a factor of 10 at a resolution of 90 × 90 would provide the accuracy needed for the interannual cumulative SMB and DMB to be accurately separated.

Quantifying the resolution level where the GRACE satellites can separate Greenland's glacial mass balance from surface mass balance

NASA Astrophysics Data System (ADS)

Bonin, J. A.; Chambers, D. P.

2015-02-01

Mass change over Greenland can be caused by either changes in the glacial mass balance (GMB) or the precipitation-based surface mass balance (SMB). The GRACE satellite gravity mission cannot directly separate the two physical causes because it measures the sum of the entire mass column with limited spatial resolution. We demonstrate one theoretical way to indirectly separate SMB from GMB with GRACE, using a least squares inversion technique with knowledge of the location of the glacier. However, we find that the limited 60 × 60 spherical harmonic representation of current GRACE data does not provide sufficient resolution to adequately accomplish the task. We determine that at a maximum degree/order of 90 × 90 or above, a noise-free gravity measurement could theoretically separate the SMB from GMB signals. However, current GRACE satellite errors are too large at present to separate the signals. A noise reduction of a factor of 9 at a resolution of 90 × 90 would provide the accuracy needed for the interannual SMB and GMB to be accurately separated.

A novel approach for the quantitation of carbohydrates in mash, wort, and beer with RP-HPLC using 1-naphthylamine for precolumn derivatization.

PubMed

Rakete, Stefan; Glomb, Marcus A

2013-04-24

A novel universal method for the determination of reducing mono-, di-, and oligosaccharides in complex matrices on RP-HPLC using 1-naphthylamine for precolumn derivatization with sodium cyanoborhydride was established to study changes in the carbohydrate profile during beer brewing. Fluorescence and mass spectrometric detection enabled very sensitive analyses of beer-relevant carbohydrates. Mass spectrometry additionally allowed the identification of the molecular weight and thereby the degree of polymerization of unknown carbohydrates. Thus, carbohydrates with up to 16 glucose units were detected. Comparison demonstrated that the novel method was superior to fluorophore-assisted carbohydrate electrophoresis (FACE). The results proved the HPLC method clearly to be more powerful in regard to sensitivity and resolution. Analogous to FACE, this method was designated fluorophore-assisted carbohydrate HPLC (FAC-HPLC).

A giant planet around a metal-poor star of extragalactic origin.

PubMed

Setiawan, Johny; Klement, Rainer J; Henning, Thomas; Rix, Hans-Walter; Rochau, Boyke; Rodmann, Jens; Schulze-Hartung, Tim

2010-12-17

Stars in their late stage of evolution, such as horizontal branch stars, are still largely unexplored for planets. We detected a planetary companion around HIP 13044, a very metal-poor star on the red horizontal branch, on the basis of radial velocity observations with a high-resolution spectrograph at the 2.2-meter Max-Planck Gesellschaft-European Southern Observatory telescope. The star's periodic radial velocity variation of P = 16.2 days caused by the planet can be distinguished from the periods of the stellar activity indicators. The minimum mass of the planet is 1.25 times the mass of Jupiter and its orbital semimajor axis is 0.116 astronomical units. Because HIP 13044 belongs to a group of stars that have been accreted from a disrupted satellite galaxy of the Milky Way, the planet most likely has an extragalactic origin.

High resolution laser mass spectrometry bioimaging.

PubMed

Murray, Kermit K; Seneviratne, Chinthaka A; Ghorai, Suman

2016-07-15

Mass spectrometry imaging (MSI) was introduced more than five decades ago with secondary ion mass spectrometry (SIMS) and a decade later with laser desorption/ionization (LDI) mass spectrometry (MS). Large biomolecule imaging by matrix-assisted laser desorption/ionization (MALDI) was developed in the 1990s and ambient laser MS a decade ago. Although SIMS has been capable of imaging with a moderate mass range at sub-micrometer lateral resolution from its inception, laser MS requires additional effort to achieve a lateral resolution of 10μm or below which is required to image at the size scale of single mammalian cells. This review covers untargeted large biomolecule MSI using lasers for desorption/ionization or laser desorption and post-ionization. These methods include laser microprobe (LDI) MSI, MALDI MSI, laser ambient and atmospheric pressure MSI, and near-field laser ablation MS. Novel approaches to improving lateral resolution are discussed, including oversampling, beam shaping, transmission geometry, reflective and through-hole objectives, microscope mode, and near-field optics. Copyright © 2016 Elsevier Inc. All rights reserved.

1998 Conference on Precision Electromagnetic Measurements Digest. Proceedings.

NASA Astrophysics Data System (ADS)

Nelson, T. L.

The following topics were dealt with: fundamental constants; caesium standards; AC-DC transfer; impedance measurement; length measurement; units; statistics; cryogenic resonators; time transfer; QED; resistance scaling and bridges; mass measurement; atomic fountains and clocks; single electron transport; Newtonian constant of gravitation; stabilised lasers and frequency measurements; cryogenic current comparators; optical frequency standards; high voltage devices and systems; international compatibility; magnetic measurement; precision power measurement; high resolution spectroscopy; DC transport standards; waveform acquisition and analysis; ion trap standards; optical metrology; quantised Hall effect; Josephson array comparisons; signal generation and measurement; Avogadro constant; microwave networks; wideband power standards; antennas, fields and EMC; quantum-based standards.

High-Resolution Mass Spectrometers

NASA Astrophysics Data System (ADS)

Marshall, Alan G.; Hendrickson, Christopher L.

2008-07-01

Over the past decade, mass spectrometry has been revolutionized by access to instruments of increasingly high mass-resolving power. For small molecules up to ˜400 Da (e.g., drugs, metabolites, and various natural organic mixtures ranging from foods to petroleum), it is possible to determine elemental compositions (CcHhNnOoSsPp…) of thousands of chemical components simultaneously from accurate mass measurements (the same can be done up to 1000 Da if additional information is included). At higher mass, it becomes possible to identify proteins (including posttranslational modifications) from proteolytic peptides, as well as lipids, glycoconjugates, and other biological components. At even higher mass (˜100,000 Da or higher), it is possible to characterize posttranslational modifications of intact proteins and to map the binding surfaces of large biomolecule complexes. Here we review the principles and techniques of the highest-resolution analytical mass spectrometers (time-of-flight and Fourier transform ion cyclotron resonance and orbitrap mass analyzers) and describe some representative high-resolution applications.

Effect of atelectasis changes on tissue mass and dose during lung radiotherapy.

PubMed

Guy, Christopher L; Weiss, Elisabeth; Jan, Nuzhat; Reshko, Leonid B; Christensen, Gary E; Hugo, Geoffrey D

2016-11-01

To characterize mass and density changes of lung parenchyma in non-small cell lung cancer (NSCLC) patients following midtreatment resolution of atelectasis and to quantify the impact this large geometric change has on normal tissue dose. Baseline and midtreatment CT images and contours were obtained for 18 NSCLC patients with atelectasis. Patients were classified based on atelectasis volume reduction between the two scans as having either full, partial, or no resolution. Relative mass and density changes from baseline to midtreatment were calculated based on voxel intensity and volume for each lung lobe. Patients also had clinical treatment plans available which were used to assess changes in normal tissue dose constraints from baseline to midtreatment. The midtreatment image was rigidly aligned with the baseline scan in two ways: (1) bony anatomy and (2) carina. Treatment parameters (beam apertures, weights, angles, monitor units, etc.) were transferred to each image. Then, dose was recalculated. Typical IMRT dose constraints were evaluated on all images, and the changes from baseline to each midtreatment image were investigated. Atelectatic lobes experienced mean (stdev) mass changes of -2.8% (36.6%), -24.4% (33.0%), and -9.2% (17.5%) and density changes of -66.0% (6.4%), -25.6% (13.6%), and -17.0% (21.1%) for full, partial, and no resolution, respectively. Means (stdev) of dose changes to spinal cord D max , esophagus D mean , and lungs D mean were 0.67 (2.99), 0.99 (2.69), and 0.50 Gy (2.05 Gy), respectively, for bone alignment and 0.14 (1.80), 0.77 (2.95), and 0.06 Gy (1.71 Gy) for carina alignment. Dose increases with bone alignment up to 10.93, 7.92, and 5.69 Gy were found for maximum spinal cord, mean esophagus, and mean lung doses, respectively, with carina alignment yielding similar values. 44% and 22% of patients had at least one metric change by at least 5 Gy (dose metrics) or 5% (volume metrics) for bone and carina alignments, respectively. Investigation of GTV coverage showed mean (stdev) changes in V Rx , D max , and D min of -5.5% (13.5%), 2.5% (4.2%), and 0.8% (8.9%), respectively, for bone alignment with similar results for carina alignment. Resolution of atelectasis caused mass and density decreases, on average, and introduced substantial changes in normal tissue dose metrics in a subset of the patient cohort.

Effect of atelectasis changes on tissue mass and dose during lung radiotherapy

PubMed Central

Guy, Christopher L.; Weiss, Elisabeth; Jan, Nuzhat; Reshko, Leonid B.; Christensen, Gary E.; Hugo, Geoffrey D.

2016-01-01

Purpose: To characterize mass and density changes of lung parenchyma in non-small cell lung cancer (NSCLC) patients following midtreatment resolution of atelectasis and to quantify the impact this large geometric change has on normal tissue dose. Methods: Baseline and midtreatment CT images and contours were obtained for 18 NSCLC patients with atelectasis. Patients were classified based on atelectasis volume reduction between the two scans as having either full, partial, or no resolution. Relative mass and density changes from baseline to midtreatment were calculated based on voxel intensity and volume for each lung lobe. Patients also had clinical treatment plans available which were used to assess changes in normal tissue dose constraints from baseline to midtreatment. The midtreatment image was rigidly aligned with the baseline scan in two ways: (1) bony anatomy and (2) carina. Treatment parameters (beam apertures, weights, angles, monitor units, etc.) were transferred to each image. Then, dose was recalculated. Typical IMRT dose constraints were evaluated on all images, and the changes from baseline to each midtreatment image were investigated. Results: Atelectatic lobes experienced mean (stdev) mass changes of −2.8% (36.6%), −24.4% (33.0%), and −9.2% (17.5%) and density changes of −66.0% (6.4%), −25.6% (13.6%), and −17.0% (21.1%) for full, partial, and no resolution, respectively. Means (stdev) of dose changes to spinal cord Dmax, esophagus Dmean, and lungs Dmean were 0.67 (2.99), 0.99 (2.69), and 0.50 Gy (2.05 Gy), respectively, for bone alignment and 0.14 (1.80), 0.77 (2.95), and 0.06 Gy (1.71 Gy) for carina alignment. Dose increases with bone alignment up to 10.93, 7.92, and 5.69 Gy were found for maximum spinal cord, mean esophagus, and mean lung doses, respectively, with carina alignment yielding similar values. 44% and 22% of patients had at least one metric change by at least 5 Gy (dose metrics) or 5% (volume metrics) for bone and carina alignments, respectively. Investigation of GTV coverage showed mean (stdev) changes in VRx, Dmax, and Dmin of −5.5% (13.5%), 2.5% (4.2%), and 0.8% (8.9%), respectively, for bone alignment with similar results for carina alignment. Conclusions: Resolution of atelectasis caused mass and density decreases, on average, and introduced substantial changes in normal tissue dose metrics in a subset of the patient cohort. PMID:27806593

Venusian tectonics: Convective coupling to the lithosphere?

NASA Technical Reports Server (NTRS)

Phillips, R. J.

1987-01-01

The relationship between the dominant global heat loss mechanism and planetary size has motivated the search for tectonic style on Venus. Prior to the American and Soviet mapping missions of the past eight years, it was thought that terrestrial style plate tectonics was operative on Venus because this planet is approximately the size of the Earth and is conjectured to have about the same heat source content per unit mass. However, surface topography mapped by the altimeter of the Pioneer Venus spacecraft did not show any physiographic expression of terrestrial style spreading ridges, trenches, volcanic arcs or transform faults, although the horizontal resolution was questionable for detection of at least some of these features. The Venera 15 and 16 radar missions mapped the northern latitudes of Venus at 1 to 2 km resolution and showed that there are significant geographic areas of deformation seemingly created by large horizontal stresses. These same high resolution images show no evidence for plate tectonic features. Thus a fundamental problem for venusian tectonics is the origin of large horizontal stresses near the surface in the apparent absence of plate tectonics.

ALTERNATIVE DISINFECTANTS FOR DRINKING WATER

EPA Science Inventory

Using a combination of spectral identification techniques - gas chromatography coupled with low-and high-resolution electron-impact mass spectrometry (GC/EI-MS), low-and high-resolution chemical ionization mass spectrometry (GC/CI-MS), and Fourier transform infrared spectroscopy ...

Listening to Shells: Galaxy Masses from Disrupted Satellites

NASA Astrophysics Data System (ADS)

Westfall, Kyle; Sanderson, R.

2014-01-01

Our ability to measure the dynamical mass of an individual galaxy is limited by the radial extent of the luminous tracers of its potential. For elliptical galaxies, it is difficult to go much beyond two effective radii using integrated light. Appealing to particle tracers like globular clusters has allowed for mass measurements out to ten effective radii. The extended atomic-gas disks of spiral galaxies allow one to measure rotation curves well beyond the optical disk to a few effective radii; however, such mass measurements are limited to a single plane and can often be confused by warps. As surface-brightness limits have pushed ever deeper, the revealed abundance of disrupted satellites in galaxy halos may present a unique opportunity for determining the enclosed mass at very large radii (more than five effective radii), provided our technology is up to the challenge. Here, we discuss the prospect of using integrated light spectroscopy of tidal shells to measure the masses of individual galaxies at redshifts of up to 0.1. Our study considers the limitations of current and projected instrumentation on 4-, 10-, and 30-meter class telescopes. The observational constraints are indeed very stringent, requiring both high sensitivity (with V-band surface brightness limits below 25 mag per square arsecond) and high spectral resolution (R>10k), whereas spatial resolution is effectively irrelevant. Bigger is not necessarily better for our application because of the limited field-of-view (FOV) of large telescopes, which dramatically limits their total grasp. We find the two most-promising setups are (1) a large FOV (1 square arcminute) integral-field unit (IFU) on a 4-meter class telescope and (2) a multiplexed suite of small FOV (10 square arcseconds) IFUs on a 10- or 30-meter class telescope. Two prospective instruments that may meet these requirements are WEAVE, an instrument currently planned for the William Herschel Telescope at La Palma, and an OPTIMOS-EVE-like instrument on the E-ELT.

Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging.

PubMed

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

2013-12-30

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

A NEW HIGH RESOLUTION MASS SPECTROMETRY TECHNIQUE FOR IDENTIFYING PHARMACEUTICALS AND POTENTIAL ENDOCRINE DISRUPTORS IN DRINKING WATER SOURCES

EPA Science Inventory

A New High Resolution Mass Spectrometry Technique for Identifying Pharmaceuticals and Potential Endocrine Disruptors in Drinking Water Sources

Andrew H. Grange and G. Wayne Sovocool U.S.EPA, ORD, NERL, ESD, ECB, P.O. Box 93478, Las Vegas, NV 891933478

Mass spectra...

High Resolution PTR-TOFMS: A New Instrument for Organic Compound Measurements

NASA Astrophysics Data System (ADS)

Hansel, A.; Graus, M.; Mueller, M.; Wisthaler, A.

2007-12-01

Over the last decade proton transfer reaction mass spectrometry (PTR-MS) has become very popular in many scientific fields. PTR-MS allows for the quantitative detection of volatile organic compounds (VOCs) at pptv-level virtually in real time. Monitoring of VOCs with a time resolution of typically a second per compound has, for instance, enabled the tracking of pollution plumes by air-borne measurements, thus revealing the photo- chemical fate of pollutants. It has also been employed in direct eddy covariant flux measurements. This rapidity, however, has been achieved at the cost of the number of compounds to be analyzed and compound selectivity. Conventional PTR-MS can, for example, not distinguish between hydrocarbons and their oxygenated isobaric species, e.g. between naphthalene and octanal or between isoprene and furan. In a mass range up to 200 Dalton, such a task would require a mass resolving power of 5500. The use of a time of flight (TOF) instead of a quadrupole mass analyzer in PTR-MS provides a sufficient high mass resolution to identify the atomic composition of product ions by their exact mass and their characteristic isotope patterns. In addition PTR-TOF-MS can record full mass spectra within a fraction of a second which is a dramatically increase in duty cycle. At the University of Innsbruck a high resolution PTR-TOFMS has recently been developed, coupling a PTR-ion source and a high resolution TOFMS. We achieved a mass resolving power of 6000 (FWHM), and a detection limit of tens to a few hundreds of pptv if integrating mass spectra for one minute. First results and future directions will be discussed in this paper.

Crystallization and preliminary X-ray analysis of copper amine oxidase from Escherichia coli K-12.

PubMed

Roh, J H; Suzuki, H; Kumagai, H; Yamashita, M; Azakami, H; Murooka, Y; Mikami, B

1994-05-13

Copper-containing monoamine oxidase (MAO) from Escherichia coli was overproduced in the periplasmic space by expression of the cloned gene. The purified MAO has been crystallized by means of the hanging drop technique using sodium citrate as a precipitant. The crystals belong to the orthorhombic system, space group P2(1)2(1)2(1), with unit cell dimensions of a = 136.1 A, b = 168.4 A and c = 81.6 A. The asymmetric unit contains one molecule of MAO, with a crystal volume per protein mass (Vm) of 2.88 A3/Da and a solvent content of 58% by volume. The crystals diffract X-rays to a resolution limit of at least 2.7 A and are resistant to X-ray radiation damage. They appear to be suitable for X-ray structure analysis.

Crystallization of mitochondrial rhodoquinol-fumarate reductase from the parasitic nematode Ascaris suum with the specific inhibitor flutolanil

PubMed Central

Osanai, Arihiro; Harada, Shigeharu; Sakamoto, Kimitoshi; Shimizu, Hironari; Inaoka, Daniel Ken; Kita, Kiyoshi

2009-01-01

In adult Ascaris suum (roundworm) mitochondrial membrane-bound complex II acts as a rhodoquinol-fumarate reductase, which is the reverse reaction to that of mammalian complex II (succinate-ubiquinone reductase). The adult A. suum rhodoquinol-fumarate reductase was crystallized in the presence of octaethyleneglycol monododecyl ether and n-dodecyl-β-d-maltopyranoside in a 3:2 weight ratio. The crystals belonged to the orthorhombic space group P212121, with unit-cell parameters a = 123.75, b = 129.08, c = 221.12 Å, and diffracted to 2.8 Å resolution using synchrotron radiation. The presence of two molecules in the asymmetric unit (120 kDa × 2) gives a crystal volume per protein mass (V M) of 3.6 Å3 Da−1. PMID:19724139

Molluscan extinction patterns across the Cenomanian-Turonian stage boundary in the western interior of the United States

USGS Publications Warehouse

Elder, W.P.

1989-01-01

High-resolution stratigraphic analysis of 18 sections spanning the Cenomanian-Turonian Stage boundary in the western interior of the United States has allowed determination of the magnitude and pattern of molluscan extinction and disruption. Composite range data from all sections show that the faunal turnover across the stage boundary occurs in a series of narrow stratigraphic zones, defined by multiple first and last occurrences, separated by intervals displaying little or no taxonomic turnover. Two of the apparent extinction steps (bottom and top of the Neocardioceras juddii Zone) may be intercontinentally developed. The additional steps apparently reflect cyclic changes in water mass and substrate characteristics in the western interior basin produced in response to orbital forcing of climate. The most affected mollusks were those having intercontinental distributions. -Author

Modelling Participatory Geographic Information System for Customary Land Conflict Resolution

NASA Astrophysics Data System (ADS)

Gyamera, E. A.; Arko-Adjei, A.; Duncan, E. E.; Kuma, J. S. Y.

2017-11-01

Since land contributes to about 73 % of most countries Gross Domestic Product (GDP), attention on land rights have tremendously increased globally. Conflicts over land have therefore become part of the major problems associated with land administration. However, the conventional mechanisms for land conflict resolution do not provide satisfactory result to disputants due to various factors. This study sought to develop a Framework of using Participatory Geographic Information System (PGIS) for customary land conflict resolution. The framework was modelled using Unified Modelling Language (UML). The PGIS framework, called butterfly model, consists of three units namely, Social Unit (SU), Technical Unit (TU) and Decision Making Unit (DMU). The name butterfly model for land conflict resolution was adopted for the framework based on its features and properties. The framework has therefore been recommended to be adopted for land conflict resolution in customary areas.

Rapid screening of drugs of abuse in human urine by high-performance liquid chromatography coupled with high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometry.

PubMed

Li, Xiaowen; Shen, Baohua; Jiang, Zheng; Huang, Yi; Zhuo, Xianyi

2013-08-09

A novel analytical toxicology method has been developed for the analysis of drugs of abuse in human urine by using a high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometer (LTQ-Orbitrap-MS). This method allows for the detection of different drugs of abuse, including amphetamines, cocaine, opiate alkaloids, cannabinoids, hallucinogens and their metabolites. After solid-phase extraction with Oasis HLB cartridges, spiked urine samples were analysed by HPLC/LTQ-Orbitrap-MS using an electrospray interface in positive ionisation mode, with resolving power of 30,000 full width at half maximum (FWHM). Gradient elution off of a Hypersil Gold PFP column (50mm×2.1mm) allowed to resolve 65 target compounds and 3 internal standards in a total chromatographic run time of 20min. Validation of this method consisted of confirmation of identity, selectivity, linearity, limit of detection (LOD), lowest limits of quantification (LLOQ), accuracy, precision, extraction recovery and matrix effect. The regression coefficients (r(2)) for the calibration curves (LLOQ - 100ng/mL) in the study were ≥0.99. The LODs for 65 validated compounds were better than 5ng/ml except for 4 compounds. The relative standard deviation (RSD), which was used to estimate repeatability at three concentrations, was always less than 15%. The recovery of extraction and matrix effects were above 50 and 70%, respectively. Mass accuracy was always better than 2ppm, corresponding to a maximum mass error of 0.8 millimass units (mmu). The accurate masses of characteristic fragments were obtained by collisional experiments for a more reliable identification of the analytes. Automated data analysis and reporting were performed using ToxID software with an exact mass database. This procedure was then successfully applied to analyse drugs of abuse in a real urine sample from subject who was assumed to be drug addict. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Optimizing landslide susceptibility zonation: Effects of DEM spatial resolution and slope unit delineation on logistic regression models

NASA Astrophysics Data System (ADS)

Schlögel, R.; Marchesini, I.; Alvioli, M.; Reichenbach, P.; Rossi, M.; Malet, J.-P.

2018-01-01

We perform landslide susceptibility zonation with slope units using three digital elevation models (DEMs) of varying spatial resolution of the Ubaye Valley (South French Alps). In so doing, we applied a recently developed algorithm automating slope unit delineation, given a number of parameters, in order to optimize simultaneously the partitioning of the terrain and the performance of a logistic regression susceptibility model. The method allowed us to obtain optimal slope units for each available DEM spatial resolution. For each resolution, we studied the susceptibility model performance by analyzing in detail the relevance of the conditioning variables. The analysis is based on landslide morphology data, considering either the whole landslide or only the source area outline as inputs. The procedure allowed us to select the most useful information, in terms of DEM spatial resolution, thematic variables and landslide inventory, in order to obtain the most reliable slope unit-based landslide susceptibility assessment.

The Copernicus Complexio: a high-resolution view of the small-scale Universe

NASA Astrophysics Data System (ADS)

Hellwing, Wojciech A.; Frenk, Carlos S.; Cautun, Marius; Bose, Sownak; Helly, John; Jenkins, Adrian; Sawala, Till; Cytowski, Maciej

2016-04-01

We introduce Copernicus Complexio (COCO), a high-resolution cosmological N-body simulation of structure formation in the ΛCDM model. COCO follows an approximately spherical region of radius ˜17.4 h-1 Mpc embedded in a much larger periodic cube that is followed at lower resolution. The high-resolution volume has a particle mass of 1.135 × 105 h-1 M⊙ (60 times higher than the Millennium-II simulation). COCO gives the dark matter halo mass function over eight orders of magnitude in halo mass; it forms ˜60 haloes of galactic size, each resolved with about 10 million particles. We confirm the power-law character of the subhalo mass function, overline{N}(>μ )∝ μ ^{-s}, down to a reduced subhalo mass Msub/M200 ≡ μ = 10-6, with a best-fitting power-law index, s = 0.94, for hosts of mass = 1012 h-1 M⊙. The concentration-mass relation of COCO haloes deviates from a single power law for masses M200 < afew × 108 h-1 M⊙, where it flattens, in agreement with results by Sanchez-Conde et al. The host mass invariance of the reduced maximum circular velocity function of subhaloes, ν ≡ Vmax/V200, hinted at in previous simulations, is clearly demonstrated over five orders of magnitude in host mass. Similarly, we find that the average, normalized radial distribution of subhaloes is approximately universal (I.e. independent of subhalo mass), as previously suggested by the Aquarius simulations of individual haloes. Finally, we find that at fixed physical subhalo size, subhaloes in lower mass hosts typically have lower central densities than those in higher mass hosts.

Ga + TOF-SIMS lineshape analysis for resolution enhancement of MALDI MS spectra of a peptide mixture

NASA Astrophysics Data System (ADS)

Malyarenko, D. I.; Chen, H.; Wilkerson, A. L.; Tracy, E. R.; Cooke, W. E.; Manos, D. M.; Sasinowski, M.; Semmes, O. J.

2004-06-01

The use of mass spectrometry to obtain molecular profiles indicative of alteration of concentrations of peptides in body fluids is currently the subject of intense investigation. For surface-based time-of-flight mass spectrometry the reliability and specificity of such profiling methods depend both on the resolution of the measuring instrument and on the preparation of samples. The present work is a part of a program to use Ga + beam TOF-SIMS alone, and as an adjunct to MALDI, in the development of reliable protein and peptide markers for diseases. Here, we describe techniques to prepare samples of relatively high-mass peptides, which serve as calibration standards and proxies for biomarkers. These are: Arg8-vasopressin, human angiotensin II, and somatostatin. Their TOF-SIMS spectra show repeatable characteristic features, with mass resolution exceeding 2000, including parent peaks and chemical adducts. The lineshape analysis for high-resolution parent peaks is shown to be useful for filter construction and deconvolution of inferior resolution SELDI-TOF spectra of calibration peptide mixture.

Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry

NASA Astrophysics Data System (ADS)

Moini, Mehdi; Rollman, Christopher M.

2016-03-01

We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry.

PubMed

Ohno, Tsutomu; Ohno, Paul E

2013-04-01

Soil organic matter (SOM) is involved in many important ecosystem processes. Ultrahigh resolution mass spectrometry has become a powerful technique in the chemical characterization of SOM, allowing assignment of elemental formulae for thousands of peaks resolved in a typical mass spectrum. We investigated how the addition of N, S, and P heteroatoms in the formula calculation stage of the mass spectra processing workflow affected the formula assignments of mass spectra peaks. Dissolved organic matter extracted from plant biomass and soil as well as the soil humic acid fraction was studied. We show that the addition of S and P into the molecular formula calculation increased peak assignments on average by 17.3 % and 10.7 %, respectively, over the assignments based on the CHON elements frequently reported by SOM researchers using ultrahigh resolution mass spectrometry. The organic matter chemical characteristics as represented by van Krevelen diagrams were appreciably affected by differences in the heteroatom pre-selection for the three organic matter samples investigated, especially so for the wheat-derived dissolved organic matter. These results show that inclusion of both S and P heteroatoms into the formula calculation step, which is not routinely done, is important to obtain a more chemically complete interpretation of the ultrahigh resolution mass spectra of SOM.

MASH Suite: a user-friendly and versatile software interface for high-resolution mass spectrometry data interpretation and visualization.

PubMed

Guner, Huseyin; Close, Patrick L; Cai, Wenxuan; Zhang, Han; Peng, Ying; Gregorich, Zachery R; Ge, Ying

2014-03-01

The rapid advancements in mass spectrometry (MS) instrumentation, particularly in Fourier transform (FT) MS, have made the acquisition of high-resolution and high-accuracy mass measurements routine. However, the software tools for the interpretation of high-resolution MS data are underdeveloped. Although several algorithms for the automatic processing of high-resolution MS data are available, there is still an urgent need for a user-friendly interface with functions that allow users to visualize and validate the computational output. Therefore, we have developed MASH Suite, a user-friendly and versatile software interface for processing high-resolution MS data. MASH Suite contains a wide range of features that allow users to easily navigate through data analysis, visualize complex high-resolution MS data, and manually validate automatically processed results. Furthermore, it provides easy, fast, and reliable interpretation of top-down, middle-down, and bottom-up MS data. MASH Suite is convenient, easily operated, and freely available. It can greatly facilitate the comprehensive interpretation and validation of high-resolution MS data with high accuracy and reliability.

High-resolution mass spectrometry of skin mucus for monitoring physiological impacts and contaminant biotransformation products in fathead minnows exposed to wastewater effluent.

PubMed

Mosley, Jonathan D; Ekman, Drew R; Cavallin, Jenna E; Villeneuve, Daniel L; Ankley, Gerald T; Collette, Timothy W

2018-03-01

High-resolution mass spectrometry is advantageous for monitoring physiological impacts and contaminant biotransformation products in fish exposed to complex wastewater effluent. We evaluated this technique using skin mucus from male and female fathead minnows (Pimephales promelas) exposed to control water or treated wastewater effluent at 5, 20, and 100% levels for 21 d, using an on-site, flow-through system providing real-time exposure. Both sex-specific and non-sex-specific responses were observed in the mucus metabolome, the latter suggesting the induction of general compensatory pathways for xenobiotic exposures. Altogether, 85 statistically significant treatment-dependent metabolite changes were observed out of the 310 total endogenous metabolites that were detected (156 of the 310 were annotated). Partial least squares-regression models revealed strong covariances between the mucus metabolomes and up-regulated hepatic messenger ribonucleic acid (mRNA) transcripts reported previously for these same fish. These regression models suggest that mucus metabolomic changes reflected, in part, processes by which the fish biotransformed xenobiotics in the effluent. In keeping with this observation, we detected a phase II transformation product of bisphenol A in the skin mucus of male fish. Collectively, these findings demonstrate the utility of mucus as a minimally invasive matrix for simultaneously assessing exposures and effects of environmentally relevant mixtures of contaminants. Environ Toxicol Chem 2018;37:788-796. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Directional Sensitivity in Light-Mass Dark Matter Searches with Single-Electron-Resolution Ionization Detectors

NASA Astrophysics Data System (ADS)

Kadribasic, Fedja; Mirabolfathi, Nader; Nordlund, Kai; Sand, Andrea E.; Holmström, Eero; Djurabekova, Flyura

2018-03-01

We propose a method using solid state detectors with directional sensitivity to dark matter interactions to detect low-mass weakly interacting massive particles (WIMPs) originating from galactic sources. In spite of a large body of literature for high-mass WIMP detectors with directional sensitivity, no available technique exists to cover WIMPs in the mass range <1 GeV /c2 . We argue that single-electron-resolution semiconductor detectors allow for directional sensitivity once properly calibrated. We examine the commonly used semiconductor material response to these low-mass WIMP interactions.

Plasma transport in an Eulerian AMR code

DOE PAGES

Vold, E. L.; Rauenzahn, R. M.; Aldrich, C. H.; ...

2017-04-04

A plasma transport model has been implemented in an Eulerian AMR radiation-hydrodynamics code, xRage, which includes plasma viscosity in the momentum tensor, viscous dissipation in the energy equations, and binary species mixing with consistent species mass and energy fluxes driven by concentration gradients, ion and electron baro-diffusion terms and temperature gradient forces. The physics basis, computational issues, numeric options, and results from several test problems are discussed. The transport coefficients are found to be relatively insensitive to the kinetic correction factors when the concentrations are expressed with the molar fractions and the ion mass differences are large. The contributions tomore » flow dynamics from plasma viscosity and mass diffusion were found to increase significantly as scale lengths decrease in an inertial confinement fusion relevant Kelvin-Helmholtz instability mix layer. The mixing scale lengths in the test case are on the order of 100 μm and smaller for viscous effects to appear and 10 μm or less for significant ion species diffusion, evident over durations on the order of nanoseconds. The temperature gradient driven mass flux is seen to deplete a high Z tracer ion at the ion shock front. The plasma transport model provides the generation of the atomic mix per unit of interfacial area between two species with no free parameters. The evolution of the total atomic mix then depends also on an accurate resolution or estimate of the interfacial area between the species mixing by plasma transport. High resolution simulations or a more Lagrangian-like treatment of species interfaces may be required to distinguish plasma transport and numerical diffusion in an Eulerian computation of complex and dynamically evolving mix regions.« less

Plasma transport in an Eulerian AMR code

NASA Astrophysics Data System (ADS)

Vold, E. L.; Rauenzahn, R. M.; Aldrich, C. H.; Molvig, K.; Simakov, A. N.; Haines, B. M.

2017-04-01

A plasma transport model has been implemented in an Eulerian AMR radiation-hydrodynamics code, xRage, which includes plasma viscosity in the momentum tensor, viscous dissipation in the energy equations, and binary species mixing with consistent species mass and energy fluxes driven by concentration gradients, ion and electron baro-diffusion terms and temperature gradient forces. The physics basis, computational issues, numeric options, and results from several test problems are discussed. The transport coefficients are found to be relatively insensitive to the kinetic correction factors when the concentrations are expressed with the molar fractions and the ion mass differences are large. The contributions to flow dynamics from plasma viscosity and mass diffusion were found to increase significantly as scale lengths decrease in an inertial confinement fusion relevant Kelvin-Helmholtz instability mix layer. The mixing scale lengths in the test case are on the order of 100 μm and smaller for viscous effects to appear and 10 μm or less for significant ion species diffusion, evident over durations on the order of nanoseconds. The temperature gradient driven mass flux is seen to deplete a high Z tracer ion at the ion shock front. The plasma transport model provides the generation of the atomic mix per unit of interfacial area between two species with no free parameters. The evolution of the total atomic mix then depends also on an accurate resolution or estimate of the interfacial area between the species mixing by plasma transport. High resolution simulations or a more Lagrangian-like treatment of species interfaces may be required to distinguish plasma transport and numerical diffusion in an Eulerian computation of complex and dynamically evolving mix regions.

The NEAR laser ranging investigation

NASA Astrophysics Data System (ADS)

Zuber, M. T.; Smith, D. E.; Cheng, A. F.; Cole, T. D.

1997-10-01

The objective of the NEAR-Earth Asteriod Rendezvous (NEAR) laser ranging investigation is to obtain high integrity profiles and grids of topography for use in geophysical, geodetic and geological studies of asteroid 433 Eros. The NEAR laser rangefinder (NLR) will determine the slant range of the NEAR spacecraft to the asteroid surface by measuring precisely the round trip time of flight of individual laser pulses. Ranges will be converted to planetary radii measured with respect to the asteroid center of mass by subtracting the spacecraft orbit determined from X band Doppler tracking. The principal components of the NLR include a 1064 nm Cr:Nd:YAG laser, a gold-coated aluminum Dall-Kirkham Cassegrain telescope, an enhanced silicon avalanche photodiode hybrid detector, a 480-MHz crystal oscillator, and a digital processing unit. The instrument has a continuous in-flight calibration capability using a fiber-optic delay assembly. The single shot vertical resolution of the NLR is <6m, and the absolute accuracy of the global grid will be ~10m with respect to the asteroid center of mass. For the current mission orbital scenario, the laser spot size on the surface of Eros will vary from ~4-11m, and the along-track resolution for the nominal pulse repetition rate of 1 Hz will be approximately comparable to the spot size, resulting in contiguous along-track profiles. The across-track resolution will depend on the orbital mapping scenario, but will likely be <500m, which will define the spatial resolution of the global topographic model. Planned science investigations include global-scale analyses related to collisional and impact history and internal density distribution that utilize topographic grids as well as spherical harmonic topographic models that will be analyzed jointly with gravity at commensurate resolution. Attempts will be made to detect possible subtle time variations in internal structure that may be present if Eros is not a single coherent body, by analysis of low degree and order spherical harmonic coefficients. Local- to regional-scale analyses will utilize high-resolution three-dimensional topographic maps of specific surface structures to address surface geologic processes. Results from the NLR investigation will contribute significantly to understanding the origin, structure, and evolution of Eros and other asteroidal bodies.

Active x-ray optics for Generation-X, the next high resolution x-ray observatory

NASA Astrophysics Data System (ADS)

Elvis, Martin; Brissenden, R. J.; Fabbiano, G.; Schwartz, D. A.; Reid, P.; Podgorski, W.; Eisenhower, M.; Juda, M.; Phillips, J.; Cohen, L.; Wolk, S.

2006-06-01

X-rays provide one of the few bands through which we can study the epoch of reionization, when the first galaxies, black holes and stars were born. To reach the sensitivity required to image these first discrete objects in the universe needs a major advance in X-ray optics. Generation-X (Gen-X) is currently the only X-ray astronomy mission concept that addresses this goal. Gen-X aims to improve substantially on the Chandra angular resolution and to do so with substantially larger effective area. These two goals can only be met if a mirror technology can be developed that yields high angular resolution at much lower mass/unit area than the Chandra optics, matching that of Constellation-X (Con-X). We describe an approach to this goal based on active X-ray optics that correct the mid-frequency departures from an ideal Wolter optic on-orbit. We concentrate on the problems of sensing figure errors, calculating the corrections required, and applying those corrections. The time needed to make this in-flight calibration is reasonable. A laboratory version of these optics has already been developed by others and is successfully operating at synchrotron light sources. With only a moderate investment in these optics the goals of Gen-X resolution can be realized.

Strategy for the elucidation of elemental compositions of trace analytes based on a mass resolution of 100,000 full width at half maximum.

PubMed

Kaufmann, Anton

2010-07-30

Elemental compositions (ECs) can be elucidated by evaluating the high-resolution mass spectra of unknown or suspected unfragmented analyte ions. Classical approaches utilize the exact mass of the monoisotopic peak (M + 0) and the relative abundance of isotope peaks (M + 1 and M + 2). The availability of high-resolution instruments like the Orbitrap currently permits mass resolutions up to 100,000 full width at half maximum. This not only allows the determination of relative isotopic abundances (RIAs), but also the extraction of other diagnostic information from the spectra, such as fully resolved signals originating from (34)S isotopes and fully or partially resolved signals related to (15)N isotopes (isotopic fine structure). Fully and partially resolved peaks can be evaluated by visual inspection of the measured peak profiles. This approach is shown to be capable of correctly discarding many of the EC candidates which were proposed by commercial EC calculating algorithms. Using this intuitive strategy significantly extends the upper mass range for the successful elucidation of ECs. Copyright 2010 John Wiley & Sons, Ltd.

High-resolution endoscopic ultrasound imaging and the number of needle passages are significant factors predicting high yield of endoscopic ultrasound-guided fine needle aspiration for pancreatic solid masses without an on-site cytopathologist

PubMed Central

Jeong, Seok Hoo; Yoon, Hyun Hwa; Kim, Eui Joo; Kim, Yoon Jae; Kim, Yeon Suk; Cho, Jae Hee

2017-01-01

Abstract Endoscopic ultrasound-guided fine needle aspiration (EUS-FNA) is the accurate diagnostic method for pancreatic masses and its accuracy is affected by various FNA methods and EUS equipment. Therefore, we aimed to elucidate the instrumental and methodologic factors for determining the diagnostic yield of EUS-FNA for pancreatic solid masses without an on-site cytopathology evaluation. We retrospectively reviewed the medical records of 260 patients (265 pancreatic solid masses) who underwent EUS-FNA. We compared historical conventional EUS groups with high-resolution imaging devices and finally analyzed various factors affecting EUS-FNA accuracy. In total, 265 pancreatic solid masses of 260 patients were included in this study. The accuracy, sensitivity, specificity, positive predictive value, and negative predictive value of EUS-FNA for pancreatic solid masses without on-site cytopathology evaluation were 83.4%, 81.8%, 100.0%, 100.0%, and 34.3%, respectively. In comparison with conventional image group, high-resolution image group showed the increased accuracy, sensitivity and specificity of EUS-FNA (71.3% vs 92.7%, 68.9% vs 91.9%, and 100% vs 100%, respectively). On the multivariate analysis with various instrumental and methodologic factors, high-resolution imaging (P = 0.040, odds ratio = 3.28) and 3 or more needle passes (P = 0.039, odds ratio = 2.41) were important factors affecting diagnostic yield of pancreatic solid masses. High-resolution imaging and 3 or more passes were the most significant factors influencing diagnostic yield of EUS-FNA in patients with pancreatic solid masses without an on-site cytopathologist. PMID:28079803

Critical comparison of mass analyzers for forensic hair analysis by ambient ionization mass spectrometry.

PubMed

Duvivier, Wilco F; van Beek, Teris A; Nielen, Michel W F

2016-11-15

Recently, several direct and/or ambient mass spectrometry (MS) approaches have been suggested for drugs of abuse imaging in hair. The use of mass spectrometers with insufficient selectivity could result in false-positive measurements due to isobaric interferences. Different mass analyzers have been evaluated regarding their selectivity and sensitivity for the detection of Δ9-tetrahydrocannabinol (THC) from intact hair samples using direct analysis in real time (DART) ionization. Four different mass analyzers, namely (1) an orbitrap, (2) a quadrupole orbitrap, (3) a triple quadrupole, and (4) a quadrupole time-of-flight (QTOF), were evaluated. Selectivity and sensitivity were assessed by analyzing secondary THC standard dilutions on stainless steel mesh screens and blank hair samples, and by the analysis of authentic cannabis user hair samples. Additionally, separation of isobaric ions by use of travelling wave ion mobility (TWIM) was investigated. The use of a triple quadrupole instrument resulted in the highest sensitivity; however, transitions used for multiple reaction monitoring were only found to be specific when using high mass resolution product ion measurements. A mass resolution of at least 30,000 FWHM at m/z 315 was necessary to avoid overlap of THC with isobaric ions originating from the hair matrix. Even though selectivity was enhanced by use of TWIM, the QTOF instrument in resolution mode could not indisputably differentiate THC from endogenous isobaric ions in drug user hair samples. Only the high resolution of the (quadrupole) orbitrap instruments and the QTOF instrument in high-resolution mode distinguished THC in hair samples from endogenous isobaric interferences. As expected, enhanced selectivity compromises sensitivity and THC was only detectable in hair from heavy users. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Atmospheric Photooxidation Products and Chemistry of Current-use Pesticides

NASA Astrophysics Data System (ADS)

Murschell, T.; Farmer, D.

2017-12-01

Pesticides are widely used in agricultural, commercial, and residential applications across the United States. Pesticides can volatilize off targets and travel long distances, with atmospheric lifetimes determined by both physical and chemical loss processes. In particular, oxidation by the hydroxyl radical (OH) can reduce the lifetime and thus atmospheric transport of pesticides, though the rates and oxidation products of atmospheric pesticide oxidation are poorly understood. Here, we investigate reactions of current-use pesticides with OH. MCPA, triclopyr, and fluroxypyr are herbicides that are often formulated together to target broadleaf weeds. We detect these species in the gas-phase using real-time high resolution chemical ionization mass spectrometry (CIMS) with both acetate and iodide reagent ions. We used an Oxidative Flow Reactor to explore OH radical oxidation and photolysis of these compounds, simulating up to 5 equivalent days of atmospheric aging by OH. Use of two ionization schemes allowed for the more complete representation of the OH radical oxidation of the three pesticides. The high resolution mass spectra allows us to deduce structures of the oxidation products and identify multi-generational chemistry. In addition, we observe nitrogen oxides, as well as isocyanic acid (HNCO), from some nitrogen-containing pesticides. We present yields of species of atmospheric importance, including NOx and halogen species and consider their impact on air quality following pesticide application.

Star formation and gas inflows in the OH Megamaser galaxy IRAS03056+2034

NASA Astrophysics Data System (ADS)

Hekatelyne, C.; Riffel, Rogemar A.; Sales, Dinalva; Robinson, Andrew; Storchi-Bergmann, Thaisa; Kharb, Preeti; Gallimore, Jack; Baum, Stefi; O'Dea, Christopher

2018-06-01

We have obtained observations of the OH Megamaser galaxy IRAS03056+0234 using Gemini Multi-Object Spectrograph (GMOS) Integral Field Unit (IFU), Very Large Array (VLA) and Hubble Space Telescope (HST). The HST data reveals spiral arms containing knots of emission associated to star forming regions. The GMOS-IFU data cover the spectral range of 4500 to 7500 Å at a velocity resolution of 90 km s-1 and spatial resolution of 506 pc. The emission-line flux distributions reveal a ring of star forming regions with radius of 786 pc centred at the nucleus of the galaxy, with an ionized gas mass of 1.2× 108M⊙, an ionizing photon luminosity of log Q[H+]=53.8 and a star formation rate of 4.9 M⊙ yr-1. The emission-line ratios and radio emission suggest that the gas at the nuclear region is excited by both starburst activity and an active galactic nucleus. The gas velocity fields are partially reproduced by rotation in the galactic plane, but show, in addition, excess redshifts to the east of the nucleus, consistent with gas inflows towards the nucleus, with velocity of ˜45 km s-1 and a mass inflow rate of ˜7.7 × 10-3 M⊙ yr-1.

Menstruation disorders in adolescents with eating disorders-target body mass index percentiles for their resolution.

PubMed

Vale, Beatriz; Brito, Sara; Paulos, Lígia; Moleiro, Pascoal

2014-04-01

To analyse the progression of body mass index in eating disorders and to determine the percentile for establishment and resolution of the disease. A retrospective descriptive cross-sectional study. Review of clinical files of adolescents with eating disorders. Of the 62 female adolescents studied with eating disorders, 51 presented with eating disorder not otherwise specified, 10 anorexia nervosa, and 1 bulimia nervosa. Twenty-one of these adolescents had menstrual disorders; in that, 14 secondary amenorrhea and 7 menstrual irregularities (6 eating disorder not otherwise specified, and 1 bulimia nervosa). In average, in anorectic adolescents, the initial body mass index was in 75th percentile; secondary amenorrhea was established 1 month after onset of the disease; minimum weight was 76.6% of ideal body mass index (at 4th percentile) at 10.2 months of disease; and resolution of amenorrhea occurred at 24 months, with average weight recovery of 93.4% of the ideal. In eating disorder not otherwise specified with menstrual disorder (n=10), the mean initial body mass index was at 85th percentile; minimal weight was in average 97.7% of the ideal value (minimum body mass index was in 52nd percentile) at 14.9 months of disease; body mass index stabilization occurred at 1.6 year of disease; and mean body mass index was in 73rd percentile. Considering eating disorder not otherwise specified with secondary amenorrhea (n=4); secondary amenorrhea occurred at 4 months, with resolution at 12 months of disease (mean 65th percentile body mass index). One-third of the eating disorder group had menstrual disorder - two-thirds presented with amenorrhea. This study indicated that for the resolution of their menstrual disturbance the body mass index percentiles to be achieved by female adolescents with eating disorders was 25-50 in anorexia nervosa, and 50-75, in eating disorder not otherwise specified.

77 FR 24766 - Call for Proposals for a Micro Support Program on International Conflict Resolution and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-25

... UNITED STATES INSTITUTE OF PEACE Call for Proposals for a Micro Support Program on International Conflict Resolution and Peacebuilding For Immediate Release AGENCY: United States Institute of Peace. ACTION: Notice. SUMMARY: Micro Support Program on International Conflict Resolution and Peacebuilding...

31 CFR 560.510 - Transactions related to the resolution of disputes between the United States or United States...

Code of Federal Regulations, 2011 CFR

2011-07-01

... of disputes between the United States or United States nationals and the Government of Iran. 560.510 Section 560.510 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE..., Authorizations and Statements of Licensing Policy § 560.510 Transactions related to the resolution of disputes...

Mascons, GRACE, and Time-variable Gravity

NASA Technical Reports Server (NTRS)

Lemoine, F.; Lutchke, S.; Rowlands, D.; Klosko, S.; Chinn, D.; Boy, J. P.

2006-01-01

The GRACE mission has been in orbit now for three years and now regularly produces snapshots of the Earth s gravity field on a monthly basis. The convenient standard approach has been to perform global solutions in spherical harmonics. Alternative local representations of mass variations using mascons show great promise and offer advantages in terms of computational efficiency, minimization of problems due to aliasing, and increased temporal resolution. In this paper, we discuss the results of processing the GRACE KBRR data from March 2003 through August 2005 to produce solutions for GRACE mass variations over mid-latitude and equatorial regions, such as South America, India and the United States, and over the polar regions (Antarctica and Greenland), with a focus on the methodology. We describe in particular mascon solutions developed on regular 4 degree x 4 degree grids, and those tailored specifically to drainage basins over these regions.

A Giant Planet Around a Metal-Poor Star of Extragalactic Origin

NASA Astrophysics Data System (ADS)

Setiawan, Johny; Klement, Rainer J.; Henning, Thomas; Rix, Hans-Walter; Rochau, Boyke; Rodmann, Jens; Schulze-Hartung, Tim

2010-12-01

Stars in their late stage of evolution, such as horizontal branch stars, are still largely unexplored for planets. We detected a planetary companion around HIP 13044, a very metal-poor star on the red horizontal branch, on the basis of radial velocity observations with a high-resolution spectrograph at the 2.2-meter Max-Planck Gesellschaft-European Southern Observatory telescope. The star’s periodic radial velocity variation of P = 16.2 days caused by the planet can be distinguished from the periods of the stellar activity indicators. The minimum mass of the planet is 1.25 times the mass of Jupiter and its orbital semimajor axis is 0.116 astronomical units. Because HIP 13044 belongs to a group of stars that have been accreted from a disrupted satellite galaxy of the Milky Way, the planet most likely has an extragalactic origin.

Webinar Presentation: Suspect Screening of Environmental Organic Acids in Human Serum Using High-resolution Mass Spectrometry (HRMS)

EPA Pesticide Factsheets

This presentation, Suspect Screening of Environmental Organic Acids in Human Serum Using High-resolution Mass Spectrometry (HRMS), was given at the NIEHS/EPA Children's Centers 2016 Webinar Series: Exposome held on May 11, 2016.

IDENTIFICATION OF NEW OZONE DISINFECTION BY PRODUCTS IN DRINKING WATER

EPA Science Inventory

Using a combination of spectral identification techniques-gas chromatography coupled with low- and high-resolution electron-impact mass spectrometry (GC/EI-MS), low- and high-resolution chemical ionization mass spectrometry (GC/CI-MS), and infrared spectroscopy (GC/ IR)-we identi...

APPLICATION OF MULTISPECTRAL TECHNIQUES TO THE PRECISE IDENTIFICATION OF ALDEHYDES IN THE ENVIRONMENT

EPA Science Inventory

By using gas chromatography coupled with low- and high-resolution electron impact mass spectrometry, low- and high-resolution chemical ionization mass spectrometry, and Fourier transform infrared spectroscopy, eight straight-chain aldehydes were identified in a water sample taken...

Structural Analysis of Titan's Tholins by Ultra-High Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Vuitton, V.; Frisari, M.; Thissen, R.; Dutuit, O.; Bonnet, J.-Y.; Quirico, E.; Sciamma O'Brien, E.; Szopa, C.; Carrasco, N.; Somogyi, A.; Smith, M.; Hörst, S. M.; Yelle, R.

2010-04-01

We propose here a systematic ultra-high resolution mass spectrometry and MS/MS study in order to provide a more coherent and complete characterization of the structure of the molecules making up the soluble fraction of the Titan tholins.

Conflict Resolution Unit.

ERIC Educational Resources Information Center

Busselle, Tish

This 7-day unit, intended for use with secondary students, contains a statement of rationale and objectives, lesson plans, class assignments, teacher and student bibliographies, and suggestions for instructional materials on conflict resolution between individuals, groups, and nations. Among the six objectives listed for the unit are: 1) explain…

Final LDRD report : development of sample preparation methods for ChIPMA-based imaging mass spectrometry of tissue samples.

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

Maharrey, Sean P.; Highley, Aaron M.; Behrens, Richard, Jr.

2007-12-01

The objective of this short-term LDRD project was to acquire the tools needed to use our chemical imaging precision mass analyzer (ChIPMA) instrument to analyze tissue samples. This effort was an outgrowth of discussions with oncologists on the need to find the cellular origin of signals in mass spectra of serum samples, which provide biomarkers for ovarian cancer. The ultimate goal would be to collect chemical images of biopsy samples allowing the chemical images of diseased and nondiseased sections of a sample to be compared. The equipment needed to prepare tissue samples have been acquired and built. This equipment includesmore » an cyro-ultramicrotome for preparing thin sections of samples and a coating unit. The coating unit uses an electrospray system to deposit small droplets of a UV-photo absorbing compound on the surface of the tissue samples. Both units are operational. The tissue sample must be coated with the organic compound to enable matrix assisted laser desorption/ionization (MALDI) and matrix enhanced secondary ion mass spectrometry (ME-SIMS) measurements with the ChIPMA instrument Initial plans to test the sample preparation using human tissue samples required development of administrative procedures beyond the scope of this LDRD. Hence, it was decided to make two types of measurements: (1) Testing the spatial resolution of ME-SIMS by preparing a substrate coated with a mixture of an organic matrix and a bio standard and etching a defined pattern in the coating using a liquid metal ion beam, and (2) preparing and imaging C. elegans worms. Difficulties arose in sectioning the C. elegans for analysis and funds and time to overcome these difficulties were not available in this project. The facilities are now available for preparing biological samples for analysis with the ChIPMA instrument. Some further investment of time and resources in sample preparation should make this a useful tool for chemical imaging applications.« less

Calculating distributed glacier mass balance for the Swiss Alps from RCM output: Development and testing of downscaling and validation methods

NASA Astrophysics Data System (ADS)

Machguth, H.; Paul, F.; Kotlarski, S.; Hoelzle, M.

2009-04-01

Climate model output has been applied in several studies on glacier mass balance calculation. Hereby, computation of mass balance has mostly been performed at the native resolution of the climate model output or data from individual cells were selected and statistically downscaled. Little attention has been given to the issue of downscaling entire fields of climate model output to a resolution fine enough to compute glacier mass balance in rugged high-mountain terrain. In this study we explore the use of gridded output from a regional climate model (RCM) to drive a distributed mass balance model for the perimeter of the Swiss Alps and the time frame 1979-2003. Our focus lies on the development and testing of downscaling and validation methods. The mass balance model runs at daily steps and 100 m spatial resolution while the RCM REMO provides daily grids (approx. 18 km resolution) of dynamically downscaled re-analysis data. Interpolation techniques and sub-grid parametrizations are combined to bridge the gap in spatial resolution and to obtain daily input fields of air temperature, global radiation and precipitation. The meteorological input fields are compared to measurements at 14 high-elevation weather stations. Computed mass balances are compared to various sets of direct measurements, including stake readings and mass balances for entire glaciers. The validation procedure is performed separately for annual, winter and summer balances. Time series of mass balances for entire glaciers obtained from the model run agree well with observed time series. On the one hand, summer melt measured at stakes on several glaciers is well reproduced by the model, on the other hand, observed accumulation is either over- or underestimated. It is shown that these shifts are systematic and correlated to regional biases in the meteorological input fields. We conclude that the gap in spatial resolution is not a large drawback, while biases in RCM output are a major limitation to model performance. The development and testing of methods to reduce regionally variable biases in entire fields of RCM output should be a focus of pursuing studies.

Peculiarities of data interpretation upon direct tissue analysis by Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Chagovets, Vtaliy; Kononikhin, Aleksey; Starodubtseva, Nataliia; Kostyukevich, Yury; Popov, Igor; Frankevich, Vladimir; Nikolaev, Eugene

2016-01-01

The importance of high-resolution mass spectrometry for the correct data interpretation of a direct tissue analysis is demonstrated with an example of its clinical application for an endometriosis study. Multivariate analysis of the data discovers lipid species differentially expressed in different tissues under investigation. High-resolution mass spectrometry allows unambiguous separation of peaks with close masses that correspond to proton and sodium adducts of phosphatidylcholines and to phosphatidylcholines differing in double bond number.

Parallel Reaction Monitoring: A Targeted Experiment Performed Using High Resolution and High Mass Accuracy Mass Spectrometry

PubMed Central

Rauniyar, Navin

2015-01-01

The parallel reaction monitoring (PRM) assay has emerged as an alternative method of targeted quantification. The PRM assay is performed in a high resolution and high mass accuracy mode on a mass spectrometer. This review presents the features that make PRM a highly specific and selective method for targeted quantification using quadrupole-Orbitrap hybrid instruments. In addition, this review discusses the label-based and label-free methods of quantification that can be performed with the targeted approach. PMID:26633379

High-resolution matrix-assisted laser desorption ionization–imaging mass spectrometry of lipids in rodent optic nerve tissue

PubMed Central

Anderson, David M. G.; Mills, Daniel; Spraggins, Jeffrey; Lambert, Wendi S.; Calkins, David J.

2013-01-01

Purpose To develop a method for generating high spatial resolution (10 µm) matrix-assisted laser desorption ionization (MALDI) images of lipids in rodent optic nerve tissue. Methods Ice-embedded optic nerve tissue from rats and mice were cryosectioned across the coronal and sagittal axes of the nerve fiber. Sections were thaw mounted on gold-coated MALDI plates and were washed with ammonium acetate to remove biologic salts before being coated in 2,5-dihydroxybenzoic acid by sublimation. MALDI images were generated in positive and negative ion modes at 10 µm spatial resolution. Lipid identification was performed with a high mass resolution Fourier transform ion cyclotron resonance mass spectrometer. Results Several lipid species were observed with high signal intensity in MALDI images of optic nerve tissue. Several lipids were localized to specific structures including in the meninges surrounding the optic nerve and in the central neuronal tissue. Specifically, phosphatidylcholine species were observed throughout the nerve tissue in positive ion mode while sulfatide species were observed in high abundance in the meninges surrounding the optic nerve in negative ion mode. Accurate mass measurements and fragmentation using sustained off-resonance irradiation with a high mass resolution Fourier transform ion cyclotron resonance mass spectrometer instrument allowed for identification of lipid species present in the small structure of the optic nerve directly from tissue sections. Conclusions An optimized sample preparation method provides excellent sensitivity for lipid species present within optic nerve tissue. This allowed the laser spot size and fluence to be reduced to obtain a high spatial resolution of 10 µm. This new imaging modality can now be applied to determine spatial and molecular changes in optic nerve tissue with disease. PMID:23559852

Strategies to avoid false negative findings in residue analysis using liquid chromatography coupled to time-of-flight mass spectrometry.

PubMed

Kaufmann, Anton; Butcher, Patrick

2006-01-01

Liquid chromatography coupled to orthogonal acceleration time-of-flight mass spectrometry (LC/TOF) provides an attractive alternative to liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS) in the field of multiresidue analysis. The sensitivity and selectivity of LC/TOF approach those of LC/MS/MS. TOF provides accurate mass information and a significantly higher mass resolution than quadrupole analyzers. The available mass resolution of commercial TOF instruments ranging from 10 000 to 18 000 full width at half maximum (FWHM) is not, however, sufficient to completely exclude the problem of isobaric interferences (co-elution of analyte ions with matrix compounds of very similar mass). Due to the required data storage capacity, TOF raw data is commonly centroided before being electronically stored. However, centroiding can lead to a loss of data quality. The co-elution of a low intensity analyte peak with an isobaric, high intensity matrix compound can cause problems. Some centroiding algorithms might not be capable of deconvoluting such partially merged signals, leading to incorrect centroids.Co-elution of isobaric compounds has been deliberately simulated by injecting diluted binary mixtures of isobaric model substances at various relative intensities. Depending on the mass differences between the two isobaric compounds and the resolution provided by the TOF instrument, significant deviations in exact mass measurements and signal intensities were observed. The extraction of a reconstructed ion chromatogram based on very narrow mass windows can even result in the complete loss of the analyte signal. Guidelines have been proposed to avoid such problems. The use of sub-2 microm HPLC packing materials is recommended to improve chromatographic resolution and to reduce the risk of co-elution. The width of the extraction mass windows for reconstructed ion chromatograms should be defined according to the resolution of the TOF instrument. Alternative approaches include the spiking of the sample with appropriate analyte concentrations. Furthermore, enhanced software, capable of deconvoluting partially merged mass peaks, may become available. Copyright (c) 2006 John Wiley & Sons, Ltd.

Young massive star clusters in the era of HST and integral field spectroscopy

NASA Astrophysics Data System (ADS)

Zeidler, Peter; Nota, Antonella; Sabbi, Elena; Grebel, Eva K.; Pasquali, Anna

2018-01-01

With an age of 1 – 2 Myr at a distance of 4 kpc and a total stellar mass of 3.7×104 M⊙, Westerlund 2 (Wd2) is one of the most massive young star clusters in the Milky Way. We present a detailed analysis of its prominent pre-main-sequence population using the data of a high-resolution multi-band survey in the optical and near-infrared with the Hubble Space Telescope (HST), in combination with our spectroscopic survey, observed with the VLT/MUSE integral field unit. With our derived high-resolution extinction map of the region, which is absolutely essential giving the dominating presences of the gas and dust, we derived the spatial dependence of the mass function and quantify the degree of mass segregation down to 0.65 M⊙ with a completeness level better than 50%. Studying the radial dependence of the mass function of Wd2 and quantifying the degree of mass segregation in this young massive star cluster showed that it consists of two sub-clumps, namely the main cluster and the northern clump. From the MUSE data, we can extract individual stellar spectra and spectral energy distributions of the stars, based on the astrometry, provided by our high-resolution HST photometric catalog. This data will provide us with an almost complete spectral classification of a young massive star cluster down to 1.0 M⊙. The combination of the MUSE data, together with 3 more years of approved HST data will allow us to obtain, for the first time, the 3D motions of the stars with an accuracy of 1-2 km s-2 to determine the stellar velocity dispersion in order to study the fate of Wd2. This information is of great importance to adjust the initial conditions in cluster evolution models in order to connect these young massive star clusters and the old globular cluster population. Additionally, the combination of the photometric and spectroscopic datasets allows us to study the stars and their feedback onto the surrounding HII region simultaneously, as well as peculiar objects such as the massive, eclipsing Wolf-Rayet binary, WR20a or a possible Herbig-Haro object in the northern clump.

Ultrahigh-resolution FT-ICR mass spectrometry characterization of a-pinene ozonolysis SOA

EPA Science Inventory

Secondary organic aerosol (SOA) of α-pinene ozonolysis with and without hydroxyl radical scavenging hexane was characterized by ultrahigh-resolution. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Molecular formulas for more than 900 negative ions were i...

High Resolution Laser Mass Spectrometry Bioimaging

PubMed Central

Murray, Kermit K.; Seneviratne, Chinthaka A.; Ghorai, Suman

2016-01-01

MSI (MSI) was introduced more than five decades ago with secondary ion mass spectrometry (SIMS) and a decade later with laser desorption/ionization (LDI) mass spectrometry (MS). Large biomolecule imaging by matrix-assisted laser desorption/ionization (MALDI) was developed in the 1990s and ambient laser MS a decade ago. Although SIMS has been capable of imaging with a moderate mass range at sub-micrometer lateral resolution from its inception, laser MS requires additional effort to achieve a lateral resolution of 10 μm or below which is required to image at the size scale of single mammalian cells. This review covers untargeted large biomolecule MSI using lasers for desorption/ionization or laser desorption and post-ionization. These methods include laser microprobe (LDI) MSI, MALDI MSI, laser ambient and atmospheric pressure MSI, and near-field laser ablation MS. Novel approaches to improving lateral resolution are discussed, including oversampling, beam shaping, transmission geometry, reflective and through-hole objectives, microscope mode, and near-field optics. PMID:26972785

Triple Quadrupole Versus High Resolution Quadrupole-Time-of-Flight Mass Spectrometry for Quantitative LC-MS/MS Analysis of 25-Hydroxyvitamin D in Human Serum

NASA Astrophysics Data System (ADS)

Geib, Timon; Sleno, Lekha; Hall, Rabea A.; Stokes, Caroline S.; Volmer, Dietrich A.

2016-08-01

We describe a systematic comparison of high and low resolution LC-MS/MS assays for quantification of 25-hydroxyvitamin D3 in human serum. Identical sample preparation, chromatography separations, electrospray ionization sources, precursor ion selection, and ion activation were used; the two assays differed only in the implemented final mass analyzer stage; viz. high resolution quadrupole-quadrupole-time-of-flight (QqTOF) versus low resolution triple quadrupole instruments. The results were assessed against measured concentration levels from a routine clinical chemiluminescence immunoassay. Isobaric interferences prevented the simple use of TOF-MS spectra for extraction of accurate masses and necessitated the application of collision-induced dissociation on the QqTOF platform. The two mass spectrometry assays provided very similar analytical figures of merit, reflecting the lack of relevant isobaric interferences in the MS/MS domain, and were successfully applied to determine the levels of 25-hydroxyvitamin D for patients with chronic liver disease.

Mass-transfer limitations for immobilized enzyme-catalyzed kinetic resolution of racemate in a fixed-bed reactor.

PubMed

Xiu, G H; Jiang, L; Li, P

2001-07-05

A mathematical model has been developed for immobilized enzyme-catalyzed kinetic resolution of racemate in a fixed-bed reactor in which the enzyme-catalyzed reaction (the irreversible uni-uni competitive Michaelis-Menten kinetics is chosen as an example) was coupled with intraparticle diffusion, external mass transfer, and axial dispersion. The effects of mass-transfer limitations, competitive inhibition of substrates, deactivation on the enzyme effective enantioselectivity, and the optical purity and yield of the desired product are examined quantitatively over a wide range of parameters using the orthogonal collocation method. For a first-order reaction, an analytical solution is derived from the mathematical model for slab-, cylindrical-, and spherical-enzyme supports. Based on the analytical solution for the steady-state resolution process, a new concise formulation is presented to predict quantitatively the mass-transfer limitations on enzyme effective enantioselectivity and optical purity and yield of the desired product for a continuous steady-state kinetic resolution process in a fixed-bed reactor. Copyright 2001 John Wiley & Sons, Inc.

AP-MALDI Mass Spectrometry Imaging of Gangliosides Using 2,6-Dihydroxyacetophenone

NASA Astrophysics Data System (ADS)

Jackson, Shelley N.; Muller, Ludovic; Roux, Aurelie; Oktem, Berk; Moskovets, Eugene; Doroshenko, Vladimir M.; Woods, Amina S.

2018-03-01

Matrix-assisted laser/desorption ionization (MALDI) mass spectrometry imaging (MSI) is widely used as a unique tool to record the distribution of a large range of biomolecules in tissues. 2,6-Dihydroxyacetophenone (DHA) matrix has been shown to provide efficient ionization of lipids, especially gangliosides. The major drawback for DHA as it applies to MS imaging is that it sublimes under vacuum (low pressure) at the extended time necessary to complete both high spatial and mass resolution MSI studies of whole organs. To overcome the problem of sublimation, we used an atmospheric pressure (AP)-MALDI source to obtain high spatial resolution images of lipids in the brain using a high mass resolution mass spectrometer. Additionally, the advantages of atmospheric pressure and DHA for imaging gangliosides are highlighted. The imaging of [M-H]- and [M-H2O-H]- mass peaks for GD1 gangliosides showed different distribution, most likely reflecting the different spatial distribution of GD1a and GD1b species in the brain. [Figure not available: see fulltext.

Design, fabrication and space suitability tests of wide field of view, ultra-compact, and high resolution telescope for space application.

PubMed

Tumarina, M; Ryazanskiy, M; Jeong, S; Hong, G; Vedenkin, N; Park, I H; Milov, A

2018-02-05

We report on the design, manufacture, and testing of an ultra-compact telescope for 16 unit (16U) CubeSats for Earth and space observation. This telescope provides 1 arcsec resolution at a 2.9 degree field of view. Dimensions are optimized to 230 × 230 × 330mm 3 with a mass of less than 6kg including support structure. Our catadioptric 5-element design consists of a full-aperture corrector, a Mangin primary mirror (PM), a secondary mirror (SM), and a 2-lens field corrector. The focal length is 745mm, and squared-circular aperture has an equivalent diameter of 241mm. The designed modulation transfer function (MTF) is 0.275 for the entire unit including baffles at a Nyquist frequency of 161 cycles/mm for the 450-800nm band. As one of the distinguishing features of our state-of-the-art design, all optical surfaces are spherical to simplify adjustment. For the best thermal stability, all optical elements are produced from fused silica. We describe the details of design, adjustment, and laboratory performance tests for space environments in accordance with the requirements for in-orbit operation onboard Earth-observation micro-satellites to be launched in 2018.

Identification of volatile and semivolatile compounds in chemical ionization GC-MS using a mass-to-structure (MTS) Search Engine with integral isotope pattern ranking.

PubMed

Liao, Wenta; Draper, William M

2013-02-21

The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of <4% and <6%, respectively, for A + 1 and A + 2 peaks. Deconvolution of interfering isotope clusters (e.g., M(+) and [M - H](+)) was required for accurate determination of the A + 1 isotope in halogenated compounds. Integrating the isotope data greatly improved the speed and accuracy of the database identifications. The database accurately identified unknowns from isobutane CI spectra in 100% of cases where as many as 40 candidates satisfied the mass tolerance. The paper describes the development and basic operation of the new MTS Search Engine and details performance testing with over 50 model compounds.

Toward a Micro Gas Chromatograph/Mass Spectrometer (GC/MS) System

NASA Technical Reports Server (NTRS)

Wiberg, D. V.; Eyre, F. B.; Orient, O.; Chutjian, A.; Garkarian, V.

2001-01-01

Miniature mass filters (e.g., quadrupoles, ion traps) have been the subject of several miniaturization efforts. A project is currently in progress at JPL to develop a miniaturized Gas Chromatograph/Mass Spectrometer (GC/MS) system, incorporating and/or developing miniature system components including turbomolecular pumps, scroll type roughing pump, quadrupole mass filter, gas chromatograph, precision power supply and other electronic components. The preponderance of the system elements will be fabricated using microelectromechanical systems (MEMS) techniques. The quadrupole mass filter will be fabricated using an X-ray lithography technique producing high precision, 5x5 arrays of quadrupoles with pole lengths of about 3 mm and a total volume of 27 cubic mm. The miniature scroll pump will also be fabricated using X-ray lithography producing arrays of scroll stages about 3 mm in diameter. The target detection range for the mass spectrometer is 1 to 300 atomic mass units (AMU) with are solution of 0.5 AMU. This resolution will allow isotopic characterization for geochronology, atmospheric studies and other science efforts dependant on the understanding of isotope ratios of chemical species. This paper will discuss the design approach, the current state-of-the art regarding the system components and the progress toward development of key elements. The full system is anticipated to be small enough in mass, volume and power consumption to allow in situ chemical analysis on highly miniaturized science craft for geochronology, atmospheric characterization and detection of life experiments applicable to outer planet roadmap missions.

Solar abundances as derived from solar energetic particles

NASA Technical Reports Server (NTRS)

Stone, E. C.

1989-01-01

Recent studies have shown that there are well defined average abundances of heavy (Z above 2) solar energetic particles (SEPs), with variations in the acceleration and propagation producing a systematic flare-to-flare fractionation that depends on the charge per unit mass of the ion. Correcting the average SEP abundances for this fractionation yields SEP-derived coronal abundances for 20 elements. High-resolution SEP studies have also provided isotopic abundances for five elements. SEP-derived abundances indicate that elements with high first ionization potentials (greater than 10 eV) are depleted in the corona relative to the photosphere and provide new information on the solar abundance of C and Ne-22.

Tip-enhanced ablation and ionization mass spectrometry for nanoscale chemical analysis

PubMed Central

Liang, Zhisen; Zhang, Shudi; Li, Xiaoping; Wang, Tongtong; Huang, Yaping; Hang, Wei; Yang, Zhilin; Li, Jianfeng; Tian, Zhongqun

2017-01-01

Spectroscopic methods with nanoscale lateral resolution are becoming essential in the fields of physics, chemistry, geology, biology, and materials science. However, the lateral resolution of laser-based mass spectrometry imaging (MSI) techniques has so far been limited to the microscale. This report presents the development of tip-enhanced ablation and ionization time-of-flight mass spectrometry (TEAI-TOFMS), using a shell-isolated apertureless silver tip. The TEAI-TOFMS results indicate the capability and reproducibility of the system for generating nanosized craters and for acquiring the corresponding mass spectral signals. Multi-elemental analysis of nine inorganic salt residues and MSI of a potassium salt residue pattern at a 50-nm lateral resolution were achieved. These results demonstrate the opportunity for the distribution of chemical compositions at the nanoscale to be visualized. PMID:29226250

Selective extraction of halogenated compounds from data measured by comprehensive multidimensional gas chromatography/high resolution time-of-flight mass spectrometry for non-target analysis of environmental and biological samples.

PubMed

Hashimoto, Shunji; Zushi, Yasuyuki; Fushimi, Akihiro; Takazawa, Yoshikatsu; Tanabe, Kiyoshi; Shibata, Yasuyuki

2013-03-22

We developed a method that selectively extracts a subset from comprehensive 2D gas chromatography (GC×GC) and high-resolution time-of-flight mass spectrometry (HRTOFMS) data to detect and identify trace levels of organohalogens. The data were obtained by measuring several environmental and biological samples, namely fly ash, soil, sediment, the atmosphere, and human urine. For global analysis, some samples were measured without purification. By using our novel software, the mass spectra of organochlorines or organobromines were then extracted into a data subset under high mass accuracy conditions that were approximately equivalent to a mass resolution of 6000 for some samples. Mass defect filtering as pre-screening for the data extraction was very effective in removing the mass spectra of hydrocarbons. Those results showed that data obtained with HRTOFMS are valuable for global analysis of organohalogens, and probably of other compounds if specific data extraction methods can be devised. Copyright © 2013 Elsevier B.V. All rights reserved.

Analysis of human plasma lipids by using comprehensive two-dimensional gas chromatography with dual detection and with the support of high-resolution time-of-flight mass spectrometry for structural elucidation.

PubMed

Salivo, Simona; Beccaria, Marco; Sullini, Giuseppe; Tranchida, Peter Q; Dugo, Paola; Mondello, Luigi

2015-01-01

The main focus of the present research is the analysis of the unsaponifiable lipid fraction of human plasma by using data derived from comprehensive two-dimensional gas chromatography with dual quadrupole mass spectrometry and flame ionization detection. This approach enabled us to attain both mass spectral information and analyte percentage data. Furthermore, gas chromatography coupled with high-resolution time-of-flight mass spectrometry was used to increase the reliability of identification of several unsaponifiable lipid constituents. The synergism between both the high-resolution gas chromatography and mass spectrometry processes enabled us to attain a more in-depth knowledge of the unsaponifiable fraction of human plasma. Additionally, information was attained on the fatty acid and triacylglycerol composition of the plasma samples, subjected to investigation by using comprehensive two-dimensional gas chromatography with dual quadrupole mass spectrometry and flame ionization detection and high-performance liquid chromatography with atmospheric pressure chemical ionization quadrupole mass spectrometry, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proof of Concept Coded Aperture Miniature Mass Spectrometer Using a Cycloidal Sector Mass Analyzer, a Carbon Nanotube (CNT) Field Emission Electron Ionization Source, and an Array Detector.

PubMed

Amsden, Jason J; Herr, Philip J; Landry, David M W; Kim, William; Vyas, Raul; Parker, Charles B; Kirley, Matthew P; Keil, Adam D; Gilchrist, Kristin H; Radauscher, Erich J; Hall, Stephen D; Carlson, James B; Baldasaro, Nicholas; Stokes, David; Di Dona, Shane T; Russell, Zachary E; Grego, Sonia; Edwards, Steven J; Sperline, Roger P; Denton, M Bonner; Stoner, Brian R; Gehm, Michael E; Glass, Jeffrey T

2018-02-01

Despite many potential applications, miniature mass spectrometers have had limited adoption in the field due to the tradeoff between throughput and resolution that limits their performance relative to laboratory instruments. Recently, a solution to this tradeoff has been demonstrated by using spatially coded apertures in magnetic sector mass spectrometers, enabling throughput and signal-to-background improvements of greater than an order of magnitude with no loss of resolution. This paper describes a proof of concept demonstration of a cycloidal coded aperture miniature mass spectrometer (C-CAMMS) demonstrating use of spatially coded apertures in a cycloidal sector mass analyzer for the first time. C-CAMMS also incorporates a miniature carbon nanotube (CNT) field emission electron ionization source and a capacitive transimpedance amplifier (CTIA) ion array detector. Results confirm the cycloidal mass analyzer's compatibility with aperture coding. A >10× increase in throughput was achieved without loss of resolution compared with a single slit instrument. Several areas where additional improvement can be realized are identified. Graphical Abstract ᅟ.

Proof of Concept Coded Aperture Miniature Mass Spectrometer Using a Cycloidal Sector Mass Analyzer, a Carbon Nanotube (CNT) Field Emission Electron Ionization Source, and an Array Detector

NASA Astrophysics Data System (ADS)

Amsden, Jason J.; Herr, Philip J.; Landry, David M. W.; Kim, William; Vyas, Raul; Parker, Charles B.; Kirley, Matthew P.; Keil, Adam D.; Gilchrist, Kristin H.; Radauscher, Erich J.; Hall, Stephen D.; Carlson, James B.; Baldasaro, Nicholas; Stokes, David; Di Dona, Shane T.; Russell, Zachary E.; Grego, Sonia; Edwards, Steven J.; Sperline, Roger P.; Denton, M. Bonner; Stoner, Brian R.; Gehm, Michael E.; Glass, Jeffrey T.

2018-02-01

Despite many potential applications, miniature mass spectrometers have had limited adoption in the field due to the tradeoff between throughput and resolution that limits their performance relative to laboratory instruments. Recently, a solution to this tradeoff has been demonstrated by using spatially coded apertures in magnetic sector mass spectrometers, enabling throughput and signal-to-background improvements of greater than an order of magnitude with no loss of resolution. This paper describes a proof of concept demonstration of a cycloidal coded aperture miniature mass spectrometer (C-CAMMS) demonstrating use of spatially coded apertures in a cycloidal sector mass analyzer for the first time. C-CAMMS also incorporates a miniature carbon nanotube (CNT) field emission electron ionization source and a capacitive transimpedance amplifier (CTIA) ion array detector. Results confirm the cycloidal mass analyzer's compatibility with aperture coding. A >10× increase in throughput was achieved without loss of resolution compared with a single slit instrument. Several areas where additional improvement can be realized are identified.

Novel Polyfluorinated Compounds Identified Using High Resolution Mass Spectrometry Downstream of Manufacturing Facilities near Decatur, Alabama

EPA Science Inventory

Concern over persistence, bioaccumulation, and toxicity has led to international regulation and phase-outs of certain perfluorinated compounds and little is known about their replacement products. High resolution mass spectrometry was used to investigate the occurrence and identi...

Pushing down the low-mass halo concentration frontier with the Lomonosov cosmological simulations

NASA Astrophysics Data System (ADS)

Pilipenko, Sergey V.; Sánchez-Conde, Miguel A.; Prada, Francisco; Yepes, Gustavo

2017-12-01

We introduce the Lomonosov suite of high-resolution N-body cosmological simulations covering a full box of size 32 h-1 Mpc with low-mass resolution particles (2 × 107 h-1 M⊙) and three zoom-in simulations of overdense, underdense and mean density regions at much higher particle resolution (4 × 104 h-1 M⊙). The main purpose of this simulation suite is to extend the concentration-mass relation of dark matter haloes down to masses below those typically available in large cosmological simulations. The three different density regions available at higher resolution provide a better understanding of the effect of the local environment on halo concentration, known to be potentially important for small simulation boxes and small halo masses. Yet, we find the correction to be small in comparison with the scatter of halo concentrations. We conclude that zoom simulations, despite their limited representativity of the volume of the Universe, can be effectively used for the measurement of halo concentrations at least at the halo masses probed by our simulations. In any case, after a precise characterization of this effect, we develop a robust technique to extrapolate the concentration values found in zoom simulations to larger volumes with greater accuracy. Altogether, Lomonosov provides a measure of the concentration-mass relation in the halo mass range 107-1010 h-1 M⊙ with superb halo statistics. This work represents a first important step to measure halo concentrations at intermediate, yet vastly unexplored halo mass scales, down to the smallest ones. All Lomonosov data and files are public for community's use.

Mass resolution of linear quadrupole ion traps with round rods.

PubMed

Douglas, D J; Konenkov, N V

2014-11-15

Auxiliary dipole excitation is widely used to eject ions from linear radio-frequency quadrupole ion traps for mass analysis. Linear quadrupoles are often constructed with round rod electrodes. The higher multipoles introduced to the electric potential by round rods might be expected to change the ion ejection process. We have therefore investigated the optimum ratio of rod radius, r, to field radius, r0, for excitation and ejection of ions. Trajectory calculations are used to determine the excitation contour, S(q), the fraction of ions ejected when trapped at q values close to the ejection (or excitation) q. Initial conditions are randomly selected from Gaussian distributions of the x and y coordinates and a thermal distribution of velocities. The N = 6 (12 pole) and N = 10 (20 pole) multipoles are added to the quadrupole potential. Peak shapes and resolution were calculated for ratios r/r0 from 1.09 to 1.20 with an excitation time of 1000 cycles of the trapping radio-frequency. Ratios r/r0 in the range 1.140 to 1.160 give the highest resolution and peaks with little tailing. Ratios outside this range give lower resolution and peaks with tails on either the low-mass side or the high-mass side of the peaks. This contrasts with the optimum ratio of 1.126-1.130 for a quadrupole mass filter operated conventionally at the tip of the first stability region. With the optimum geometry the resolution is 2.7 times greater than with an ideal quadrupole field. Adding only a 2.0% hexapole field to a quadrupole field increases the resolution by a factor of 1.6 compared with an ideal quadrupole field. Addition of a 2.0% octopole lowers resolution and degrades peak shape. With the optimum value of r/r0 , the resolution increases with the ejection time (measured in cycles of the trapping rf, n) approximately as R0.5 = 6.64n, in contrast to a pure quadrupole field where R0.5 = 1.94n. Adding weak nonlinear fields to a quadrupole field can improve the resolution with mass-selective ejection of ions by up to a factor of 2.7. The optimum ratio r/r0 is 1.14 to 1.16, which differs from the optimum ratio for a mass filter of 1.128-1.130. Copyright © 2014 John Wiley & Sons, Ltd.

Determination of fluspirilene in human plasma by liquid chromatography-tandem mass spectrometry with electrospray ionisation.

PubMed

Swart, K J; Sutherland, F C; van Essen, G H; Hundt, H K; Hundt, A F

1998-12-18

An ultra-sensitive method for the determination of fluspirilene in plasma was established, using high-performance liquid chromatographic separation with tandem mass spectrometric detection. The samples were extracted with hexane/isoamyl alcohol, separated on a Phenomenex Luna C18 5 mu 150 x 2.1 mm column with a mobile phase consisting of methanol-water-acetic acid (600:400:1) at a flow-rate of 0.3 ml/min. Detection was achieved by a Finnigan Matt mass spectrometer (LCQ) at unit resolution in full scan mode scanning the product ion spectrum from m/z 130-500 and monitoring the transition of the protonated molecular ion at m/z 476.2, to the sum of the largest product ions m/z 371, 342 and 274 (MS-MS). Electrospray ionisation was used for ion production. The mean recovery for fluspirilene was 90% with a lower limit of quantification of 21.50 pg/ml using 1 ml plasma for extraction. This is the first chromatographic method described for the determination of fluspirilene in plasma that is accurate and sensitive enough to be used in pharmacokinetic studies.

High Sensitivity Combined with Extended Structural Coverage of Labile Compounds via Nanoelectrospray Ionization at Subambient Pressures

DOE PAGES

Cox, Jonathan T.; Kronewitter, Scott R.; Shukla, Anil K.; ...

2014-09-15

Subambient pressure ionization with nanoelectrospray (SPIN) has proven to be effective in producing ions with high efficiency and transmitting them to low pressures for high sensitivity mass spectrometry (MS) analysis. Here we present evidence that not only does the SPIN source improve MS sensitivity but also allows for gentler ionization conditions. The gentleness of a conventional heated capillary electrospray ionization (ESI) source and the SPIN source was compared by the liquid chromatography mass spectrometry (LC-MS) analysis of colominic acid. Colominic acid is a mixture of sialic acid polymers of different lengths containing labile glycosidic linkages between monomer units necessitating amore » gentle ion source. By coupling the SPIN source with high resolution mass spectrometry and using advanced data processing tools, we demonstrate much extended coverage of sialic acid polymer chains as compared to using the conventional ESI source. Additionally we show that SPIN-LC-MS is effective in elucidating polymer features with high efficiency and high sensitivity previously unattainable by the conventional ESI-LC-MS methods.« less

Non-refractory PM1 in SE Asia: Chemically speciated aerosol fluxes and concentrations above contrasting land-uses in SE Asia.

NASA Astrophysics Data System (ADS)

Phillips, Gavin; Farmer, Delphine; di Marco, Chiara; Misztal, Pawel; Sueper, Donna; Kimmel, Joel; Jimenez, Jose; Fowler, David; Nemitz, Eiko

2010-05-01

New measurements of VOC emissions (measured with leaf cuvettes, and ecosystem fluxes obtained from eddy covariance measurements) suggest that oil palm (Elaeis guineensis Jacq) is a significantly larger source of isoprene than tropical forest, in Borneo. These larger sources of isoprene measured over oil palm, allied with a larger anthropogenic component of local emissions, contrasts with the composition of the atmosphere in the semi-remote tropical forest environment. The difference in the atmospheric composition above different land-uses has the potential to lead to contrasting chemistry and physics controlling the formation and processing of particulate matter. Thus land use changes, driven by the economics of biofuels, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions, chemical processing and composition of organic aerosol over both (semi-)natural and anthropogenic land uses in the tropical environment. Ecosystem flux measurements of chemically-speciated non-refractory PM1 were made over two contrasting land uses in the Malaysian state of Sabah, on the island of Borneo during 2008. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at the Global Atmospheric Watch (GAW) site at a tropical rain forest location as well as the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as a collaboration between three UK NERC funded projects (OP3, APPRAISE/ACES and DIASPORA). Recent technical developments using ToF detectors allow us to record 10 Hz full mass spectra at both high resolution (HR) and unit-mass resolution (UMR), suitable for the calculation of local eddy-covariance fluxes. The measurements provide information on the deposition rate of anthropogenic aerosol components (e.g. sulphate, nitrate, ammonium and hydrocarbon-like aerosol) to tropical forest and oil palm. At the same time, any biogenic secondary organic aerosol components formed through fast chemistry below the measurement height would appear as an upward flux, and the direct flux measurement therefore provides an alternative approach to probing BSOA formation mechanisms. In particular, through the calculation of mass spectra in terms of flux and deposition velocity those masses and aerosol fragments can be identified that show similar behaviour. In addition, the contribution of the various chemical species (e.g. nitrate, sulphate, OA sub-types) to the total mass flux will be elucidated.

Comprehensive comparison of liquid chromatography selectivity as provided by two types of liquid chromatography detectors (high resolution mass spectrometry and tandem mass spectrometry): "where is the crossover point?".

PubMed

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

2010-07-12

The selectivity of mass traces obtained by monitoring liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was compared. A number of blank extracts (fish, pork kidney, pork liver and honey) were separated by ultra performance liquid chromatography (UPLC). Detected were some 100 dummy transitions respectively dummy exact masses (traces). These dummy masses were the product of a random generator. The range of the permitted masses corresponded to those which are typical for analytes (e.g. veterinary drugs). The large number of monitored dummy traces ensured that endogenous compounds present in the matrix extract, produced a significant number of detectable chromatographic peaks. All obtained chromatographic peaks were integrated and standardized. Standardisation was done by dividing these absolute peak areas by the average response of a set of 7 different veterinary drugs. This permitted a direct comparison between the LC-HRMS and LC-MS/MS data. The data indicated that the selectivity of LC-HRMS exceeds LC-MS/MS, if high resolution mass spectrometry (HRMS) data is recorded with a resolution of 50,000 full width at half maximum (FWHM) and a corresponding mass window. This conclusion was further supported by experimental data (MS/MS based trace analysis), where a false positive finding was observed. An endogenous matrix compound present in honey matrix behaved like a banned nitroimidazole drug. This included identical retention time and two MRM traces, producing an MRM ratio between them, which perfectly matched the ratio observed in the external standard. HRMS measurement clearly resolved the interfering matrix compound and unmasked the false positive MS/MS finding. Copyright 2010 Elsevier B.V. All rights reserved.

Chemical analysis of solids with sub-nm depth resolution by using a miniature LIMS system designed for in situ space research

NASA Astrophysics Data System (ADS)

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

2015-04-01

Sensitive elemental and isotope analysis of solid samples are of considerable interest in nowadays in situ space research. For context in situ analysis, high spatial resolution is also of substantial importance. While the measurements conducted with high lateral resolution can provide compositional details of the surface of highly heterogeneous materials, depth profiling measurements yield information on compositional details of surface and subsurface. The mass spectrometric analysis with the vertical resolution at sub-µm levels is of special consideration and can deliver important information on processes, which may have modified the surface. Information on space weathering effects can be readily determined when the sample composition of the surface and sub-surface is studied with high vertical resolution. In this contribution we will present vertical depth resolution measurements conducted by our sensitive miniature laser ablation ionization time-of-flight mass spectrometer (160mm x Ø 60mm) designed for in situ space research [1-3]. The mass spectrometer is equipped with a fs-laser system (~190fs pulse width, λ = 775nm), which is used for ablation and ionization of the sample material [2]. Laser radiation is focussed on the target material to a spot size of about 10-20 µm in diameter. Mass spectrometric measurements are conducted with a mass resolution (m/Δm) of about 400-500 (at 56Fe mass peak) and with a superior dynamic range of more than eight orders of magnitude. The depth profiling performance studies were conducted on 10µm thick Cu films that were deposited by an additive-assisted electrochemical procedure on Si-wafers. The presented measurement study will show that the current instrument prototype is able to conduct quantitative chemical (elemental and isotope) analysis of solids with a vertical resolution at sub-nm level. Contaminants, incorporated by using additives (polymers containing e.g. C, N, O, S) and with layer thickness of a few nanometres, can be fully resolved [1]. The current measurement performance, including the sensitivity and the high vertical depth resolution, opens new perspectives for future applications in the laboratory, e.g. measurements of Genesis samples, and new measurement capabilities for in situ space research. References 1)V. Grimaudo, P. Moreno-García, M.B. Neuland, M. Tulej, P. Broekmann, P. Wurz and A. Riedo, "High-resolution chemical depth profiling of solid material using a miniature laser ablation/ionization mass spectrometer", Anal. Chem., 2015, submitted. 2)A. Riedo, M. Neuland, S. Meyer, M. Tulej, and P. Wurz, "Coupling of LMS with a fs-laser ablation ion source: elemental and isotope composition measurements", J. Anal. At. Spectrom., 2013, 28, 1256. 3)Tulej et al. CAMAM: A Miniature Laser Ablation Ionisation Mass Spectrometer and Microscope-Camera System for In Situ Investigation of the Composition and Morphology of Extraterrestrial Materials, Geostand. Geoanal. Res., 2014, doi: 10.1111/j.1751-908X.2014.00302.x

High-resolution Mass Spectrometry of Skin Mucus for Monitoring Physiological Impacts in Fish Exposed to Wastewater Effluent at a Great Lakes AOC

EPA Science Inventory

High-resolution mass spectrometry is advantageous for monitoring physiological impacts and contaminant biotransformation products in fish exposed to complex wastewater effluent. We evaluated this technique using skin mucus from male and female fathead minnows (Pimephales promela...

High‐resolution mass spectrometry of skin mucus for monitoring physiological impacts and contaminant biotransformation products in fathead minnows exposed to wastewater effluent

EPA Science Inventory

High‐resolution mass spectrometry is advantageous for monitoring physiological impacts and contaminant biotransformation products in fish exposed to complex wastewater effluent. We evaluated this technique using skin mucus from male and female fathead minnows (Pimephales pr...

Environmental Chemistry Compound Identification Using High Resolution Mass Spectrometry Data Integrated to the EPA Chemistry Dashboard (EAS)

EPA Science Inventory

There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chromatograph...

High-resolution simulations of the final assembly of Earth-like planets. 2. Water delivery and planetary habitability.

PubMed

Raymond, Sean N; Quinn, Thomas; Lunine, Jonathan I

2007-02-01

The water content and habitability of terrestrial planets are determined during their final assembly, from perhaps 100 1,000-km "planetary embryos " and a swarm of billions of 1-10-km "planetesimals. " During this process, we assume that water-rich material is accreted by terrestrial planets via impacts of water-rich bodies that originate in the outer asteroid region. We present analysis of water delivery and planetary habitability in five high-resolution simulations containing about 10 times more particles than in previous simulations. These simulations formed 15 terrestrial planets from 0.4 to 2.6 Earth masses, including five planets in the habitable zone. Every planet from each simulation accreted at least the Earth's current water budget; most accreted several times that amount (assuming no impact depletion). Each planet accreted at least five water-rich embryos and planetesimals from the past 2.5 astronomical units; most accreted 10-20 water-rich bodies. We present a new model for water delivery to terrestrial planets in dynamically calm systems, with low-eccentricity or low-mass giant planets-such systems may be very common in the Galaxy. We suggest that water is accreted in comparable amounts from a few planetary embryos in a " hit or miss " way and from millions of planetesimals in a statistically robust process. Variations in water content are likely to be caused by fluctuations in the number of water-rich embryos accreted, as well as from systematic effects, such as planetary mass and location, and giant planet properties.

Quantitative metrics for assessment of chemical image quality and spatial resolution

DOE PAGES

Kertesz, Vilmos; Cahill, John F.; Van Berkel, Gary J.

2016-02-28

Rationale: Currently objective/quantitative descriptions of the quality and spatial resolution of mass spectrometry derived chemical images are not standardized. Development of these standardized metrics is required to objectively describe chemical imaging capabilities of existing and/or new mass spectrometry imaging technologies. Such metrics would allow unbiased judgment of intra-laboratory advancement and/or inter-laboratory comparison for these technologies if used together with standardized surfaces. Methods: We developed two image metrics, viz., chemical image contrast (ChemIC) based on signal-to-noise related statistical measures on chemical image pixels and corrected resolving power factor (cRPF) constructed from statistical analysis of mass-to-charge chronograms across features of interest inmore » an image. These metrics, quantifying chemical image quality and spatial resolution, respectively, were used to evaluate chemical images of a model photoresist patterned surface collected using a laser ablation/liquid vortex capture mass spectrometry imaging system under different instrument operational parameters. Results: The calculated ChemIC and cRPF metrics determined in an unbiased fashion the relative ranking of chemical image quality obtained with the laser ablation/liquid vortex capture mass spectrometry imaging system. These rankings were used to show that both chemical image contrast and spatial resolution deteriorated with increasing surface scan speed, increased lane spacing and decreasing size of surface features. Conclusions: ChemIC and cRPF, respectively, were developed and successfully applied for the objective description of chemical image quality and spatial resolution of chemical images collected from model surfaces using a laser ablation/liquid vortex capture mass spectrometry imaging system.« less

A new generation of high resolution mass analyzer to study organic and mineral matters simulating those of Titan and Enceladus: the Cosmorbitrap project

NASA Astrophysics Data System (ADS)

Selliez-Vandernotte, Laura; Briois, Christelle; Carrasco, Nathalie; Thirkell, Laurent; Cosmorbitrap Team

2016-10-01

Cassini mission highlighted for the first time, among many discoveries, the chemistry occurring in Titan atmosphere (with the detection of positive and negative ions at very high masses) and the presence of organic matter hidden in Enceladus plumes (1; 2). Can you imagine which results would have been obtained with a better resolution?Today, in lab, a new generation of high resolution mass analyzer called OrbitrapTM can reach a resolution of 106 at m/z=200 (3; 4). It gives a precise reading of the mass on charge, using a purely electric field and applying a Fourier transform. A project named Cosmorbitrap is trying to incorporate an OrbitrapTM analyzer, as a part of a mass spectrometer instrument, in order to propose it for a future mission toward the Saturn moons but also toward many other objects in the Solar System (5).Among the various tests required, we are optimizing the analysis of mineral and organic matter. This includes mass precision, resolution, isotopic detection, isotopic ratios and identification of unknown molecules. Starting with simple molecules, we will study more and more complex molecules and mixtures like Titan and Enceladus analogs. This meeting could be a great opportunity to explain our last results, to present benefits and limits of this instrument.(1) Waite et al, 2007, Science(2) Waite et al, 2009, Nature(3) Makarov, 2000(4) Denisov et al, 2012(5) Briois et al, 2016, Planetary and Space Science (in press)

Quantitative metrics for assessment of chemical image quality and spatial resolution

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

Kertesz, Vilmos; Cahill, John F.; Van Berkel, Gary J.

Rationale: Currently objective/quantitative descriptions of the quality and spatial resolution of mass spectrometry derived chemical images are not standardized. Development of these standardized metrics is required to objectively describe chemical imaging capabilities of existing and/or new mass spectrometry imaging technologies. Such metrics would allow unbiased judgment of intra-laboratory advancement and/or inter-laboratory comparison for these technologies if used together with standardized surfaces. Methods: We developed two image metrics, viz., chemical image contrast (ChemIC) based on signal-to-noise related statistical measures on chemical image pixels and corrected resolving power factor (cRPF) constructed from statistical analysis of mass-to-charge chronograms across features of interest inmore » an image. These metrics, quantifying chemical image quality and spatial resolution, respectively, were used to evaluate chemical images of a model photoresist patterned surface collected using a laser ablation/liquid vortex capture mass spectrometry imaging system under different instrument operational parameters. Results: The calculated ChemIC and cRPF metrics determined in an unbiased fashion the relative ranking of chemical image quality obtained with the laser ablation/liquid vortex capture mass spectrometry imaging system. These rankings were used to show that both chemical image contrast and spatial resolution deteriorated with increasing surface scan speed, increased lane spacing and decreasing size of surface features. Conclusions: ChemIC and cRPF, respectively, were developed and successfully applied for the objective description of chemical image quality and spatial resolution of chemical images collected from model surfaces using a laser ablation/liquid vortex capture mass spectrometry imaging system.« less

Analysis of very-high-resolution Galileo images of Europa: Implications for small-scale structure and surface evolution

NASA Astrophysics Data System (ADS)

Leonard, E. J.; Pappalardo, R. T.; Yin, A.; Prockter, L. M.; Patthoff, D. A.

2014-12-01

The Galileo Solid State Imager (SSI) recorded nine very high-resolution frames (8 at 12 m/pixel and 1 at 6 m/pixel) during the E12 flyby of Europa in Dec. 1997. To understand the implications for the small-scale structure and evolution of Europa, we mosaicked these frames (observations 12ESMOTTLE01 and 02, incidence ≈18°, emission ≈77°) into their regional context (part of observation 11ESREGMAP01, 220 m/pixel, incidence ≈74°, emission ≈23°), despite their very different viewing and lighting conditions. We created a map of geological units based on morphology, structure, and albedo along with stereoscopic images where the frames overlapped. The highly diverse units range from: high albedo sub-parallel ridge and grooved terrain; to variegated-albedo hummocky terrain; to low albedo and relatively smooth terrain. We classified and analyzed the diverse units solely based on the high-resolution image mosaic, prior to comparison to the context image, to obtain an in-depth look at possible surface evolution and underlying formational processes. We infer that some of these units represent different stages and forms of resurfacing, including cryovolcanic and tectonic resurfacing. However, significant morphological variation among units in the region indicates that there are different degrees of resurfacing at work. We have created candidate morphological sequences that provide insight into the conversion of ridged plains to chaotic terrain—generally, a process of subduing formerly sharp features through tectonic modification and/or cryovolcanism. When the map of the high-resolution area is compared to the regional context, features that appear to be one unit at regional resolution are comprised of several distinct units at high resolution, and features that appear to be smooth in the context image are found to show distinct textures. Moreover, in the context image, transitions from ridged units to disrupted units appear to be gradual; however the high-resolution image reveals them to be abrupt, suggesting tectonic control of these boundaries. These discrepancies could have important implications for a future landed exploration.

HPLC-high-resolution mass spectrometry with polarity switching for increasing throughput of human in vitro cocktail drug-drug interaction assay.

PubMed

Ramanathan, Ragu; Ghosal, Anima; Ramanathan, Lakshmi; Comstock, Kate; Shen, Helen; Ramanathan, Dil

2018-05-01

Evaluation of HPLC-high-resolution mass spectrometry (HPLC-HRMS) full scan with polarity switching for increasing throughput of human in vitro cocktail drug-drug interaction assay. Microsomal incubates were analyzed using a high resolution and high mass accuracy Q-Exactive mass spectrometer to collect integrated qualitative and quantitative (qual/quant) data. Within assay, positive-to-negative polarity switching HPLC-HRMS method allowed quantification of eight and two probe compounds in the positive and negative ionization modes, respectively, while monitoring for LOR and its metabolites. LOR-inhibited CYP2C19 and showed higher activity for CYP2D6, CYP2E1 and CYP3A4. Overall, LC-HRMS-based nontargeted full scan quantitation allowed to improve the throughput of the in vitro cocktail drug-drug interaction assay.

Applications of Fourier Transform Ion Cyclotron Resonance (FT-ICR) and Orbitrap Based High Resolution Mass Spectrometry in Metabolomics and Lipidomics.

PubMed

Ghaste, Manoj; Mistrik, Robert; Shulaev, Vladimir

2016-05-25

Metabolomics, along with other "omics" approaches, is rapidly becoming one of the major approaches aimed at understanding the organization and dynamics of metabolic networks. Mass spectrometry is often a technique of choice for metabolomics studies due to its high sensitivity, reproducibility and wide dynamic range. High resolution mass spectrometry (HRMS) is a widely practiced technique in analytical and bioanalytical sciences. It offers exceptionally high resolution and the highest degree of structural confirmation. Many metabolomics studies have been conducted using HRMS over the past decade. In this review, we will explore the latest developments in Fourier transform mass spectrometry (FTMS) and Orbitrap based metabolomics technology, its advantages and drawbacks for using in metabolomics and lipidomics studies, and development of novel approaches for processing HRMS data.

Applications of Fourier Transform Ion Cyclotron Resonance (FT-ICR) and Orbitrap Based High Resolution Mass Spectrometry in Metabolomics and Lipidomics

PubMed Central

Ghaste, Manoj; Mistrik, Robert; Shulaev, Vladimir

2016-01-01

Metabolomics, along with other “omics” approaches, is rapidly becoming one of the major approaches aimed at understanding the organization and dynamics of metabolic networks. Mass spectrometry is often a technique of choice for metabolomics studies due to its high sensitivity, reproducibility and wide dynamic range. High resolution mass spectrometry (HRMS) is a widely practiced technique in analytical and bioanalytical sciences. It offers exceptionally high resolution and the highest degree of structural confirmation. Many metabolomics studies have been conducted using HRMS over the past decade. In this review, we will explore the latest developments in Fourier transform mass spectrometry (FTMS) and Orbitrap based metabolomics technology, its advantages and drawbacks for using in metabolomics and lipidomics studies, and development of novel approaches for processing HRMS data. PMID:27231903

Surface Dimming by the 2013 Rim Fire Simulated by a Sectional Aerosol Model

NASA Technical Reports Server (NTRS)

Yu, Pengfei; Toon, Owen B.; Bardeen, Charles G; Bucholtz, Anthony; Rosenlof, Karen; Saide, Pablo E.; Da Silva, Arlindo M.; Ziemba, Luke D.; Thornhill, Kenneth L.; Jimenez, Jose-Luis;

Surface dimming by the 2013 Rim Fire simulated by a sectional aerosol model.

PubMed

Yu, Pengfei; Toon, Owen B; Bardeen, Charles G; Bucholtz, Anthony; Rosenlof, Karen H; Saide, Pablo E; Da Silva, Arlindo; Ziemba, Luke D; Thornhill, Kenneth L; Jimenez, Jose-Luis; Campuzano-Jost, Pedro; Schwarz, Joshua P; Perring, Anne E; Froyd, Karl D; Wagner, N L; Mills, Michael J; Reid, Jeffrey S

2016-06-27

The Rim Fire of 2013, the third largest area burned by fire recorded in California history, is simulated by a climate model coupled with a size-resolved aerosol model. Modeled aerosol mass, number, and particle size distribution are within variability of data obtained from multiple-airborne in situ measurements. Simulations suggest that Rim Fire smoke may block 4-6% of sunlight energy reaching the surface, with a dimming efficiency around 120-150 W m -2 per unit aerosol optical depth in the midvisible at 13:00-15:00 local time. Underestimation of simulated smoke single scattering albedo at midvisible by 0.04 suggests that the model overestimates either the particle size or the absorption due to black carbon. This study shows that exceptional events like the 2013 Rim Fire can be simulated by a climate model with 1° resolution with overall good skill, although that resolution is still not sufficient to resolve the smoke peak near the source region.

Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry

PubMed Central

Prokai, Laszlo; Stevens, Stanley M.

2016-01-01

Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae. PMID:26784186

Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry.

PubMed

Prokai, Laszlo; Stevens, Stanley M

2016-01-16

Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae.

Matching soil grid unit resolutions with polygon unit scales for DNDC modelling of regional SOC pool

NASA Astrophysics Data System (ADS)

Zhang, H. D.; Yu, D. S.; Ni, Y. L.; Zhang, L. M.; Shi, X. Z.

2015-03-01

Matching soil grid unit resolution with polygon unit map scale is important to minimize uncertainty of regional soil organic carbon (SOC) pool simulation as their strong influences on the uncertainty. A series of soil grid units at varying cell sizes were derived from soil polygon units at the six map scales of 1:50 000 (C5), 1:200 000 (D2), 1:500 000 (P5), 1:1 000 000 (N1), 1:4 000 000 (N4) and 1:14 000 000 (N14), respectively, in the Tai lake region of China. Both format soil units were used for regional SOC pool simulation with DeNitrification-DeComposition (DNDC) process-based model, which runs span the time period 1982 to 2000 at the six map scales, respectively. Four indices, soil type number (STN) and area (AREA), average SOC density (ASOCD) and total SOC stocks (SOCS) of surface paddy soils simulated with the DNDC, were attributed from all these soil polygon and grid units, respectively. Subjecting to the four index values (IV) from the parent polygon units, the variation of an index value (VIV, %) from the grid units was used to assess its dataset accuracy and redundancy, which reflects uncertainty in the simulation of SOC. Optimal soil grid unit resolutions were generated and suggested for the DNDC simulation of regional SOC pool, matching with soil polygon units map scales, respectively. With the optimal raster resolution the soil grid units dataset can hold the same accuracy as its parent polygon units dataset without any redundancy, when VIV < 1% of all the four indices was assumed as criteria to the assessment. An quadratic curve regression model y = -8.0 × 10-6x2 + 0.228x + 0.211 (R2 = 0.9994, p < 0.05) was revealed, which describes the relationship between optimal soil grid unit resolution (y, km) and soil polygon unit map scale (1:x). The knowledge may serve for grid partitioning of regions focused on the investigation and simulation of SOC pool dynamics at certain map scale.

Mass Spectrometric Imaging Using Laser Ablation and Solvent Capture by Aspiration (LASCA)

NASA Astrophysics Data System (ADS)

Brauer, Jonathan I.; Beech, Iwona B.; Sunner, Jan

2015-09-01

A novel interface for ambient, laser ablation-based mass spectrometric imaging (MSI) referred to as laser ablation and solvent capture by aspiration (LASCA) is presented and its performance demonstrated using selected, unaltered biological materials. LASCA employs a pulsed 2.94 μm laser beam for specimen ablation. Ablated materials in the laser plumes are collected on a hanging solvent droplet with electric field-enhanced trapping, followed by aspiration of droplets and remaining plume material in the form of a coarse aerosol into a collection capillary. The gas and liquid phases are subsequently separated in a 10 μL-volume separatory funnel, and the solution is analyzed with electrospray ionization in a high mass resolution Q-ToF mass spectrometer. The LASCA system separates the sampling and ionization steps in MSI and combines high efficiencies of laser plume sampling and of electrospray ionization (ESI) with high mass resolution MS. Up to 2000 different compounds are detected from a single ablation spot (pixel). Using the LASCA platform, rapid (6 s per pixel), high sensitivity, high mass-resolution ambient imaging of "as-received" biological material is achieved routinely and reproducibly.

LM-3: A High-resolution Lake Michigan Mass Balance Water Quality Model

EPA Science Inventory

This report is a user’s manual that describes the high-resolution mass balance model known as LM3. LM3 has been applied to Lake Michigan to describe the transport and fate of atrazine, PCB congeners, and chloride in that system. The model has also been used to model eutrophicat...

The EPA iCSS Chemistry Dashboard to Support Compound Identification Using High Resolution Mass Spectrometry Data (ACS Fall meeting)

EPA Science Inventory

Abstract: There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chr...

Linking high resolution mass spectrometry data with exposure and toxicity forecasts to advance high-throughput environmental monitoring

EPA Science Inventory

There is a growing need in the field of exposure science for monitoring methods that rapidly screen environmental media for suspect contaminants. Measurement and analysis platforms, based on high resolution mass spectrometry (HRMS), now exist to meet this need. Here we describe r...

Measuring Two Decades of Ice Mass Loss using GRACE and SLR

NASA Astrophysics Data System (ADS)

Bonin, J. A.; Chambers, D. P.

2016-12-01

We use Satellite Laser Ranging (SLR) to extend the time series of ice mass change back in time to 1994. The SLR series is of far lesser spatial resolution than GRACE, so we apply a constrained inversion technique to better localize the signal. We approximate the likely errors due to SLR's measurement errors combined with the inversion errors from using a low-resolution series, then estimate the interannual mass change over Greenland and Antarctica.

Quantification of polychlorinated dibenzo-p-dioxins and dibenzofurans by direct injection of sample extract into the comprehensive multidimensional gas chromatograph/high-resolution time-of-flight mass spectrometer.

PubMed

Shunji, Hashimoto; Yoshikatsu, Takazawa; Akihiro, Fushimi; Hiroyasu, Ito; Kiyoshi, Tanabe; Yasuyuki, Shibata; Masa-aki, Ubukata; Akihiko, Kusai; Kazuo, Tanaka; Hideyuki, Otsuka; Katsunori, Anezaki

2008-01-18

Polychlorinated dibenzo-p-dioxins and dibenzofurans in crude extracts of fly ash and flue gas from municipal waste incinerators were quantified using a comprehensive multidimensional gas chromatograph (GC x GC) coupled to a high-resolution time-of-flight mass spectrometer (HR-TOFMS). For identification and quantification, we developed our own program to prepare 3D chromatograms of selected mass numbers from the data of the GC x GC/HR-TOFMS. Isolation of all congeners with a TCDD toxic equivalency factor from the other isomers by only one injection was confirmed. The instrumental detection limit of TCDD on the GC x GC/HR-TOFMS was 0.9 pg by the relative calibration method. Quantification of these substances in the crude extracts was achieved by direct injection to the GC x GC/HR-TOFMS. The results agree with the values obtained using a generic gas chromatography/high-resolution mass spectrometry (GC/HRMS) system. It was confirmed that measurement by high-resolution TOFMS and GC x GC effectively reduces interference from other chemicals.

Does Explosive Nuclear Burning Occur in Tidal Disruption Events of White Dwarfs by Intermediate-mass Black Holes?

NASA Astrophysics Data System (ADS)

Tanikawa, Ataru; Sato, Yushi; Nomoto, Ken'ichi; Maeda, Keiichi; Nakasato, Naohito; Hachisu, Izumi

2017-04-01

We investigate nucleosynthesis in tidal disruption events (TDEs) of white dwarfs (WDs) by intermediate-mass black holes. We consider various types of WDs with different masses and compositions by means of three-dimensional (3D) smoothed particle hydrodynamics (SPH) simulations. We model these WDs with different numbers of SPH particles, N, from a few 104 to a few 107 in order to check mass resolution convergence, where SPH simulations with N > 107 (or a space resolution of several 106 cm) have unprecedentedly high resolution in this kind of simulation. We find that nuclear reactions become less active with increasing N and that these nuclear reactions are excited by spurious heating due to low resolution. Moreover, we find no shock wave generation. In order to investigate the reason for the absence of a shock wave, we additionally perform one-dimensional (1D) SPH and mesh-based simulations with a space resolution ranging from 104 to 107 cm, using a characteristic flow structure extracted from the 3D SPH simulations. We find shock waves in these 1D high-resolution simulations, one of which triggers a detonation wave. However, we must be careful of the fact that, if the shock wave emerged in an outer region, it could not trigger the detonation wave due to low density. Note that the 1D initial conditions lack accuracy to precisely determine where a shock wave emerges. We need to perform 3D simulations with ≲106 cm space resolution in order to conclude that WD TDEs become optical transients powered by radioactive nuclei.

A new processing scheme for ultra-high resolution direct infusion mass spectrometry data

NASA Astrophysics Data System (ADS)

Zielinski, Arthur T.; Kourtchev, Ivan; Bortolini, Claudio; Fuller, Stephen J.; Giorio, Chiara; Popoola, Olalekan A. M.; Bogialli, Sara; Tapparo, Andrea; Jones, Roderic L.; Kalberer, Markus

2018-04-01

High resolution, high accuracy mass spectrometry is widely used to characterise environmental or biological samples with highly complex composition enabling the identification of chemical composition of often unknown compounds. Despite instrumental advancements, the accurate molecular assignment of compounds acquired in high resolution mass spectra remains time consuming and requires automated algorithms, especially for samples covering a wide mass range and large numbers of compounds. A new processing scheme is introduced implementing filtering methods based on element assignment, instrumental error, and blank subtraction. Optional post-processing incorporates common ion selection across replicate measurements and shoulder ion removal. The scheme allows both positive and negative direct infusion electrospray ionisation (ESI) and atmospheric pressure photoionisation (APPI) acquisition with the same programs. An example application to atmospheric organic aerosol samples using an Orbitrap mass spectrometer is reported for both ionisation techniques resulting in final spectra with 0.8% and 8.4% of the peaks retained from the raw spectra for APPI positive and ESI negative acquisition, respectively.

Estimating NOx emissions and surface concentrations at high spatial resolution using OMI

NASA Astrophysics Data System (ADS)

Goldberg, D. L.; Lamsal, L. N.; Loughner, C.; Swartz, W. H.; Saide, P. E.; Carmichael, G. R.; Henze, D. K.; Lu, Z.; Streets, D. G.

2017-12-01

In many instances, NOx emissions are not measured at the source. In these cases, remote sensing techniques are extremely useful in quantifying NOx emissions. Using an exponential modified Gaussian (EMG) fitting of oversampled Ozone Monitoring Instrument (OMI) NO2 data, we estimate NOx emissions and lifetimes in regions where these emissions are uncertain. This work also presents a new high-resolution OMI NO2 dataset derived from the NASA retrieval that can be used to estimate surface level concentrations in the eastern United States and South Korea. To better estimate vertical profile shape factors, we use high-resolution model simulations (Community Multi-scale Air Quality (CMAQ) and WRF-Chem) constrained by in situ aircraft observations to re-calculate tropospheric air mass factors and tropospheric NO2 vertical columns during summertime. The correlation between our satellite product and ground NO2 monitors in urban areas has improved dramatically: r2 = 0.60 in new product, r2 = 0.39 in operational product, signifying that this new product is a better indicator of surface concentrations than the operational product. Our work emphasizes the need to use both high-resolution and high-fidelity models in order to re-calculate vertical column data in areas with large spatial heterogeneities in NOx emissions. The methodologies developed in this work can be applied to other world regions and other satellite data sets to produce high-quality region-specific emissions estimates.

FLUX-BASED METHODS FOR DNAPL REMEDIATION DESIGN AND ASSESSMENT

EPA Science Inventory

One tool that has been investigated for use in DNAPL site characterization and remediation is mass flux (mass per unit area per unit time) and mass discharge (mass per unit time) measurements. These measurements, when collected across one or more control planes located down grad...

Hurdles in low k1 mass production

NASA Astrophysics Data System (ADS)

Yim, Donggyu; Yang, Hyunjo; Park, Chanha; Hong, Jongkyun; Choi, Jaeseung

2005-05-01

As the optical lithography pushes toward its theoretical resolution limit 0.25k1, the application of aggressive Resolution Enhancement Techniques (RETs) are required in order to ensure necessary resolution, sufficient process window, and reasonable MEEF in critical layers. When chip makers are adopting RETs in low k1 device, there are a lot of crucial factors to take into account in the development and mass production. Those hurdles are not only difficult to overcome but also highly risky to the company, which adopts low k1 mass production strategy. But, low k1 production strategy is very attractive to all chip makers, owing to improving production capacity and cost of ownership. So, low k1 technology has been investigated by many lithography engineers. Lots of materials have been introduced. Most of them are just in RnD level. In this study, low k1 mass production issues shall be introduced, mainly. The definition of low k1 in mass production shall be suggested. And, a lot of low_k1 issues shall be introduced, also. Most of them were investigated/experienced in RnD development stage and final mass production line. Low k1 mass production, is some what different from only RnD development.

Using Power Spectrum Analysis to Evaluate 18O-Water Labeling Data Acquired from Low Resolution Mass Spectrometers

PubMed Central

Sadygov, Rovshan G.; Zhao, Yingxin; Haidacher, Sigmund J.; Starkey, Jonathan M.; Tilton, Ronald G.; Denner, Larry

2010-01-01

We describe a method for ratio estimations in 18O-water labeling experiments acquired from low resolution isotopically resolved data. The method is implemented in a software package specifically designed for use in experiments making use of zoom-scan mode data acquisition. Zoom-scan mode data allows commonly used ion trap mass spectrometers to attain isotopic resolution, which make them amenable to use in labeling schemes such as 18O-water labeling, but algorithms and software developed for high resolution instruments may not be appropriate for the lower resolution data acquired in zoom-scan mode. The use of power spectrum analysis is proposed as a general approach which may be uniquely suited to these data types. The software implementation uses power spectrum to remove high-frequency noise, and band-filter contributions from co-eluting species of differing charge states. From the elemental composition of a peptide sequence we generate theoretical isotope envelopes of heavy-light peptide pairs in five different ratios; these theoretical envelopes are correlated with the filtered experimental zoom scans. To automate peptide quantification in high-throughput experiments, we have implemented our approach in a computer program, MassXplorer. We demonstrate the application of MassXplorer to two model mixtures of known proteins, and to a complex mixture of mouse kidney cortical extract. Comparison with another algorithm for ratio estimations demonstrates the increased precision and automation of MassXplorer. PMID:20568695

40 CFR 766.16 - Developing the analytical test method.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Resolution Gas Chromatography (HRGC) with High Resolution Mass Spectrometry (HRMS) is the method of choice... meet the requirements of the chemical matrix. (d) Analysis. The method of choice is High Resolution Gas...

40 CFR 766.16 - Developing the analytical test method.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Resolution Gas Chromatography (HRGC) with High Resolution Mass Spectrometry (HRMS) is the method of choice... meet the requirements of the chemical matrix. (d) Analysis. The method of choice is High Resolution Gas...

A compact time-of-flight mass spectrometer for ion source characterization

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

Chen, L., E-mail: l.chen03@gmail.com; Wan, X.; Jin, D. Z.

2015-03-15

A compact time-of-flight mass spectrometer with overall dimension of about 413 × 250 × 414 mm based on orthogonal injection and angle reflection has been developed for ion source characterization. Configuration and principle of the time-of-flight mass spectrometer are introduced in this paper. The mass resolution is optimized to be about 1690 (FWHM), and the ion energy detection range is tested to be between about 3 and 163 eV with the help of electron impact ion source. High mass resolution and compact configuration make this spectrometer useful to provide a valuable diagnostic for ion spectra fundamental research and study themore » mass to charge composition of plasma with wide range of parameters.« less

Unbalanced Stability: Applying Lessons from American Cities in Stability Operations

DTIC Science & Technology

2011-05-19

teenagers congregating on street corners, public solicitation for prostitution, begging, public drinking, verbal harassment of women on the street, and...United Nations Security Council, “United Nations Security Council Resolution 1590 (2005).” http://www.un.org/ga/search/view_doc.asp?symbol=S/RES/ 1590 (2005...Security Council. “United Nations Security Council Resolution 1590 (2005).” United Nations. http://www.un.org/ga/search/view_doc.asp?symbol=S/RES/ 1590

Pre-processing liquid chromatography/high-resolution mass spectrometry data: extracting pure mass spectra by deconvolution from the invariance of isotopic distribution.

PubMed

Krishnan, Shaji; Verheij, Elwin E R; Bas, Richard C; Hendriks, Margriet W B; Hankemeier, Thomas; Thissen, Uwe; Coulier, Leon

2013-05-15

Mass spectra obtained by deconvolution of liquid chromatography/high-resolution mass spectrometry (LC/HRMS) data can be impaired by non-informative mass-over-charge (m/z) channels. This impairment of mass spectra can have significant negative influence on further post-processing, like quantification and identification. A metric derived from the knowledge of errors in isotopic distribution patterns, and quality of the signal within a pre-defined mass chromatogram block, has been developed to pre-select all informative m/z channels. This procedure results in the clean-up of deconvoluted mass spectra by maintaining the intensity counts from m/z channels that originate from a specific compound/molecular ion, for example, molecular ion, adducts, (13) C-isotopes, multiply charged ions and removing all m/z channels that are not related to the specific peak. The methodology has been successfully demonstrated for two sets of high-resolution LC/MS data. The approach described is therefore thought to be a useful tool in the automatic processing of LC/HRMS data. It clearly shows the advantages compared to other approaches like peak picking and de-isotoping in the sense that all information is retained while non-informative data is removed automatically. Copyright © 2013 John Wiley & Sons, Ltd.

THINGS: THE H I NEARBY GALAXY SURVEY

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

Walter, Fabian; Bigiel, Frank; Leroy, Adam

2008-12-15

We present 'The H I Nearby Galaxy Survey (THINGS)', a high spectral ({<=}5.2 km s{sup -1}) and spatial ({approx}6'') resolution survey of H I emission in 34 nearby galaxies obtained using the NRAO Very Large Array (VLA). The overarching scientific goal of THINGS is to investigate fundamental characteristics of the interstellar medium (ISM) related to galaxy morphology, star formation, and mass distribution across the Hubble sequence. Unique characteristics of the THINGS database are the homogeneous sensitivity as well as spatial and velocity resolution of the H I data, which is at the limit of what can be achieved with themore » VLA for a significant number of galaxies. A sample of 34 objects at distances 2 {approx}< D {approx}< 15 Mpc (resulting in linear resolutions of {approx}100 to 500 pc) are targeted in THINGS, covering a wide range of star formation rates ({approx}10{sup -3} to 6 M{sub sun} yr{sup -1}), total H I masses M{sub HI} (0.01 to 14 x 10{sup 9} M{sub sun}), absolute luminosities M{sub B} (-11.5 to -21.7 mag), and metallicities (7.5 to 9.2 in units of 12+log[O/H]). We describe the setup of the VLA observations, the data reduction procedures, and the creation of the final THINGS data products. We present an atlas of the integrated H I maps, the velocity fields, the second moment (velocity dispersion) maps and individual channel maps of each THINGS galaxy. The THINGS data products are made publicly available through a dedicated webpage. Accompanying THINGS papers (in this issue of the Astronomical Journal) address issues such as the small-scale structure of the ISM, the (dark) matter distribution in THINGS galaxies, and the processes leading to star formation.« less

High resolution seismic stratigraphy and Mass Transport Deposits of the proximal continental margin, offshore Quarteira, South Portugal: Preliminary Results.

NASA Astrophysics Data System (ADS)

Duarte, Débora; Santos, Joana; Terrinha, Pedro; Brito, Pedro; Noiva, João; Ribeiro, Carlos; Roque, Cristina

2017-04-01

More than 300 nautical miles of multichannel seismic reflection data were acquired in the scope of the ASTARTE project (Assessment Strategy and Risk Reduction for Tsunamis in Europe), off Quarteira, Algarve, South Portugal. The main goal of this very high resolution multichannel seismic survey was to obtain high-resolution images of the sedimentary record to try to discern the existence of high energy events, possibly tsunami backwash deposits associated with large magnitude earthquakes generated at the Africa-Eurasia plate boundary This seismic dataset was processed at the Instituto Português do Mar e da Atmosfera (IPMA), with the SeisSpace PROMAX Seismic Processing software. A tailor-made processing flow was applied, focusing in the removal of the seafloor multiple and in the enhancement of the superficial layers. A sparker source, using with 300 J of energy and a fire rate of 0,5 s was used onboard Xunauta, an 18 m long vessel. The preliminary seismostratigraphic interpretation of the Algarve ASTARTE seismic dataset allowed the identification of a complex sequence seismic units of progradational and agradational bodies as well as Mass Transported Deposits (MTD). The MTD package of sediments has a very complex internal structure, 20m of thickness, is apparently spatially controlled by an escarpment probably associated to past sea level low stands. The MTD covers across an area, approximately parallel to an ancient coastline, with >30 km (length) x 5 km (across). Acknowledgements: This work was developed as part of the project ASTARTE (603839 FP7) supported by the grant agreement No 603839 of the European Union's Seventh. The Instituto Portugues do Mar e da Atmosfera acknowledges support by Landmark Graphics (SeisWorks) via the Landmark University Grant Program.

Identification of Radar Facies and Linked Process-Based Palaeo-environmental Interpretations, Cooloola Sand Mass, Queensland, Australia

NASA Astrophysics Data System (ADS)

Gontz, A. M.; McCallum, A. B.; Moss, P. T.; Shulmeister, J.

2015-12-01

During 2015 and 2014, nearly 60 km of high-resolution ground penetrating radar data were acquired on the Cooloola Sand Mass (CSM) in southeastern coastal Queensland. The CSM is part of the world's largest downdrift sand system. It contains three of the world's largest sand islands, several National Parks, a UNESCO World Heritage Site and covers 500 km of the eastern Australian coastline in northern New South Wales and southern Queensland. The large (>200 m) composite dunes of the CSM exhibit multiple activation phases, coastally eroding bluffs and dune development is not obvious from surficial exposures. This provides an ideal environment for ground penetrating radar. The dune sequences have been provisionally dated to the mid Quaternary through present and represent the potential for a large palaeo-environmental proxy dataset. GPR imagery was collected using a MALA GeoSciences Ground Explorer (GX) system with 160 and 450 MHz antennae from the numerous physiographic and ecological provinces as well as mapped surficial soil units at the CSM. These data were used to determine the subsurface architecture, identify radar facies and develop environmental interpretations. In the clean, aeolian quartz-rich sands, radar wave penetration exceeded 30 m (radar velocity = 0.07 m/ns) with the 160 MHz antenna. From the interpreted environmental units including palaeosol, dune slip face, dune stoss face, sand blow, beach, estuarine and fluvial, we are developing maps to relate the units and focus a detailed sampling regime that includes OSL, sediment geochemistry and sedimentology, The interpreted units, stratigraphic correlation and spatial distribution of the facies is the first step in a broader project to unravel the Quaternary environmental and climate records that are archived within the sediments of the CSM.

Characterization of extreme ultraviolet laser ablation mass spectrometry for actinide trace analysis and nanoscale isotopic imaging

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

Green, Tyler; Kuznetsov, Ilya; Willingham, David

The purpose of this research was to characterize Extreme Ultraviolet Time-of-Flight (EUV TOF) Laser Ablation Mass Spectrometry for high spatial resolution elemental and isotopic analysis. We compare EUV TOF results with Secondary Ionization Mass Spectrometry (SIMS) to orient the EUV TOF method within the overall field of analytical mass spectrometry. Using the well-characterized NIST 61x glasses, we show that the EUV ionization approach produces relatively few molecular ion interferences in comparison to TOF SIMS. We demonstrate that the ratio of element ion to element oxide ion is adjustable with EUV laser pulse energy and that the EUV TOF instrument hasmore » a sample utilization efficiency of 0.014%. The EUV TOF system also achieves a lateral resolution of 80 nm and we demonstrate this lateral resolution with isotopic imaging of closely spaced particles or uranium isotopic standard materials.« less

Three-dimensional nanoscale molecular imaging by extreme ultraviolet laser ablation mass spectrometry

PubMed Central

Kuznetsov, Ilya; Filevich, Jorge; Dong, Feng; Woolston, Mark; Chao, Weilun; Anderson, Erik H.; Bernstein, Elliot R.; Crick, Dean C.; Rocca, Jorge J.; Menoni, Carmen S.

2015-01-01

Analytical probes capable of mapping molecular composition at the nanoscale are of critical importance to materials research, biology and medicine. Mass spectral imaging makes it possible to visualize the spatial organization of multiple molecular components at a sample's surface. However, it is challenging for mass spectral imaging to map molecular composition in three dimensions (3D) with submicron resolution. Here we describe a mass spectral imaging method that exploits the high 3D localization of absorbed extreme ultraviolet laser light and its fundamentally distinct interaction with matter to determine molecular composition from a volume as small as 50 zl in a single laser shot. Molecular imaging with a lateral resolution of 75 nm and a depth resolution of 20 nm is demonstrated. These results open opportunities to visualize chemical composition and chemical changes in 3D at the nanoscale. PMID:25903827

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

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

Zhou, Mowei; Yan, Jing; Romano, Christine A.

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase Mnx from Bacillus sp. PL-12 has been successfully overexpressed in active form, unexpectedly, as a protein complex with a molecular weight of 211 kDa with no homology to known proteins in the database. We have recently used surface induced dissociation (SID) and ion mobility – mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data frommore » the native mass spectrometry experiment led to a plausible model of this unknown multicopper oxidase which has been difficult to study by conventional structural biology methods. However, because each subunit of Mnx binds copper ions as cofactor at varying ratios, there were remaining ambiguities in assigning some of the observed peaks to metal-binding species because of the sample heterogeneity and limited mass resolution. In this study, we performed SID in a modified Fourier transform – ion cyclotron resonance (FT-ICR) mass spectrometer for obtaining the ultimate resolution on the released subcomplexes of Mnx. The high mass accuracy and resolution unveiled unexpected artificial modifications in the protein that have been previously thought to be iron bound species based on lower resolution data. Additionally, most released subcomplexes were isotopically resolved for defining metal binding stoichiometry at each structural level. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes.« less

High-sensitivity Leak-testing Method with High-Resolution Integration Technique

NASA Astrophysics Data System (ADS)

Fujiyoshi, Motohiro; Nonomura, Yutaka; Senda, Hidemi

A high-resolution leak-testing method named HR (High-Resolution) Integration Technique has been developed for MEMS (Micro Electro Mechanical Systems) sensors such as a vibrating angular-rate sensor housed in a vacuum package. Procedures of the method to obtain high leak-rate resolution were as follows. A package filled with helium gas was kept in a small accumulation chamber to accumulate helium gas leaking from the package. After the accumulation, the accumulated helium gas was introduced into a mass spectrometer in a short period of time, and the flux of the helium gas was measured by the mass spectrometer as a transient phenomenon. The leak-rate of the package was calculated from the detected transient waveform of the mass spectrometer and the accumulation time of the helium gas in the accumulation chamber. Because the density of the helium gas in the vacuum chamber increased and the accumulated helium gas was measured in a very short period of time with the mass spectrometer, the peak strength of the transient waveform became high and the signal to noise ratio was much improved. The detectable leak-rate resolution of the technique reached 1×10-15 (Pa·m3/s). This resolution is 103 times superior to that of the conventional helium vacuum integration method. The accuracy of the measuring system was verified with a standard helium gas leak source. The results were well matched between theoretical calculation based on the leak-rate of the source and the experimental results within only 2% error.

Science Observations of Deep Space One

NASA Technical Reports Server (NTRS)

Nelson, Robert M.; Baganal, Fran; Boice, Daniel C.; Britt, Daniel T.; Brown, Robert H.; Buratti, Bonnie J.; Creary, Frank; Ip, Wing-Huan; Meier, Roland; Oberst, Juergen

1999-01-01

During the Deep Space One (DS1) primary mission, the spacecraft will fly by asteroid 1992 KD and possibly comet Borrelly. There are two technologies being validated on DS1 that will provide science observations of these targets, the Miniature Integrated Camera Spectrometer (MICAS) and the Plasma Experiment for Planetary Exploration (PEPE). MICAS encompasses a camera, an ultraviolet imaging spectrometer and an infrared imaging spectrometer. PEPE combines an ion and electron analyzer designed to determine the three-dimensional distribution of plasma over its field of view. MICAS includes two visible wavelength imaging channels, an ultraviolet imaging spectrometer, and an infrared imaging spectrometer all of which share a single 10-cm diameter telescope. Two types of visible wavelength detectors, both operating between about 500 and 1000 nm are used: a CCD with 13-microrad pixels and an 18-microrad-per-pixel, metal-on-silicon active pixel sensor (APS). Unlike the CCD the APS includes the timing and control electronics on the chip along with the detector. The UV spectrometer spans 80 to 185 nm with 0.64-nm spectral resolution and 316-microrad pixels. The IR spectrometer covers the range from 1200 to 2400 nm with 6.6-nm resolution and 54-microrad pixels PEPE includes a very low-power, low-mass micro-calorimeter to help understand plasma-surface interactions and a plasma analyzer to identify de individual molecules and atoms in the immediate vicinity of the spacecraft that have been eroded off the surface of asteroid 1992 KD. It employs common apertures with separate electrostatic energy analyzers. It measures electron and ion energies spanning a range of 3 eV to 30 keV, with a resolution of five percent. and measures ion mass from one to 135 atomic mass units with 5 percent resolution. It electrostatically sweeps its field of view both in elevation and azimuth. Both MICAS and PEPE represent a new direction for the evolution of science instruments for interplanetary spacecraft. These two instruments incorporate a large fraction of the capability of five instruments that had typically flown on NASA's deep space missions The Deep Space One science team acknowledges the support of Philip Varghese, David H. Lehman, Leslie Livesay, and Marc Rayman for providing invaluable assistance in making the science observations possible.

Meter-scale morphology of the north polar region of Mars.

PubMed

Herkenhoff, K E; Byrne, S; Russell, P S; Fishbaugh, K E; McEwen, A S

2007-09-21

Mars' north pole is covered by a dome of layered ice deposits. Detailed ( approximately 30 centimeters per pixel) images of this region were obtained with the High-Resolution Imaging Science Experiment on board the Mars Reconnaissance Orbiter (MRO). Planum Boreum basal unit scarps reveal cross-bedding and show evidence for recent mass wasting, flow, and debris accumulation. The north polar layers themselves are as thin as 10 centimeters but appear to be covered by a dusty veneer in places, which may obscure thinner layers. Repetition of particular layer types implies that quasi-periodic climate changes influenced the stratigraphic sequence in the polar layered deposits, informing models for recent climate variations on Mars.

UNSEDATED COMPUTED TOMOGRAPHY FOR DIAGNOSIS OF PELVIC CANAL OBSTRUCTION IN A LEOPARD GECKO (EUBLEPHARIS MACULARIUS).

PubMed

DeCourcy, Kelly; Hostnik, Eric T; Lorbach, Josh; Knoblaugh, Sue

2016-12-01

An adult leopard gecko ( Eublepharis macularius ) presented for lethargy, hyporexia, weight loss, decreased passage of waste, and a palpable caudal coelomic mass. Computed tomography showed a heterogeneous hyperattenuating (∼143 Hounsfield units) structure within the right caudal coelom. The distal colon-coprodeum lumen or urinary bladder was hypothesized as the most likely location for the heterogeneous structure. Medical support consisted of warm water and lubricant enema, as well as a heated environment. Medical intervention aided the passage of a plug comprised centrally of cholesterol and urates with peripheral stratified layers of fibrin, macrophages, heterophils, and bacteria. Within 24 hr, a follow-up computed tomography scan showed resolution of the pelvic canal plug.

Meter-scale morphology of the north polar region of mars

USGS Publications Warehouse

Herkenhoff, K. E.; Byrne, S.; Russell, P.S.; Fishbaugh, K.E.; McEwen, A.S.

2007-01-01

Mars' north pole is covered by a dome of layered ice deposits. Detailed (???30 centimeters per pixel) images of this region were obtained with the High-Resolution Imaging Science Experiment on board the Mars Reconnaissance Orbiter (MRO). Planum Boreum basal unit scarps reveal cross-bedding and show evidence for recent mass wasting, flow, and debris accumulation. The north polar layers themselves are as thin as 10 centimeters but appear to be covered by a dusty veneer in places, which may obscure thinner layers. Repetition of particular layer types implies that quasi-periodic climate changes influenced the stratigraphic sequence in the polar layered deposits, informing models for recent climate variations on Mars.

Development, calibration, and sensitivity analyses of a high-resolution dissolved oxygen mass balance model for the northern Gulf of Mexico

EPA Science Inventory

A high-resolution dissolved oxygen mass balance model was developed for the Louisiana coastal shelf in the northern Gulf of Mexico. GoMDOM (Gulf of Mexico Dissolved Oxygen Model) was developed to assist in evaluating the impacts of nutrient loading on hypoxia development and exte...

Identifying Complex Mixtures in the Environment with Cheminformatics and Non-targeted High Resolution Mass Spectrometry (SETAC NA Focused Topic Meeting : Risk Assessment of Chemical Mixtures)

EPA Science Inventory

Non-target high resolution mass spectrometry techniques combined with advanced cheminformatics offer huge potential for exploring complex mixtures in our environment – yet also offers plenty of challenges. Peak inventories of several non-target studies from within Europe reveal t...

Light-absorbing oligomer formation in secondary organic aerosol from reactive uptake of isoprene epoxydiols.

PubMed

Lin, Ying-Hsuan; Budisulistiorini, Sri Hapsari; Chu, Kevin; Siejack, Richard A; Zhang, Haofei; Riva, Matthieu; Zhang, Zhenfa; Gold, Avram; Kautzman, Kathryn E; Surratt, Jason D

2014-10-21

Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

NASA Astrophysics Data System (ADS)

Zhou, Mowei; Yan, Jing; Romano, Christine A.; Tebo, Bradley M.; Wysocki, Vicki H.; Paša-Tolić, Ljiljana

2018-01-01

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes. [Figure not available: see fulltext.

Crystallization and preliminary X-ray diffraction studies of the lipopolysaccharide core biosynthetic enzyme ADP-L-glycero-D-mannoheptose 6-epimerase from Escherichia coli K-12.

PubMed

Ding, L; Zhang, Y; Deacon, A M; Ealick, S E; Ni, Y; Sun, P; Coleman, W G

1999-03-01

ADP-L-glycero-D-mannoheptose 6-epimerase is a 240 kDa NAD-dependent nucleotide diphosphosugar epimerase from Escherichia coli K12 which catalyzes the interconversion of ADP-D-glycero-D-mannoheptose and ADP-L-glycero-D-mannoheptose. ADP-L-glycero-D-mannoheptose is a required intermediate for lipopolysaccharide inner-core and outer-membrane biosynthesis in several genera of pathogenic and non-pathogenic Gram-negative bacteria. ADP-L-glycero-D-mannoheptose 6-epimerase was overexpressed in E. coli and purified to apparent homogeneity by chromatographic methods. Three crystal forms of the epimerase were obtained by a hanging-drop vapor-diffusion method. A native data set for crystal form III was collected in-house on a Rigaku R-AXIS-IIC image plate at 3.0 A resolution. The form III crystals belong to the monoclinic space group P21. The unit-cell parameters are a = 98.94, b = 110.53, c = 180.68 A and beta = 90.94 degrees. Our recent results show that these crystals diffract to 2.0 A resolution at the Cornell High Energy Synchrotron Source. The crystal probably contains six 40 kDa monomers per asymmetric unit, with a corresponding volume per protein mass (Vm) of 4.11 A3 Da-1 and a solvent fraction of 70%.

Crystallization of Spätzle, a cystine-knot protein involved in embryonic development and innate immunity in Drosophila melanogaster

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

Hoffmann, Anita; Neumann, Piotr; Schierhorn, Angelika

2008-08-01

Crystallization of the cystine-knot protein Spätzle occurred following serendipitous limited degradation of the pro-Spätzle propeptide during the crystallization experiment. The Spätzle protein is involved in both the definition of the dorsal–ventral axis during embryonic development and in the adult innate immune response. The disulfide-linked dimeric cystine-knot protein has been expressed as a proprotein in inclusion bodies in Escherichia coli and refolded in vitro by rapid dilution. Initial orthorhombic crystals that diffracted to 7 Å resolution were obtained after three months by the sitting-drop vapour-diffusion method. Optimization of the crystallization conditions resulted in orthorhombic crystals (space group P2{sub 1}2{sub 1}2{sub 1},more » with unit-cell parameters a = 53.0, b = 59.2, c = 62.5 Å) that diffracted to 2.8 Å resolution in-house. The small volume of the asymmetric unit indicated that it was not possible for the crystals to contain the complete pro-Spätzle dimer. Mass spectrometry, N-terminal sequencing and Western-blot analysis revealed that the crystals contained the C-terminal disulfide-linked cystine-knot dimer. Comparison of various crystallization experiments indicated that degradation of the N-terminal prodomain was dependent on the buffer conditions.« less

Tempest: GPU-CPU computing for high-throughput database spectral matching.

PubMed

Milloy, Jeffrey A; Faherty, Brendan K; Gerber, Scott A

2012-07-06

Modern mass spectrometers are now capable of producing hundreds of thousands of tandem (MS/MS) spectra per experiment, making the translation of these fragmentation spectra into peptide matches a common bottleneck in proteomics research. When coupled with experimental designs that enrich for post-translational modifications such as phosphorylation and/or include isotopically labeled amino acids for quantification, additional burdens are placed on this computational infrastructure by shotgun sequencing. To address this issue, we have developed a new database searching program that utilizes the massively parallel compute capabilities of a graphical processing unit (GPU) to produce peptide spectral matches in a very high throughput fashion. Our program, named Tempest, combines efficient database digestion and MS/MS spectral indexing on a CPU with fast similarity scoring on a GPU. In our implementation, the entire similarity score, including the generation of full theoretical peptide candidate fragmentation spectra and its comparison to experimental spectra, is conducted on the GPU. Although Tempest uses the classical SEQUEST XCorr score as a primary metric for evaluating similarity for spectra collected at unit resolution, we have developed a new "Accelerated Score" for MS/MS spectra collected at high resolution that is based on a computationally inexpensive dot product but exhibits scoring accuracy similar to that of the classical XCorr. In our experience, Tempest provides compute-cluster level performance in an affordable desktop computer.

Does Explosive Nuclear Burning Occur in Tidal Disruption Events of White Dwarfs by Intermediate-mass Black Holes?

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

Tanikawa, Ataru; Sato, Yushi; Hachisu, Izumi

We investigate nucleosynthesis in tidal disruption events (TDEs) of white dwarfs (WDs) by intermediate-mass black holes. We consider various types of WDs with different masses and compositions by means of three-dimensional (3D) smoothed particle hydrodynamics (SPH) simulations. We model these WDs with different numbers of SPH particles, N , from a few 10{sup 4} to a few 10{sup 7} in order to check mass resolution convergence, where SPH simulations with N > 10{sup 7} (or a space resolution of several 10{sup 6} cm) have unprecedentedly high resolution in this kind of simulation. We find that nuclear reactions become less activemore » with increasing N and that these nuclear reactions are excited by spurious heating due to low resolution. Moreover, we find no shock wave generation. In order to investigate the reason for the absence of a shock wave, we additionally perform one-dimensional (1D) SPH and mesh-based simulations with a space resolution ranging from 10{sup 4} to 10{sup 7} cm, using a characteristic flow structure extracted from the 3D SPH simulations. We find shock waves in these 1D high-resolution simulations, one of which triggers a detonation wave. However, we must be careful of the fact that, if the shock wave emerged in an outer region, it could not trigger the detonation wave due to low density. Note that the 1D initial conditions lack accuracy to precisely determine where a shock wave emerges. We need to perform 3D simulations with ≲10{sup 6} cm space resolution in order to conclude that WD TDEs become optical transients powered by radioactive nuclei.« less

Contemporary instrumentation and application of charge exchange neutral particle diagnostics in magnetic fusion energy experiments.

PubMed

Medley, S S; Donné, A J H; Kaita, R; Kislyakov, A I; Petrov, M P; Roquemore, A L

2008-01-01

An overview of the developments postcirca 1980s in the instrumentation and application of charge exchange neutral particle diagnostics on magnetic fusion energy experiments is presented. First, spectrometers that employ only electric fields and hence provide ion energy resolution but not mass resolution are discussed. Next, spectrometers that use various geometrical combinations of both electric and magnetic fields to provide both energy and mass resolutions are reviewed. Finally, neutral particle diagnostics based on utilization of time-of-flight techniques are presented.

Parallel Spectral Acquisition with an Ion Cyclotron Resonance Cell Array.

PubMed

Park, Sung-Gun; Anderson, Gordon A; Navare, Arti T; Bruce, James E

2016-01-19

Mass measurement accuracy is a critical analytical figure-of-merit in most areas of mass spectrometry application. However, the time required for acquisition of high-resolution, high mass accuracy data limits many applications and is an aspect under continual pressure for development. Current efforts target implementation of higher electrostatic and magnetic fields because ion oscillatory frequencies increase linearly with field strength. As such, the time required for spectral acquisition of a given resolving power and mass accuracy decreases linearly with increasing fields. Mass spectrometer developments to include multiple high-resolution detectors that can be operated in parallel could further decrease the acquisition time by a factor of n, the number of detectors. Efforts described here resulted in development of an instrument with a set of Fourier transform ion cyclotron resonance (ICR) cells as detectors that constitute the first MS array capable of parallel high-resolution spectral acquisition. ICR cell array systems consisting of three or five cells were constructed with printed circuit boards and installed within a single superconducting magnet and vacuum system. Independent ion populations were injected and trapped within each cell in the array. Upon filling the array, all ions in all cells were simultaneously excited and ICR signals from each cell were independently amplified and recorded in parallel. Presented here are the initial results of successful parallel spectral acquisition, parallel mass spectrometry (MS) and MS/MS measurements, and parallel high-resolution acquisition with the MS array system.

Preventive doping control screening analysis of prohibited substances in human urine using rapid-resolution liquid chromatography/high-resolution time-of-flight mass spectrometry.

PubMed

Vonaparti, A; Lyris, E; Angelis, Y S; Panderi, I; Koupparis, M; Tsantili-Kakoulidou, A; Peters, R J B; Nielen, M W F; Georgakopoulos, C

2010-06-15

Unification of the screening protocols for a wide range of doping agents has become an important issue for doping control laboratories. This study presents the development and validation of a generic liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) screening method of 241 small molecule analytes from various categories of prohibited substances (stimulants, narcotics, diuretics, beta(2)-agonists, beta-blockers, hormone antagonists and modulators, glucocorticosteroids and anabolic agents). It is based on a single-step liquid-liquid extraction of hydrolyzed urine and the use of a rapid-resolution liquid chromatography/high-resolution time-of-flight mass spectrometric system acquiring continuous full scan data. Electrospray ionization in the positive mode was used. Validation parameters consisted of identification capability, limit of detection, specificity, ion suppression, extraction recovery, repeatability and mass accuracy. Detection criteria were established on the basis of retention time reproducibility and mass accuracy. The suitability of the methodology for doping control was demonstrated with positive urine samples. The preventive role of the method was proved by the case where full scan acquisition with accurate mass measurement allowed the retrospective reprocessing of acquired data from past doping control samples for the detection of a designer drug, the stimulant 4-methyl-2-hexanamine, which resulted in re-reporting a number of stored samples as positives for this particular substance, when, initially, they had been reported as negatives. Copyright (c) 2010 John Wiley & Sons, Ltd.

40 CFR 60.1795 - May I conduct stack testing less often?

Code of Federal Regulations, 2010 CFR

2010-07-01

... dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter... meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter (total mass) for... 15 nanograms per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry...

40 CFR 60.1795 - May I conduct stack testing less often?

Code of Federal Regulations, 2012 CFR

2012-07-01

... dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter... meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter (total mass) for... 15 nanograms per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry...

40 CFR 60.1795 - May I conduct stack testing less often?

Code of Federal Regulations, 2014 CFR

2014-07-01

... dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter... meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter (total mass) for... 15 nanograms per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry...

Case study of water-soluble metal containing organic constituents of biomass burning aerosol.

PubMed

Chang-Graham, Alexandra L; Profeta, Luisa T M; Johnson, Timothy J; Yokelson, Robert J; Laskin, Alexander; Laskin, Julia

2011-02-15

Natural and prescribed biomass fires are a major source of aerosols that may persist in the atmosphere for several weeks. Biomass burning aerosols (BBA) can be associated with long-range transport of water-soluble N-, S-, P-, and metal-containing species. In this study, BBA samples were collected using a particle-into-liquid sampler (PILS) from laboratory burns of vegetation collected on military bases in the southeastern and southwestern United States. The samples were then analyzed using high resolution electrospray ionization mass spectrometry (ESI/HR-MS) that enabled accurate mass measurements for hundreds of species with m/z values between 70 and 1000 and assignment of elemental formulas. Mg, Al, Ca, Cr, Mn, Fe, Ni, Cu, Zn, and Ba-containing organometallic species were identified. The results suggest that the biomass may have accumulated metal-containing species that were re-emitted during biomass burning. Further research into the sources, dispersion, and persistence of metal-containing aerosols, as well as their environmental effects, is needed.

Fourier Transform Mass Spectrometry.

ERIC Educational Resources Information Center

Gross, Michael L.; Rempel, Don L.

1984-01-01

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

Science Priorities of the RadioAstron Space VLBI Mission

NASA Astrophysics Data System (ADS)

Langston, Glen; Kardashev, N.; International Space VLBI Collaboration

2006-12-01

The main scientific goal of the RadioAstron Space VLBI mission is study of Active Galactic Nuclei (AGN), Masers and other astronomical objects with unprecedented angular resolution, up to few millionths of an arc-second. The resolution achieved with RadioAstron will allow study the following phenomena and problems: * Central engine of AGN and physical processes near super massive black holes providing an acceleration of cosmic rays size, velocity and shape of emitting region in the core, spectrum, polarization and variability of emitting components; * Cosmological models, dark matter and dark energy by studying dependence of above mentioned AGN's parameters with redshift, and by observing gravitational lensing; * Structure and dynamics of star and planets forming regions in our Galaxy and in AGN by studying maser and Mega maser radio emission; * Neutron (quark?) stars and black holes in our Galaxy, their structure and dynamics by VLBI and measurements of visibility scintillations, proper motions and parallaxes; * Structure and distribution of interstellar and interplanetary plasma by fringe visibility scintillations of pulsars; The RadioAstron mission uses the satellite SPECTR (astrophysical module), developed by Lavochkin Association of Russian Aviation and Space Agency (RASA). This module will be used in several other scientific missions. The total mass of the scientific payload is about 2500 kg, of which the unfolding parabolic 10-m radio astronomy antenna's mass is about 1500 kg, and scientific package holding the receivers, power supply, synthesizers, control units, frequency standards and data transmission radio system. The mass of the whole system (satellite and scientific payload) to be carried into orbit by the powerful "Zenit-2SB"-"Fregat-2CB" launcher is about 5000 kg. The RadioAstron project is an international collaboration between RASA and ground radio telescope facilities around the world.

Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry

PubMed Central

Souda, Puneet; Ryan, Christopher M.; Cramer, William A.; Whitelegge, Julian

2011-01-01

Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein’s native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electroncapture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. PMID:21982782

Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry.

PubMed

Souda, Puneet; Ryan, Christopher M; Cramer, William A; Whitelegge, Julian

2011-12-01

Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein's native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electron-capture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. Copyright © 2011 Elsevier Inc. All rights reserved.

Stimulated Motion Suppression (STMS): a New Approach to Break the Resolution Barrier for Ion Trap Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhou, Xiaoyu; Liu, Xinwei; Chiang, Spencer; Cao, Wenbo; Li, Ming; Ouyang, Zheng

2018-05-01

Ion trap is an excellent platform to perform tandem mass spectrometry (MS/MS), but has an intrinsic drawback in resolving power. Using ion resonant ejection as an example, the resolution degradation can be largely attributed to the broadening of the resonant frequency band (RFB) between ion motion and driving alternative-current (AC). To solve this problem, stimulated motion suppression (STMS) was developed. The key idea of STMS is the use of two suppression alternative-current (SAC) signals, which both have reversed initial phases to the main AC. The SACs can block the unexpected sideband ion resonances (or ejections), therefore playing a key role in sharpening the RFB. The proof-of-concept has been demonstrated through ion trajectory simulations and validated experimentally. STMS provides a new and versatile means for the improvement of the ion trap resolution, which for a long time has reached the bottleneck through conventional methods, e.g., increasing the radio-frequency (RF) voltage and decreasing the mass scan rate. At the end, it is worth noting that the idea of STMS is very general and principally can be applied in any RF device for the purposes of high-resolution mass analysis and ion isolation.

Initial mass function of planetesimals formed by the streaming instability

NASA Astrophysics Data System (ADS)

Schäfer, Urs; Yang, Chao-Chin; Johansen, Anders

2017-01-01

The streaming instability is a mechanism to concentrate solid particles into overdense filaments that undergo gravitational collapse and form planetesimals. However, it remains unclear how the initial mass function of these planetesimals depends on the box dimensions of numerical simulations. To resolve this, we perform simulations of planetesimal formation with the largest box dimensions to date, allowing planetesimals to form simultaneously in multiple filaments that can only emerge within such large simulation boxes. In our simulations, planetesimals with sizes between 80 km and several hundred kilometers form. We find that a power law with a rather shallow exponential cutoff at the high-mass end represents the cumulative birth mass function better than an integrated power law. The steepness of the exponential cutoff is largely independent of box dimensions and resolution, while the exponent of the power law is not constrained at the resolutions we employ. Moreover, we find that the characteristic mass scale of the exponential cutoff correlates with the mass budget in each filament. Together with previous studies of high-resolution simulations with small box domains, our results therefore imply that the cumulative birth mass function of planetesimals is consistent with an exponentially tapered power law with a power-law exponent of approximately -1.6 and a steepness of the exponential cutoff in the range of 0.3-0.4.

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer.

PubMed

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D; Wolff, Jeremy J; Somogyi, Árpád; Pedder, Randall E; Quintyn, Royston S; Morrison, Lindsay J; Easterling, Michael L; Paša-Tolić, Ljiljana; Wysocki, Vicki H

2017-01-03

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on noncovalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. In this study, an SID device was designed and successfully installed in a hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.

Design and development of a fast ion mass spectrometer

NASA Technical Reports Server (NTRS)

Burch, J. L.

1983-01-01

Two Fast Ion Mass Spectrometers (FIMS A and FIMS B) were developed. The design, development, construction, calibration, integration, and flight of these instruments, along with early results from the data analysis efforts are summarized. A medium energy ion mass spectrometer that covers mass velocity space with significantly higher time resolution, improved mass resolution, (particularly for heavier ions), and wider energy range than existing instruments had achieved was completed. The initial design consisted of a dual channel cylindrical electrostatic analyzer followed by a dual channel cylindrical velocity filter. The gain versus count rate characteristics of the high current channel electron multipliers (CEM's), which were chosen for ion detection, revealed a systematic behavior that can be used as a criterion for selection of CEM's for long counting lifetimes.

High-Resolution Metabolomics Assessment of Military Personnel: Evaluating Analytical Strategies for Chemical Detection.

PubMed

Liu, Ken H; Walker, Douglas I; Uppal, Karan; Tran, ViLinh; Rohrbeck, Patricia; Mallon, Timothy M; Jones, Dean P

2016-08-01

The aim of this study was to maximize detection of serum metabolites with high-resolution metabolomics (HRM). Department of Defense Serum Repository (DoDSR) samples were analyzed using ultrahigh resolution mass spectrometry with three complementary chromatographic phases and four ionization modes. Chemical coverage was evaluated by number of ions detected and accurate mass matches to a human metabolomics database. Individual HRM platforms provided accurate mass matches for up to 58% of the KEGG metabolite database. Combining two analytical methods increased matches to 72% and included metabolites in most major human metabolic pathways and chemical classes. Detection and feature quality varied by analytical configuration. Dual chromatography HRM with positive and negative electrospray ionization provides an effective generalized method for metabolic assessment of military personnel.

High-resolution metabolomics assessment of military personnel: Evaluating analytical strategies for chemical detection

PubMed Central

Liu, Ken H.; Walker, Douglas I.; Uppal, Karan; Tran, ViLinh; Rohrbeck, Patricia; Mallon, Timothy M.; Jones, Dean P.

2016-01-01

Objective To maximize detection of serum metabolites with high-resolution metabolomics (HRM). Methods Department of Defense Serum Repository (DoDSR) samples were analyzed using ultra-high resolution mass spectrometry with three complementary chromatographic phases and four ionization modes. Chemical coverage was evaluated by number of ions detected and accurate mass matches to a human metabolomics database. Results Individual HRM platforms provided accurate mass matches for up to 58% of the KEGG metabolite database. Combining two analytical methods increased matches to 72%, and included metabolites in most major human metabolic pathways and chemical classes. Detection and feature quality varied by analytical configuration. Conclusions Dual chromatography HRM with positive and negative electrospray ionization provides an effective generalized method for metabolic assessment of military personnel. PMID:27501105

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.

Orthogonal time-of-flight mass spectrometry of an ion beam with a broad kinetic energy profile.

PubMed

Miller, S W; Prince, B D; Bemish, R J

2017-10-01

A combined experimental and modeling effort is undertaken to assess a detection system composed of an orthogonal extraction time-of-flight (TOF) mass spectrometer coupled to a continuous ion source emitting an ion beam with kinetic energy of several hundred eV. The continuous ion source comprises an electrospray capillary system employing an undiluted ionic liquid emitting directly into vacuum. The resulting ion beam consists of ions with kinetic energy distributions of width greater than a hundred of eV and mass-to-charge (m/q) ratios ranging from 111 to 500 000 amu/q. In particular, the investigation aims to demonstrate the kinetic energy resolution along the ion beam axis (axial) of orthogonally extracted ions in measurements of the axial kinetic energy-specific mass spectrum, mass flow rate, and total ion current. The described instrument is capable of simultaneous measurement of a broad m/q range in a single acquisition cycle with approximately 25 eV/q axial kinetic energy resolution. Mass resolutions of ∼340 (M/ΔM, FWHM) were obtained for ions at m/q = 1974. Comparison of the orthogonally extracted TOF mass spectrum to mass flow and ion current measurements obtained with a quartz-crystal microbalance and Faraday cup, respectively, shows reasonable numeric agreement and qualitative agreement in the trend as a function of energy defect.

16 CFR 500.9 - Units of weight or mass, how expressed.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 16 Commercial Practices 1 2011-01-01 2011-01-01 false Units of weight or mass, how expressed. 500... UNDER SECTION 4 OF THE FAIR PACKAGING AND LABELING ACT § 500.9 Units of weight or mass, how expressed. (a) The term net weight or net mass may be used in stating the net quantity of contents in terms of...

16 CFR 500.9 - Units of weight or mass, how expressed.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Units of weight or mass, how expressed. 500... UNDER SECTION 4 OF THE FAIR PACKAGING AND LABELING ACT § 500.9 Units of weight or mass, how expressed. (a) The term net weight or net mass may be used in stating the net quantity of contents in terms of...

Mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-09-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, Daniel D.; Keville, Robert F.

1995-01-01

An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

Evolution of Orbitrap Mass Spectrometry Instrumentation

NASA Astrophysics Data System (ADS)

Eliuk, Shannon; Makarov, Alexander

2015-07-01

We discuss the evolution of OrbitrapTM mass spectrometry (MS) from its birth in the late 1990s to its current role as one of the most prominent techniques for MS. The Orbitrap mass analyzer is the first high-performance mass analyzer that employs trapping of ions in electrostatic fields. Tight integration with the ion injection process enables the high-resolution, mass accuracy, and sensitivity that have become essential for addressing analytical needs in numerous areas of research, as well as in routine analysis. We examine three major families of instruments (related to the LTQ Orbitrap, Q Exactive, and Orbitrap Fusion mass spectrometers) in the context of their historical development over the past ten eventful years. We discuss as well future trends and perspectives of Orbitrap MS. We illustrate the compelling potential of Orbitrap-based mass spectrometers as (ultra) high-resolution platforms, not only for high-end proteomic applications, but also for routine targeted analysis.

Advances in imaging secondary ion mass spectrometry for biological samples

DOE PAGES

Boxer, Steven G.; Kraft, Mary L.; Weber, Peter K.

2008-12-16

Imaging mass spectrometry combines the power of mass spectrometry to identify complex molecules based on mass with sample imaging. Recent advances in secondary ion mass spectrometry have improved sensitivity and spatial resolution, so that these methods have the potential to bridge between high-resolution structures obtained by X-ray crystallography and cyro-electron microscopy and ultrastructure visualized by conventional light microscopy. Following background information on the method and instrumentation, we address the key issue of sample preparation. Because mass spectrometry is performed in high vacuum, it is essential to preserve the lateral organization of the sample while removing bulk water, and this hasmore » been a major barrier for applications to biological systems. Furthermore, recent applications of imaging mass spectrometry to cell biology, microbial communities, and biosynthetic pathways are summarized briefly, and studies of biological membrane organization are described in greater depth.« less

Next-generation technologies for spatial proteomics: Integrating ultra-high speed MALDI-TOF and high mass resolution MALDI FTICR imaging mass spectrometry for protein analysis.

PubMed

Spraggins, Jeffrey M; Rizzo, David G; Moore, Jessica L; Noto, Michael J; Skaar, Eric P; Caprioli, Richard M

2016-06-01

MALDI imaging mass spectrometry is a powerful analytical tool enabling the visualization of biomolecules in tissue. However, there are unique challenges associated with protein imaging experiments including the need for higher spatial resolution capabilities, improved image acquisition rates, and better molecular specificity. Here we demonstrate the capabilities of ultra-high speed MALDI-TOF and high mass resolution MALDI FTICR IMS platforms as they relate to these challenges. High spatial resolution MALDI-TOF protein images of rat brain tissue and cystic fibrosis lung tissue were acquired at image acquisition rates >25 pixels/s. Structures as small as 50 μm were spatially resolved and proteins associated with host immune response were observed in cystic fibrosis lung tissue. Ultra-high speed MALDI-TOF enables unique applications including megapixel molecular imaging as demonstrated for lipid analysis of cystic fibrosis lung tissue. Additionally, imaging experiments using MALDI FTICR IMS were shown to produce data with high mass accuracy (<5 ppm) and resolving power (∼75 000 at m/z 5000) for proteins up to ∼20 kDa. Analysis of clear cell renal cell carcinoma using MALDI FTICR IMS identified specific proteins localized to healthy tissue regions, within the tumor, and also in areas of increased vascularization around the tumor. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS).

PubMed

Agarande, M; Benzoubir, S; Bouisset, P; Calmet, D

2001-08-01

Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry.

Capillary electrophoresis-high resolution sector field inductively coupled plasma mass spectrometry.

PubMed

Sonke, Jeroen E; Salters, Vincent J M

2007-08-03

The background and applications of high resolution sector field inductively coupled plasma mass spectrometry (HR-ICP-MS) as a detector for capillary (CE) and gel electrophoretic separations are reviewed. Notable progress has been made in the fields of bioinorganic and environmental (geo-) chemistry. Metallomics, the study of metal species interactions and functions in biological systems, puts substantial technical demands on speciation analysis. The combination of high species resolving power (CE) and high sensitivity-high mass resolving power (HR-ICP-MS) provides a solid base to meet such demands.

Sympathy for the Devil: Detailing the Effects of Planning-Unit Size, Thematic Resolution of Reef Classes, and Socioeconomic Costs on Spatial Priorities for Marine Conservation

PubMed Central

Pressey, Robert L.; Weeks, Rebecca; Andréfouët, Serge; Moloney, James

2016-01-01

Spatial data characteristics have the potential to influence various aspects of prioritising biodiversity areas for systematic conservation planning. There has been some exploration of the combined effects of size of planning units and level of classification of physical environments on the pattern and extent of priority areas. However, these data characteristics have yet to be explicitly investigated in terms of their interaction with different socioeconomic cost data during the spatial prioritisation process. We quantify the individual and interacting effects of three factors—planning-unit size, thematic resolution of reef classes, and spatial variability of socioeconomic costs—on spatial priorities for marine conservation, in typical marine planning exercises that use reef classification maps as a proxy for biodiversity. We assess these factors by creating 20 unique prioritisation scenarios involving combinations of different levels of each factor. Because output data from these scenarios are analogous to ecological data, we applied ecological statistics to determine spatial similarities between reserve designs. All three factors influenced prioritisations to different extents, with cost variability having the largest influence, followed by planning-unit size and thematic resolution of reef classes. The effect of thematic resolution on spatial design depended on the variability of cost data used. In terms of incidental representation of conservation objectives derived from finer-resolution data, scenarios prioritised with uniform cost outperformed those prioritised with variable cost. Following our analyses, we make recommendations to help maximise the spatial and cost efficiency and potential effectiveness of future marine conservation plans in similar planning scenarios. We recommend that planners: employ the smallest planning-unit size practical; invest in data at the highest possible resolution; and, when planning across regional extents with the intention of incidentally representing fine-resolution features, prioritise the whole region with uniform costs rather than using coarse-resolution data on variable costs. PMID:27829042

Sympathy for the Devil: Detailing the Effects of Planning-Unit Size, Thematic Resolution of Reef Classes, and Socioeconomic Costs on Spatial Priorities for Marine Conservation.

PubMed

Cheok, Jessica; Pressey, Robert L; Weeks, Rebecca; Andréfouët, Serge; Moloney, James

2016-01-01

Spatial data characteristics have the potential to influence various aspects of prioritising biodiversity areas for systematic conservation planning. There has been some exploration of the combined effects of size of planning units and level of classification of physical environments on the pattern and extent of priority areas. However, these data characteristics have yet to be explicitly investigated in terms of their interaction with different socioeconomic cost data during the spatial prioritisation process. We quantify the individual and interacting effects of three factors-planning-unit size, thematic resolution of reef classes, and spatial variability of socioeconomic costs-on spatial priorities for marine conservation, in typical marine planning exercises that use reef classification maps as a proxy for biodiversity. We assess these factors by creating 20 unique prioritisation scenarios involving combinations of different levels of each factor. Because output data from these scenarios are analogous to ecological data, we applied ecological statistics to determine spatial similarities between reserve designs. All three factors influenced prioritisations to different extents, with cost variability having the largest influence, followed by planning-unit size and thematic resolution of reef classes. The effect of thematic resolution on spatial design depended on the variability of cost data used. In terms of incidental representation of conservation objectives derived from finer-resolution data, scenarios prioritised with uniform cost outperformed those prioritised with variable cost. Following our analyses, we make recommendations to help maximise the spatial and cost efficiency and potential effectiveness of future marine conservation plans in similar planning scenarios. We recommend that planners: employ the smallest planning-unit size practical; invest in data at the highest possible resolution; and, when planning across regional extents with the intention of incidentally representing fine-resolution features, prioritise the whole region with uniform costs rather than using coarse-resolution data on variable costs.

Toward Adaptive X-Ray Telescopes

NASA Technical Reports Server (NTRS)

O'Dell, Stephen L.; Atkins, Carolyn; Button, Tim W.; Cotroneo, Vincenzo; Davis, William N.; Doel, Peer; Feldman, Charlotte H.; Freeman, Mark D.; Gubarev, Mikhail V.; Kolodziejczak, Jeffrey J.;

Toward active x-ray telescopes

NASA Astrophysics Data System (ADS)

O'Dell, Stephen L.; Atkins, Carolyn; Button, Timothy W.; Cotroneo, Vincenzo; Davis, William N.; Doel, Peter; Feldman, Charlotte H.; Freeman, Mark D.; Gubarev, Mikhail V.; Kolodziejczak, Jeffery J.; Michette, Alan G.; Ramsey, Brian D.; Reid, Paul B.; Rodriguez Sanmartin, Daniel; Saha, Timo T.; Schwartz, Daniel A.; Trolier-McKinstry, Susan; Wilke, Rudeger H. T.; Willingale, Richard; Zhang, William W.

2011-09-01

Future x-ray observatories will require high-resolution (< 1") optics with very-large-aperture (> 25 m2) areas. Even with the next generation of heavy-lift launch vehicles, launch-mass constraints and aperture-area requirements will limit the areal density of the grazing-incidence mirrors to about 1 kg/m2 or less. Achieving sub-arcsecond x-ray imaging with such lightweight mirrors will require excellent mirror surfaces, precise and stable alignment, and exceptional stiffness or deformation compensation. Attaining and maintaining alignment and figure control will likely involve active (in-space adjustable) x-ray optics. In contrast with infrared and visible astronomy, active optics for x-ray astronomy is in its infancy. In the middle of the past decade, two efforts began to advance technologies for adaptive x-ray telescopes: The Smart X-ray Optics (SXO) Basic Technology project in the United Kingdom (UK) and the Generation-X (Gen-X) concept studies in the United States (US). This paper discusses relevant technological issues and summarizes progress toward active x-ray telescopes.

Crystallization and preliminary X-ray crystallographic analysis of carboxyl-terminal region 4 of SigR from Streptomyces coelicolor A3(2)

PubMed Central

Kim, Keon Young; Kim, Sunmin; Park, Jeong Kuk; Song, HyoJin; Park, SangYoun

2014-01-01

Full-length SigR from Streptomyces coelicolor A3(2) was overexpressed in Escherichia coli, purified and submitted to crystallization trials using either polyethylene glycol 3350 or 4000 as a precipitant. X-ray diffraction data were collected to 2.60 Å resolution under cryoconditions using synchrotron X-rays. The crystal packs in space group P43212, with unit-cell parameters a = b = 42.14, c = 102.02 Å. According to the Matthews coefficient, the crystal asymmetric unit cannot contain the full-length protein. Molecular replacement with the known structures of region 2 and region 4 as independent search models indicates that the crystal contains only the −35 element-binding carboxyl-terminal region 4 of full-length SigR. Mass-spectrometric analysis of the harvested crystal confirms this, suggesting a crystal volume per protein weight (V M) of 2.24 Å3 Da−1 and 45.1% solvent content. PMID:24915084

Fourier Transform Mass Spectrometry: The Transformation of Modern Environmental Analyses

PubMed Central

Lim, Lucy; Yan, Fangzhi; Bach, Stephen; Pihakari, Katianna; Klein, David

2016-01-01

Unknown compounds in environmental samples are difficult to identify using standard mass spectrometric methods. Fourier transform mass spectrometry (FTMS) has revolutionized how environmental analyses are performed. With its unsurpassed mass accuracy, high resolution and sensitivity, researchers now have a tool for difficult and complex environmental analyses. Two features of FTMS are responsible for changing the face of how complex analyses are accomplished. First is the ability to quickly and with high mass accuracy determine the presence of unknown chemical residues in samples. For years, the field has been limited by mass spectrometric methods that were based on knowing what compounds of interest were. Secondly, by utilizing the high resolution capabilities coupled with the low detection limits of FTMS, analysts also could dilute the sample sufficiently to minimize the ionization changes from varied matrices. PMID:26784175

Liquid extraction surface analysis (LESA) of food surfaces employing chip-based nano-electrospray mass spectrometry.

PubMed

Eikel, Daniel; Henion, Jack

2011-08-30

An automated surface-sampling technique called liquid extraction surface analysis (LESA), coupled with infusion nano-electrospray high-resolution mass spectrometry and tandem mass spectrometry (MS/MS), is described and applied to the qualitative determination of surface chemical residues resulting from the artificial spraying of selected fresh fruits and vegetables with representative pesticides. Each of the targeted pesticides was readily detected with both high-resolution and full-scan collision-induced dissociation (CID) mass spectra. In the case of simazine and sevin, a mass resolution of 100,000 was insufficient to distinguish the isobaric protonated molecules for these compounds. When the surface of a spinach leaf was analyzed by LESA, trace levels of diazinon were readily detected on the spinach purchased directly from a supermarket before they were sprayed with the five-pesticide mixture. A 30 s rinse under hot running tap water appeared to quantitatively remove all remaining residues of this pesticide. Diazinon was readily detected by LESA analysis on the skin of the artificially sprayed spinach. Finally, incurred pyrimethanil at a level of 169 ppb in a batch slurry of homogenized apples was analyzed by LESA and this pesticide was readily detected by both high-resolution mass spectrometry and full-scan CID mass spectrometry, thus showing that pesticides may also be detected in whole fruit homogenized samples. This report shows that representative pesticides on fruit and vegetable surfaces present at levels 20-fold below generally allowed EPA tolerance levels are readily detected and confirmed by the title technologies making LESA-MS as interesting screening method for food safety purposes. Copyright © 2011 John Wiley & Sons, Ltd.

Cloning, expression, purification, crystallization and preliminary X-ray characterization of the full-length single-stranded DNA-binding protein from the hyperthermophilic bacterium Aquifex aeolicus.

PubMed

Clarke, David J; Northey, Christopher G; Mack, Lynsey A; McNae, Iain W; Alexeev, Dmitriy; Sawyer, Lindsay; Campopiano, Dominic J

2004-11-01

Single-stranded DNA-binding (SSB) proteins stabilize single-stranded DNA, which is exposed by separation of the duplex during DNA replication, recombination and repair. The SSB protein from the hyperthermophile Aquifex aeolicus has been overexpressed in Escherichia coli, purified and characterized and crystals of the full-length protein (147 amino acids; M(r) 17 131.20) have been grown by vapour diffusion from ammonium sulfate pH 7.5 in both the absence and presence of ssDNA [dT(pT)(68)]. All crystals diffract to around 2.9 A resolution and those without bound DNA (native) belong to space group P2(1), with two tetramers in the asymmetric unit and unit-cell parameters a = 80.97, b = 73.40, c = 109.76 A, beta = 95.11 degrees . Crystals containing DNA have unit-cell parameters a = 108.65, b = 108.51, c = 113.24 A and could belong to three closely related space groups (I222, I2(1)2(1)2(1) or I4(1)) with one tetramer in the asymmetric unit. Electrospray mass spectrometry of the crystals confirmed that the protein was intact. Molecular replacement with a truncated E. coli SSB structure has revealed the position of the molecules in the unit cell and refinement of both native and DNA-bound forms is under way.

Extracting biomolecule collision cross sections from the high-resolution FT-ICR mass spectral linewidths.

PubMed

Jiang, Ting; Chen, Yu; Mao, Lu; Marshall, Alan G; Xu, Wei

2016-01-14

It is known that the ion collision cross section (CCS) may be calculated from the linewidth of a Fourier transform ion cyclotron resonance (FT-ICR) mass spectral peak at elevated pressure (e.g., ∼10(-6) Torr). However, the high mass resolution of FT-ICR is sacrificed in those experiments due to high buffer gas pressure. In this study, we describe a linewidth correction method to eliminate the windowing-induced peak broadening effect. Together with the energetic ion-neutral collision model previously developed by our group, this method enables the extraction of CCSs of biomolecules from high-resolution FT-ICR mass spectral linewidths, obtained at a typical operating buffer gas pressure of modern FT-ICR instruments (∼10(-10) Torr). CCS values of peptides including MRFA, angiotensin I, and bradykinin measured by the proposed method agree well with ion mobility measurements, and the unfolding of protein ions (ubiquitin) at higher charge states is also observed.

Ion optical design of a collinear laser-negative ion beam apparatus.

PubMed

Diehl, C; Wendt, K; Lindahl, A O; Andersson, P; Hanstorp, D

2011-05-01

An apparatus for photodetachment studies on atomic and molecular negative ions of medium up to heavy mass (M ≃ 500) has been designed and constructed. Laser and ion beams are merged in the apparatus in a collinear geometry and atoms, neutral molecules and negative ions are detected in the forward direction. The ion optical design and the components used to optimize the mass resolution and the transmission through the extended field-free interaction region are described. A 90° sector field magnet with 50 cm bending radius in combination with two slits is used for mass dispersion providing a resolution of M∕ΔM≅800 for molecular ions and M∕ΔM≅400 for atomic ions. The difference in mass resolution for atomic and molecular ions is attributed to different energy distributions of the sputtered ions. With 1 mm slits, transmission from the source through the interaction region to the final ion detector was determined to be about 0.14%.

40 CFR 503.31 - Special definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 503.31 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SEWAGE SLUDGE STANDARDS... microorganisms in the absence of air. (c) Density of microorganisms is the number of microorganisms per unit mass...) Specific oxygen uptake rate (SOUR) is the mass of oxygen consumed per unit time per unit mass of total...

Precise determination of cosmogenic Ne in CREU-1 quartz standard, using the Helix-MC Plus mass spectrometer

NASA Astrophysics Data System (ADS)

Hamilton, D.; Honda, M.; Zhang, X.; Phillips, D.; Matchan, E.

2017-12-01

The Helix-MC Plus multi-collector noble gas mass spectrometer at the Australian National University is uniquely equipped with three high mass resolution collectors on H2, Axial and L2 positions. Their mass resolution and mass resolving power are as high as 1,800 and 8,000, respectively. The Helix-MC Plus can totally separate 20Ne+ from 40Ar++ isobaric interference and also partially separate 21Ne+ from 20NeH+ and 22Ne+ from 12C16O2++. By adjusting collector positions, we are able to measure interference-free Ne isotope intensities and have re-determined the 21Ne abundance in air [1]. Analyses by Honda et al. [1] demonstrated that 20Ne1H contributes approximately 2% to previously determined atmospheric 21Ne values [2], and a new atmospheric 21Ne/20Ne ratio of 0.002906 was calculated. Using the Helix-MC Plus mass spectrometer, we measured Ne abundances in the CREU-1 quartz standard [3] and determined cosmogenic concentrations by subtraction of atmospheric Ne with the new atmospheric 21Ne/20Ne value. The average concentration of cosmogenic 21Ne determined from four repeated analyses is 338 ± 12 × 106 atom/g (2σ). This compares with the average concentration of 348 ± 10 × 106 atom/g (2σ) from 45 analyses determined by several laboratories [3], where Ne isotope analyses were undertaken by conventional low resolution mass spectrometers and atmospheric Ne was subtracted using the conventional atmospheric 21Ne/20Ne [2]. On this basis, for a sample with abundant cosmogenic Ne, like CREU-1 quartz, previously measured by low mass resolution mass spectrometers are likely valid and their geological implications are unaffected. However, for low 21Ne concentration samples, combining new generation of mass spectrometers as well as the new atmospheric ratio may have significance for cosmogenic 21Ne surface exposure dating. References: [1] Honda M., et. al., International Journal of Mass Spectrometry, 387, 1 (2015). [2] Eberhardt P., et. al., Zeitschrift fur Naturforschung, 20a, 623 (1965). [3] Vermeesch P., et. al., Quaternary Geochronology, 26, 20 (2015).

Fourier transform ion cyclotron resonance mass resolution and dynamic range limits calculated by computer modeling of ion cloud motion.

PubMed

Vladimirov, Gleb; Hendrickson, Christopher L; Blakney, Greg T; Marshall, Alan G; Heeren, Ron M A; Nikolaev, Eugene N

2012-02-01

Particle-in-Cell (PIC) ion trajectory calculations provide the most realistic simulation of Fourier transform ion cyclotron resonance (FT-ICR) experiments by efficient and accurate calculation of the forces acting on each ion in an ensemble (cloud), including Coulomb interactions (space charge), the electric field of the ICR trap electrodes, image charges on the trap electrodes, the magnetic field, and collisions with neutral gas molecules. It has been shown recently that ion cloud collective behavior is required to generate an FT-ICR signal and that two main phenomena influence mass resolution and dynamic range. The first is formation of an ellipsoidal ion cloud (termed "condensation") at a critical ion number (density), which facilitates signal generation in an FT-ICR cell of arbitrary geometry because the condensed cloud behaves as a quasi-ion. The second phenomenon is peak coalescence. Ion resonances that are closely spaced in m/z coalesce into one resonance if the ion number (density) exceeds a threshold that depends on magnetic field strength, ion cyclotron radius, ion masses and mass difference, and ion initial spatial distribution. These two phenomena decrease dynamic range by rapid cloud dephasing at small ion density and by cloud coalescence at high ion density. Here, we use PIC simulations to quantitate the dependence of coalescence on each critical parameter. Transitions between independent and coalesced motion were observed in a series of the experiments that systematically varied ion number, magnetic field strength, ion radius, ion m/z, ion m/z difference, and ion initial spatial distribution (the present simulations begin from elliptically-shaped ion clouds with constant ion density distribution). Our simulations show that mass resolution is constant at a given magnetic field strength with increasing ion number until a critical value (N) is reached. N dependence on magnetic field strength, cyclotron radius, ion mass, and difference between ion masses was determined for two ion ensembles of different m/z, equal abundance, and equal cyclotron radius. We find that N and dynamic range depend quadratically on magnetic field strength in the range 1-21 Tesla. Dependences on cyclotron radius and Δm/z are linear. N depends on m/z as (m/z)(-2). Empirical expressions for mass resolution as a function of each of the experimental parameters are presented. Here, we provide the first exposition of the origin and extent of trade-off between FT-ICR MS dynamic range and mass resolution (defined not as line width, but as the separation between the most closely resolved masses). © American Society for Mass Spectrometry, 2011

Preferred Styles of Conflict Resolution. Mexico and the United States.

ERIC Educational Resources Information Center

Gabrielidis, Cristina; Stephan, Walter G.; Ybarra, Oscar; Pearson, Virginia Dos Santos; Villareal, Lucila

1997-01-01

Examined cultural differences in preferences for conflict resolution styles using the dual-concern model with 103 college students in Mexico (collectivistic culture) and 91 college students in the United States (individualistic culture). Results suggest that independence of the self and interdependence of the self may be separate dimensions,…

The Assessment of Selectivity in Different Quadrupole-Orbitrap Mass Spectrometry Acquisition Modes

NASA Astrophysics Data System (ADS)

Berendsen, Bjorn J. A.; Wegh, Robin S.; Meijer, Thijs; Nielen, Michel W. F.

2015-02-01

Selectivity of the confirmation of identity in liquid chromatography (tandem) mass spectrometry using Q-Orbitrap instrumentation was assessed using different acquisition modes based on a representative experimental data set constructed from 108 samples, including six different matrix extracts and containing over 100 analytes each. Single stage full scan, all ion fragmentation, and product ion scanning were applied. By generating reconstructed ion chromatograms using unit mass window in targeted MS2, selected reaction monitoring (SRM), regularly applied using triple-quadrupole instruments, was mimicked. This facilitated the comparison of single stage full scan, all ion fragmentation, (mimicked) SRM, and product ion scanning applying a mass window down to 1 ppm. Single factor Analysis of Variance was carried out on the variance (s2) of the mass error to determine which factors and interactions are significant parameters with respect to selectivity. We conclude that selectivity is related to the target compound (mainly the mass defect), the matrix, sample clean-up, concentration, and mass resolution. Selectivity of the different instrumental configurations was quantified by counting the number of interfering peaks observed in the chromatograms. We conclude that precursor ion selection significantly contributes to selectivity: monitoring of a single product ion at high mass accuracy with a 1 Da precursor ion window proved to be equally selective or better to monitoring two transition products in mimicked SRM. In contrast, monitoring a single fragment in all ion fragmentation mode results in significantly lower selectivity versus mimicked SRM. After a thorough inter-laboratory evaluation study, the results of this study can be used for a critical reassessment of the current identification points system and contribute to the next generation of evidence-based and robust performance criteria in residue analysis and sports doping.

Gravity-induced stresses in stratified rock masses

USGS Publications Warehouse

Amadei, B.; Swolfs, H.S.; Savage, W.Z.

1988-01-01

This paper presents closed-form solutions for the stress field induced by gravity in anisotropic and stratified rock masses. These rocks are assumed to be laterally restrained. The rock mass consists of finite mechanical units, each unit being modeled as a homogeneous, transversely isotropic or isotropic linearly elastic material. The following results are found. The nature of the gravity induced stress field in a stratified rock mass depends on the elastic properties of each rock unit and how these properties vary with depth. It is thermodynamically admissible for the induced horizontal stress component in a given stratified rock mass to exceed the vertical stress component in certain units and to be smaller in other units; this is not possible for the classical unstratified isotropic solution. Examples are presented to explore the nature of the gravity induced stress field in stratified rock masses. It is found that a decrease in rock mass anisotropy and a stiffening of rock masses with depth can generate stress distributions comparable to empirical hyperbolic distributions previously proposed in the literature. ?? 1988 Springer-Verlag.

Secondary Ion Mass Spectrometry Imaging of Tissues, Cells, and Microbial Systems

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

Anderton, Christopher R.; Gamble, Lara J.

2016-03-01

Mass spectrometry imaging (MSI) techniques are increasingly being utilized within many biological fields, including medicine, pathology, microbial ecology, and more. Of the MSI methods available, secondary ion mass spectrometry (SIMS) offers the highest lateral resolution of any technique. Moreover, SIMS versatility in the number of different operating modes and types of mass spectrometers available has made it an increasing popular method for bio-related measurements. Here, we discuss SIMS ability to image tissues, single cells, and microbes with a particular emphasis on the types chemical and spatial information that can be ascertained by the different types of SIMS instruments and methods.more » The recently developed Fourier transform ion cyclotron resonance (FTICR) SIMS located at PNNL is capable of generating molecular maps of tissues with an unprecedented mass resolving power and mass accuracy, with respect to SIMS measurements. ToF-SIMS can generate chemical maps, where detection of small molecules and fragments can be acquired with an order of magnitude better lateral resolution than the FTICR-SIMS. Furthermore, many of commercially available ToF-SIMS instruments are capable of depth profiling measurements, offering the ability to attain three-dimensional information of one’s sample. The NanoSIMS instrument offers the highest lateral resolution of any MSI method available. In practice, NanoSIMS regularly achieves sub-100 nm resolution of atomic and diatomic secondary ions within biological samples. The strengths of the different SIMS methods are more and more being leveraged in both multimodal-imaging endeavors that use complementary MSI techniques as well with optical, fluorescence, and force microscopy methods.« less

AssayR: A Simple Mass Spectrometry Software Tool for Targeted Metabolic and Stable Isotope Tracer Analyses.

PubMed

Wills, Jimi; Edwards-Hicks, Joy; Finch, Andrew J

2017-09-19

Metabolic analyses generally fall into two classes: unbiased metabolomic analyses and analyses that are targeted toward specific metabolites. Both techniques have been revolutionized by the advent of mass spectrometers with detectors that afford high mass accuracy and resolution, such as time-of-flights (TOFs) and Orbitraps. One particular area where this technology is key is in the field of metabolic flux analysis because the resolution of these spectrometers allows for discrimination between 13 C-containing isotopologues and those containing 15 N or other isotopes. While XCMS-based software is freely available for untargeted analysis of mass spectrometric data sets, it does not always identify metabolites of interest in a targeted assay. Furthermore, there is a paucity of vendor-independent software that deals with targeted analyses of metabolites and of isotopologues in particular. Here, we present AssayR, an R package that takes high resolution wide-scan liquid chromatography-mass spectrometry (LC-MS) data sets and tailors peak detection for each metabolite through a simple, iterative user interface. It automatically integrates peak areas for all isotopologues and outputs extracted ion chromatograms (EICs), absolute and relative stacked bar charts for all isotopologues, and a .csv data file. We demonstrate several examples where AssayR provides more accurate and robust quantitation than XCMS, and we propose that tailored peak detection should be the preferred approach for targeted assays. In summary, AssayR provides easy and robust targeted metabolite and stable isotope analyses on wide-scan data sets from high resolution mass spectrometers.

AssayR: A Simple Mass Spectrometry Software Tool for Targeted Metabolic and Stable Isotope Tracer Analyses

PubMed Central

2017-01-01

Metabolic analyses generally fall into two classes: unbiased metabolomic analyses and analyses that are targeted toward specific metabolites. Both techniques have been revolutionized by the advent of mass spectrometers with detectors that afford high mass accuracy and resolution, such as time-of-flights (TOFs) and Orbitraps. One particular area where this technology is key is in the field of metabolic flux analysis because the resolution of these spectrometers allows for discrimination between 13C-containing isotopologues and those containing 15N or other isotopes. While XCMS-based software is freely available for untargeted analysis of mass spectrometric data sets, it does not always identify metabolites of interest in a targeted assay. Furthermore, there is a paucity of vendor-independent software that deals with targeted analyses of metabolites and of isotopologues in particular. Here, we present AssayR, an R package that takes high resolution wide-scan liquid chromatography–mass spectrometry (LC-MS) data sets and tailors peak detection for each metabolite through a simple, iterative user interface. It automatically integrates peak areas for all isotopologues and outputs extracted ion chromatograms (EICs), absolute and relative stacked bar charts for all isotopologues, and a .csv data file. We demonstrate several examples where AssayR provides more accurate and robust quantitation than XCMS, and we propose that tailored peak detection should be the preferred approach for targeted assays. In summary, AssayR provides easy and robust targeted metabolite and stable isotope analyses on wide-scan data sets from high resolution mass spectrometers. PMID:28850215

Non-targeted analysis of electronics waste by comprehensive two-dimensional gas chromatography combined with high-resolution mass spectrometry: Using accurate mass information and mass defect analysis to explore the data.

PubMed

Ubukata, Masaaki; Jobst, Karl J; Reiner, Eric J; Reichenbach, Stephen E; Tao, Qingping; Hang, Jiliang; Wu, Zhanpin; Dane, A John; Cody, Robert B

2015-05-22

Comprehensive two-dimensional gas chromatography (GC×GC) and high-resolution mass spectrometry (HRMS) offer the best possible separation of their respective techniques. Recent commercialization of combined GC×GC-HRMS systems offers new possibilities for the analysis of complex mixtures. However, such experiments yield enormous data sets that require new informatics tools to facilitate the interpretation of the rich information content. This study reports on the analysis of dust obtained from an electronics recycling facility by using GC×GC in combination with a new high-resolution time-of-flight (TOF) mass spectrometer. New software tools for (non-traditional) Kendrick mass defect analysis were developed in this research and greatly aided in the identification of compounds containing chlorine and bromine, elements that feature in most persistent organic pollutants (POPs). In essence, the mass defect plot serves as a visual aid from which halogenated compounds are recognizable on the basis of their mass defect and isotope patterns. Mass chromatograms were generated based on specific ions identified in the plots as well as region of the plot predominantly occupied by halogenated contaminants. Tentative identification was aided by database searches, complementary electron-capture negative ionization experiments and elemental composition determinations from the exact mass data. These included known and emerging flame retardants, such as polybrominated diphenyl ethers (PBDEs), hexabromobenzene, tetrabromo bisphenol A and tris (1-chloro-2-propyl) phosphate (TCPP), as well as other legacy contaminants such as polychlorinated biphenyls (PCBs) and polychlorinated terphenyls (PCTs). Copyright © 2015 Elsevier B.V. All rights reserved.

Turbidite megabeds in an Oceanic Rift Valley recording jokulhlaups of late Pleistocene glacial lakes of the western United States

USGS Publications Warehouse

Zuffa, G.G.; Normark, W.R.; Serra, F.; Brunner, C.A.

2000-01-01

Escanaba Trough is the southernmost segment of the Gorda Ridge and is filled by sandy turbidites locally exceeding 500 m in thickness. New results from Ocean Drilling Program (ODP) Sites 1037 and 1038 that include accelerator mass spectrometry (AMS) 14C dates and revised petrographic evaluation of the sediment provenance, combined with high-resolution seismic-reflection profiles, provide a lithostratigraphic framework for the turbidite deposits. Three fining-upward units of sandy turbidites from the upper 365 m at ODP Site 1037 can be correlated with sediment recovered at ODP Site 1038 and Deep Sea Drilling Program (DSDP) Site 35. Six AMS 14C ages in the upper 317 m of the sequence at Site 1037 indicate that average deposition rates exceeded 10 m/k.yr. between 32 and 11 ka, with nearly instantaneous deposition of one ~60-m interval of sand. Petrography of the sand beds is consistent with a Columbia River source for the entire sedimentary sequence in Escanaba Trough. High-resolution acoustic stratigraphy shows that the turbidites in the upper 60 m at Site 1037 provide a characteristic sequence of key reflectors that occurs across the floor of the entire Escanaba Trough. Recent mapping of turbidite systems in the northeast Pacific Ocean suggests that the turbidity currents reached the Escanaba Trough along an 1100-km-long pathway from the Columbia River to the west flank of the Gorda Ridge. The age of the upper fining-upward unit of sandy turbidites appears to correspond to the latest Wisconsinan outburst of glacial Lake Missoula. Many of the outbursts, or jokulhlaups, from the glacial lakes probably continued flowing as hyperpycnally generated turbidity currents on entering the sea at the mouth of the Columbia River.

Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments

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

Tonks, James P., E-mail: james.tonks@awe.co.uk; AWE Plc, Aldermaston, Reading, Berkshire RG7 4PR; Galloway, Ewan C., E-mail: ewan.galloway@awe.co.uk

2016-08-15

A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systemsmore » designed for only one of these techniques.« less

Re-assessing Present Day Global Mass Transport and Glacial Isostatic Adjustment From a Data Driven Approach

NASA Astrophysics Data System (ADS)

Wu, X.; Jiang, Y.; Simonsen, S.; van den Broeke, M. R.; Ligtenberg, S.; Kuipers Munneke, P.; van der Wal, W.; Vermeersen, B. L. A.

2017-12-01

Determining present-day mass transport (PDMT) is complicated by the fact that most observations contain signals from both present day ice melting and Glacial Isostatic Adjustment (GIA). Despite decades of progress in geodynamic modeling and new observations, significant uncertainties remain in both. The key to separate present-day ice mass change and signals from GIA is to include data of different physical characteristics. We designed an approach to separate PDMT and GIA signatures by estimating them simultaneously using globally distributed interdisciplinary data with distinct physical information and a dynamically constructed a priori GIA model. We conducted a high-resolution global reappraisal of present-day ice mass balance with focus on Earth's polar regions and its contribution to global sea-level rise using a combination of ICESat, GRACE gravity, surface geodetic velocity data, and an ocean bottom pressure model. Adding ice altimetry supplies critically needed dual data types over the interiors of ice covered regions to enhance separation of PDMT and GIA signatures, and achieve half an order of magnitude expected higher accuracies for GIA and consequently ice mass balance estimates. The global data based approach can adequately address issues of PDMT and GIA induced geocenter motion and long-wavelength signatures important for large areas such as Antarctica and global mean sea level. In conjunction with the dense altimetry data, we solved for PDMT coefficients up to degree and order 180 by using a higher-resolution GRACE data set, and a high-resolution a priori PDMT model that includes detailed geographic boundaries. The high-resolution approach solves the problem of multiple resolutions in various data types, greatly reduces aliased errors from a low-degree truncation, and at the same time, enhances separation of signatures from adjacent regions such as Greenland and Canadian Arctic territories.

CAMECA IMS 1300-HR3: The New Generation Ion Microprobe

NASA Astrophysics Data System (ADS)

Peres, P.; Choi, S. Y.; Renaud, L.; Saliot, P.; Larson, D. J.

2016-12-01

The success of secondary ion mass spectrometry (SIMS) in Geo- and Cosmo-chemistry relies on its performance in terms of: 1) very high sensitivity (mandatory for high precision measurements or to achieve low detection limits); 2) a broad mass range of elemental and isotopic species, from low mass (H) to high mass (U and above); 3) in-situ analysis of any solid flat polished surface; and 4) high spatial resolution from tens of microns down to sub-micron scale. The IMS 1300-HR3 (High Reproducibility, High spatial Resolution, High mass Resolution) is the latest generation of CAMECA's large geometry magnetic sector SIMS (or ion microprobe), successor to the internationally recognized IMS 1280-HR. The 1300-HR3delivers unmatched analytical performance for a wide range of applications (stable isotopes, geochronology, trace elements, nuclear safeguards and environmental studies…) due to: • High brightness RF-plasma oxygen ion source with enhanced beam density and current stability, dramatically improving spatial resolution, data reproducibility, and throughput • Automated sample loading system with motorized sample height (Z) adjustment, significantly increasing analysis precision, ease-of-use, and productivity • UV-light microscope for enhanced optical image resolution, together with dedicated software for easy sample navigation (developed by University of Wisconsin, USA) • Low noise 1012Ω resistor Faraday cup preamplifier boards for measuring low signal intensities In addition, improvements in electronics and software have been integrated into the new instrument. In order to meet a growing demand from geochronologists, CAMECA also introduces the KLEORA, which is a fully optimized ion microprobe for advanced mineral dating derived from the IMS 1300-HR3. Instrumental developments as well as data obtained for stable isotope and U-Pb dating applications will be presented in detail.

Fast neutral beam ion source coupled to a Fourier transform ion cyclotron resonance mass spectrometer

NASA Astrophysics Data System (ADS)

Hill, Nicholas C.; Limbach, Patrick A.; Shomo, Ronald E., II; Marshall, Alan G.; Appelhans, Anthony D.; Delmore, James E.

1991-11-01

The coupling of an autoneutralizing SF-6 fast ion-beam gun to a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer is described. The fast neutral beam provides for secondary-ion-type FT/ICR mass analysis [e.g., production of abundant pseudomolecular (M+H)+ ions] of involatile samples without the need for external ion injection, since ions are formed at the entrance to the ICR ion trap. The design, construction, and testing of the hybrid instrument are described. The feasibility of the experiment (for both broadband and high-resolution FT/ICR positive-ion mass spectra) is demonstrated with tetra-butylammonium bromide and a Tylenol■ sample. The ability to analyze high molecular weight polymers with high mass resolution is demonstrated for Teflon■. All of the advantages of the fast neutral beam ion source previously demonstrated with quadrupole mass analysis are preserved, and the additional advantages of FT/ICR mass analysis (e.g., high mass resolving power, ion trapping) are retained.

A resolution recognizing the importance and sustainability of the United States hardwoods industry and urging that United States hardwoods and the products derived from United States hardwoods be given full consideration in any program to promote construction of environmentally preferable commercial, public, or private buildings.

THOMAS, 111th Congress

Sen. Lincoln, Blanche L. [D-AR

2010-02-09

Senate - 08/05/2010 Resolution agreed to in Senate without amendment and with a preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

New high-resolution electrostatic ion mass analyzer using time of flight

NASA Technical Reports Server (NTRS)

Hamilton, D. C.; Gloeckler, G.; Ipavich, F. M.; Lundgren, R. A.; Sheldon, R. B.

1990-01-01

The design of a high-resolution ion-mass analyzer is described, which is based on an accurate measurement of the time of flight (TOF) of ions within a region configured to produce a harmonic potential. In this device, the TOF, which is independent of ion energy, is determined from a start pulse from secondary electrons produced when the ion passes through a thin carbon foil at the entrance of the TOF region and at a stop pulse from the ion striking a microchannel plate upon exciting the region. A laboratory prototype instrument called 'VMASS' was built and was tested at the Goddard Space Flight Center electrostatic accelerator, showing a good mass resolution of the instrument. Sensors of the VMASS type will form part of the WIND Solar Wind and Suprathermal Ion experiment, the Soho mission, and the Advanced Composition Explorer.

Analysis of bovine milk caseins on organic monolithic columns: an integrated capillary liquid chromatography-high resolution mass spectrometry approach for the study of time-dependent casein degradation.

PubMed

Pierri, Giuseppe; Kotoni, Dorina; Simone, Patrizia; Villani, Claudio; Pepe, Giacomo; Campiglia, Pietro; Dugo, Paola; Gasparrini, Francesco

2013-10-25

Casein proteins constitute approximately 80% of the proteins present in bovine milk and account for many of its nutritional and technological properties. The analysis of the casein fraction in commercially available pasteurized milk and the study of its time-dependent degradation is of considerable interest in the agro-food industry. Here we present new analytical methods for the study of caseins in fresh and expired bovine milk, based on the use of lab-made capillary organic monolithic columns. An integrated capillary high performance liquid chromatography and high-resolution mass spectrometry (Cap-LC-HRMS) approach was developed, exploiting the excellent resolution, permeability and biocompatibility of organic monoliths, which is easily adaptable to the analysis of intact proteins. The resolution obtained on the lab-made Protein-Cap-RP-Lauryl-γ-Monolithic column (270 mm × 0.250 mm length × internal diameter, L × I.D.) in the analysis of commercial standard caseins (αS-CN, β-CN and κ-CN) through Cap-HPLC-UV was compared to the one observe using two packed capillary C4 columns, the ACE C4 (3 μm, 150 mm × 0.300 mm, L × I.D.) and the Jupiter C4 column (5 μm, 150 mm × 0.300 mm, L × I.D.). Thanks to the higher resolution observed, the monolithic capillary column was chosen for the successive degradation studies of casein fractions extracted from bovine milk 1-4 weeks after expiry date. The comparison of the UV chromatographic profiles of skim, semi-skim and whole milk showed a major stability of whole milk towards time-dependent degradation of caseins, which was further sustained by high-resolution analysis on a 50-cm long monolithic column using a 120-min time gradient. Contemporarily, the exact monoisotopic and average molecular masses of intact αS-CN and β-CN protein standards were obtained through high resolution mass spectrometry and used for casein identification in Cap-LC-HRMS analysis. Finally, the proteolytic degradation of β-CN in skim milk and the contemporary formation of low-molecular-weight proteose-peptones (PP) with exact monoisotopic Mr between 9444.0989 Da and 14098.9861 Da was confirmed through the deconvolution of high resolution mass spectra and literature data. Copyright © 2013 Elsevier B.V. All rights reserved.

Expression, crystallization and preliminary crystallographic studies of a novel bifunctional N-­acetylglutamate synthase/kinase from Xanthomonas campestris homologous to vertebrate N-acetylglutamate synthase

PubMed Central

Shi, Dashuang; Caldovic, Ljubica; Jin, Zhongmin; Yu, Xiaolin; Qu, Qiuhao; Roth, Lauren; Morizono, Hiroki; Hathout, Yetrib; Allewell, Norma M.; Tuchman, Mendel

2006-01-01

A novel N-acetylglutamate synthase/kinase bifunctional enzyme of arginine biosynthesis that was homologous to vertebrate N-acetylglutamate synthases was identified in Xanthomonas campestris. The protein was overexpressed, purified and crystallized. The crystals belong to the hexagonal space group P6222, with unit-cell parameters a = b = 134.60, c = 192.11 Å, and diffract to about 3.0 Å resolution. Selenomethionine-substituted recombinant protein was produced and selenomethionine substitution was verified by mass spectroscopy. Multiple anomalous dispersion (MAD) data were collected at three wavelengths at SER-CAT, Advanced Photon Source, Argonne National Laboratory. Structure determination is under way using the MAD phasing method. PMID:17142901

CD-ROM technology at the EROS data center

USGS Publications Warehouse

Madigan, Michael E.; Weinheimer, Mary C.

1993-01-01

The vast amount of digital spatial data often required by a single user has created a demand for media alternatives to 1/2" magnetic tape. One such medium that has been recently adopted at the U.S. Geological Survey's EROS Data Center is the compact disc (CD). CD's are a versatile, dynamic, and low-cost method for providing a variety of data on a single media device and are compatible with various computer platforms. CD drives are available for personal computers, UNIX workstations, and mainframe systems, either directly connected, or through a network. This medium furnishes a quick method of reproducing and distributing large amounts of data on a single CD. Several data sets are already available on CD's, including collections of historical Landsat multispectral scanner data and biweekly composites of Advanced Very High Resolution Radiometer data for the conterminous United States. The EROS Data Center intends to provide even more data sets on CD's. Plans include specific data sets on a customized disc to fulfill individual requests, and mass production of unique data sets for large-scale distribution. Requests for a single compact disc-read only memory (CD-ROM) containing a large volume of data either for archiving or for one-time distribution can be addressed with a CD-write once (CD-WO) unit. Mass production and large-scale distribution will require CD-ROM replication and mastering.

Observing Exoplanets with High-dispersion Coronagraphy. II. Demonstration of an Active Single-mode Fiber Injection Unit

NASA Astrophysics Data System (ADS)

Mawet, D.; Ruane, G.; Xuan, W.; Echeverri, D.; Klimovich, N.; Randolph, M.; Fucik, J.; Wallace, J. K.; Wang, J.; Vasisht, G.; Dekany, R.; Mennesson, B.; Choquet, E.; Delorme, J.-R.; Serabyn, E.

2017-04-01

High-dispersion coronagraphy (HDC) optimally combines high-contrast imaging techniques such as adaptive optics/wavefront control plus coronagraphy to high spectral resolution spectroscopy. HDC is a critical pathway toward fully characterizing exoplanet atmospheres across a broad range of masses from giant gaseous planets down to Earth-like planets. In addition to determining the molecular composition of exoplanet atmospheres, HDC also enables Doppler mapping of atmosphere inhomogeneities (temperature, clouds, wind), as well as precise measurements of exoplanet rotational velocities. Here, we demonstrate an innovative concept for injecting the directly imaged planet light into a single-mode fiber, linking a high-contrast adaptively corrected coronagraph to a high-resolution spectrograph (diffraction-limited or not). Our laboratory demonstration includes three key milestones: close-to-theoretical injection efficiency, accurate pointing and tracking, and on-fiber coherent modulation and speckle nulling of spurious starlight signal coupling into the fiber. Using the extreme modal selectivity of single-mode fibers, we also demonstrated speckle suppression gains that outperform conventional image-based speckle nulling by at least two orders of magnitude.

Annual variation of gravity-wave activity at middle and high latitudes in a high-resolution GCM

NASA Astrophysics Data System (ADS)

Becker, E.

2017-12-01

A high-resolution version of the Kuehlungsborn Mechanistic general Circulation Model (KMCM) with resolved gravity waves (GWs) is employed to analyze the annual variation of GW activity in both hemispheres at middle and high latitudes. The geographical distributions of GW hotspots in the winter stratosphere are consistent with existing satellite data. Vertical profiles up to the lower thermosphere agree with ground-based measurements for both season. The model confirms the semi-annual variation of GW energy in the upper mesosphere that was found previously in radar-measurements in the northern hemisphere Furthermore, the GW potential energy per unit mass during winter shows two maxima, one around 50-70 km and one around 80-100 km. We interpret the upper maximum as a result of secondary GWs that are generated in the stratopause region due to the intermittent body forces of primary GWs. In a recent study we showed that these secondary GWs produce a significant eastward drag in the mesopause region during austral winter. This mechanism is found to be important in the northern winter as well.

Does resolution of flow field observation influence apparent habitat use and energy expenditure in juvenile coho salmon?

NASA Astrophysics Data System (ADS)

Tullos, D. D.; Walter, C.; Dunham, J.

2016-12-01

This study investigated how the resolution of observation influences interpretation of how fish, juvenile Coho Salmon (Oncorhynchus kisutch), exploit the hydraulic environment in streams. Our objectives were to evaluate how spatial resolution of the flow field observation influenced: 1) the velocities considered to be representative of habitat units; 2) patterns of use of the hydraulic environment by fish; and 3) estimates of energy expenditure. We addressed these objectives using observations within a 1:1 scale physical model of a full-channel log jam in an outdoor experimental stream. Velocities were measured with Acoustic Doppler Velocimetry at a 10 cm grid spacing, whereas fish locations and tailbeat frequencies were documented over time using underwater videogrammetry. Results highlighted that resolution of observation did impact perceived habitat use and energy expenditure, as did the location of measurement within habitat units and the use of averaging to summarize velocities within a habitat unit. In this experiment, the range of velocities and energy expenditure estimates increased with coarsening resolution, reducing the likelihood of measuring the velocities locally experienced by fish. In addition, the coarser resolutions contributed to fish appearing to select velocities that were higher than what was measured at finer resolutions. These findings indicate the need for careful attention to and communication of resolution of observation in investigating the hydraulic environment and in determining the habitat needs and bioenergetics of aquatic biota.

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

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

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on noncovalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. Here in this study, an SID device was designed and successfully installed in amore » hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. Lastly, SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.« less

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

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

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on non-covalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. In this study, an SID device was designed and successfully installed in a hybridmore » FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 kDa to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.« less

Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

DOE PAGES

Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.; ...

2016-12-02

Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on noncovalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. Here in this study, an SID device was designed and successfully installed in amore » hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. Lastly, SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.« less

Stratigraphy and Surface Ages of Dwarf Planet (1) Ceres: Results from Geologic and Topographic Mapping in Survey, HAMO and LAMO Data of the Dawn Framing Camera Images

NASA Astrophysics Data System (ADS)

Wagner, R. J.; Schmedemann, N.; Stephan, K.; Jaumann, R.; Neesemann, A.; Preusker, F.; Kersten, E.; Roatsch, T.; Hiesinger, H.; Williams, D. A.; Yingst, R. A.; Crown, D. A.; Mest, S. C.; Raymond, C. A.; Russell, C. T.

2017-12-01

Since March 6, 2015, the surface of dwarf planet (1) Ceres is being imaged by the FC framing camera aboard the Dawn spacecraft from orbit at various altitudes [1]. For this study we focus on images from the Survey orbit phase (4424 km altitude) with spatial resolutions of 400 m/pxl and use images and topographic data from DTMs (digital terrain models) for global geologic mapping. On Ceres' surface cratered plains are ubiquitous, with variations in superimposed crater frequency indicating different ages and processes. Here, we take the topography into account for geologic mapping and discriminate cratered plains units according to their topographic level - high-standing, medium, or low-lying - in order to examine a possible correlation between topography and surface age. Absolute model ages (AMAs) are derived from two impact cratering chronology models discussed in detail by [2] (henceforth termed LDM: lunar-derived model, and ADM: asteroid-derived model). We also apply an improved method to obtain relative ages and AMAs from crater frequency measurements termed Poisson timing analysis [3]. Our ongoing analysis shows no trend that the topographic level has an influence on the age of the geologic units. Both high-standing and low-lying cratered plains have AMAs ranging from 3.5 to 1.5 Ga (LDM), versus 4.2 to 0.5 Ga (ADM). Some areas of measurement within these units, however, show effects of resurfacing processes in their crater distributions and feature an older and a younger age. We use LAMO data (altitude: 375 km; resolution 30 m/pxl) and/or HAMO data (altitude: 1475 km; resolution 140 m/pxl) to study local geologic units and their ages, e.g., smaller impact craters, especially those not dated so far with crater measurements and/or those with specific spectral properties [4], deposits of mass wasting (e.g., landslides), and mountains, such as Ahuna Mons. Crater frequencies are used to set these geologic units into the context of Ceres' time-stratigraphic system and chronologic periods [5]. References: [1] Russell C. T., et al. (2016), Science 353, doi:10.1126/science.aaf4219. [2] Hiesinger H. H. et al. (2016), Science 353, doi:10.1126/science.aaf4759. [3] Michael G. G. et al. (2016), Icarus 277, 279-285. [4] Stephan K. et al. (2017), submitted to Icarus. [5] Mest S. C. et al. (2017), LPSC XLVIII, abstr. No. 2512.

A Jet Source of Event Horizon Telescope Correlated Flux in M87

NASA Astrophysics Data System (ADS)

Punsly, Brian

2017-12-01

Event Horizon Telescope (EHT) observations at 230 GHz are combined with Very Long Baseline Interferometry (VLBI) observations at 86 GHz and high-resolution Hubble Space Telescope optical observations in order to constrain the broadband spectrum of the emission from the base of the jet in M87. The recent VLBI observations of Hada et al. provide much stricter limits on the 86 GHz luminosity and component acceleration in the jet base than were available to previous modelers. They reveal an almost hollow jet on sub-mas scales. Thus, tubular models of the jet base emanating from the innermost accretion disk are considered within the region responsible for the EHT correlated flux. There is substantial synchrotron self-absorbed opacity at 86 GHz. A parametric analysis indicates that the jet dimensions and power depend strongly on the 86 GHz flux density and the black hole spin, but depend weakly on other parameters, such as jet speed, 230 GHz flux density, and optical flux. The entire power budget of the M87 jet, ≲ {10}44 {erg} {{{s}}}-1, can be accommodated by the tubular jet. No invisible, powerful spine is required. Even though this analysis never employs the resolution of the EHT, the spectral shape implies a dimension transverse to the jet direction of 12-21 μ {as} (˜ 24{--}27 μ {as}) for 0.99> a/M> 0.95 (a/M˜ 0.7), where M is the mass and a is the angular momentum per unit mass of the central black hole.

Bio-oil Analysis Using Negative Electrospray Ionization: Comparative Study of High-Resolution Mass Spectrometers and Phenolic versus Sugaric Components

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

Smith, Erica A.; Park, Soojin; Klein, Adam T.

2012-05-16

We have previously demonstrated that a petroleomic analysis could be performed for bio-oils and revealed the complex nature of bio-oils for the nonvolatile phenolic compounds (Smith, E.; Lee, Y. J. Energy Fuels 2010, 24, 5190−5198). As a subsequent study, we have adapted electrospray ionization in negative-ion mode to characterize a wide variety of bio-oil compounds. A comparative study of three common high-resolution mass spectrometers was performed to validate the methodology and to investigate the differences in mass discrimination and resolution. The mass spectrum is dominated by low mass compounds with m/z of 100–250, with some compounds being analyzable by gasmore » chromatography–mass spectrometry (GC–MS). We could characterize over 800 chemical compositions, with only about 40 of them being previously known in GC–MS. This unveiled a much more complex nature of bio-oils than typically shown by GC–MS. The pyrolysis products of cellulose and hemicellulose, particularly polyhydroxy cyclic hydrocarbons (or what we call “sugaric” compounds), such as levoglucosan, could be effectively characterized with this approach. Phenolic compounds from lignin pyrolysis could be clearly distinguished in a contour map of double bond equivalent (DBE) versus the number of carbons from these sugaric compounds.« less

High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray Desorption Electrospray Ionization Mass Spectrometry

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

Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew

Nanospray desorption electrospray ionization (nano-DESI) combined with tandem mass spectrometry (MS/MS), high-resolution mass analysis (m/m=17,500 at m/z 200), and rapid spectral acquisition enabled simultaneous imaging and identification of more than 300 molecules from 92 selected m/z windows (± 1 Da) with a spatial resolution of better than 150 um. Uterine sections of implantation sites on day 6 of pregnancy were analyzed in the ambient environment without any sample pre-treatment. MS/MS imaging was performed by scanning the sample under the nano-DESI probe at 10 um/s while acquiring higher-energy collision-induced dissociation (HCD) spectra for a targeted inclusion list of 92 m/z valuesmore » at a rate of ~6.3 spectra/s. Molecular ions and their corresponding fragments, separated using high-resolution mass analysis, were assigned based on accurate mass measurement. Using this approach, we were able to identify and image both abundant and low-abundance isobaric species within each m/z window. MS/MS analysis enabled efficient separation and identification of isobaric sodium and potassium adducts of phospholipids. Furthermore, we identified several metabolites associated with early pregnancy and obtained the first 2D images of these molecules.« less

G.A.M.E.: GPU-accelerated mixture elucidator.

PubMed

Schurz, Alioune; Su, Bo-Han; Tu, Yi-Shu; Lu, Tony Tsung-Yu; Lin, Olivia A; Tseng, Yufeng J

2017-09-15

GPU acceleration is useful in solving complex chemical information problems. Identifying unknown structures from the mass spectra of natural product mixtures has been a desirable yet unresolved issue in metabolomics. However, this elucidation process has been hampered by complex experimental data and the inability of instruments to completely separate different compounds. Fortunately, with current high-resolution mass spectrometry, one feasible strategy is to define this problem as extending a scaffold database with sidechains of different probabilities to match the high-resolution mass obtained from a high-resolution mass spectrum. By introducing a dynamic programming (DP) algorithm, it is possible to solve this NP-complete problem in pseudo-polynomial time. However, the running time of the DP algorithm grows by orders of magnitude as the number of mass decimal digits increases, thus limiting the boost in structural prediction capabilities. By harnessing the heavily parallel architecture of modern GPUs, we designed a "compute unified device architecture" (CUDA)-based GPU-accelerated mixture elucidator (G.A.M.E.) that considerably improves the performance of the DP, allowing up to five decimal digits for input mass data. As exemplified by four testing datasets with verified constitutions from natural products, G.A.M.E. allows for efficient and automatic structural elucidation of unknown mixtures for practical procedures. Graphical abstract .

High-Resolution Enabled 12-Plex DiLeu Isobaric Tags for Quantitative Proteomics

PubMed Central

2015-01-01

Multiplex isobaric tags (e.g., tandem mass tags (TMT) and isobaric tags for relative and absolute quantification (iTRAQ)) are a valuable tool for high-throughput mass spectrometry based quantitative proteomics. We have developed our own multiplex isobaric tags, DiLeu, that feature quantitative performance on par with commercial offerings but can be readily synthesized in-house as a cost-effective alternative. In this work, we achieve a 3-fold increase in the multiplexing capacity of the DiLeu reagent without increasing structural complexity by exploiting mass defects that arise from selective incorporation of 13C, 15N, and 2H stable isotopes in the reporter group. The inclusion of eight new reporter isotopologues that differ in mass from the existing four reporters by intervals of 6 mDa yields a 12-plex isobaric set that preserves the synthetic simplicity and quantitative performance of the original implementation. We show that the new reporter variants can be baseline-resolved in high-resolution higher-energy C-trap dissociation (HCD) spectra, and we demonstrate accurate 12-plex quantitation of a DiLeu-labeled Saccharomyces cerevisiae lysate digest via high-resolution nano liquid chromatography–tandem mass spectrometry (nanoLC–MS2) analysis on an Orbitrap Elite mass spectrometer. PMID:25405479

Using an SLR inversion to measure the mass balance of Greenland before and during GRACE

NASA Astrophysics Data System (ADS)

Bonin, Jennifer

2016-04-01

The GRACE mission has done an admirable job of measuring large-scale mass changes over Greenland since its launch in 2002. However before that time, measurements of large-scale ice mass balance were few and far between, leading to a lack of baseline knowledge. High-quality Satellite Laser Ranging (SLR) data existed a decade earlier, but normally has too low a spatial resolution to be used for this purpose. I demonstrate that a least squares inversion technique can reconstitute the SLR data and use it to measure ice loss over Greenland. To do so, I first simulate the problem by degrading today's GRACE data to a level comparable with SLR, then demonstrating that the inversion can re-localize Greenland's contribution to the low-resolution signal, giving an accurate time series of mass change over all of Greenland which compares well with the full-resolution GRACE estimates. I then utilize that method on the actual SLR data, resulting in an independent 1994-2014 time series of mass change over Greenland. I find favorable agreement between the pure-SLR inverted results and the 2012 Ice-sheet Mass Balance Inter-comparison Exercise (IMBIE) results, which are largely based on the "input-output" modeling method before GRACE's launch.

The Legal Situation of Latin American and Caribbean Women as Defined according to the Resolutions and Mandates of the United Nations System. Volume II: File Sheets of Resolutions on the Legal Situation of Women.

ERIC Educational Resources Information Center

United Nations Economic and Social Council, New York, NY.

This document contains a systematized inventory of the measures relating to the legal and social status of women adopted in various regional and world forums. The inventory was used to study the legal situation of Latin American and Caribbean women, defined according to the resolutions and mandates of the United Nations system. Organized by forum…

Lensfree on-chip microscopy over a wide field-of-view using pixel super-resolution

PubMed Central

Bishara, Waheb; Su, Ting-Wei; Coskun, Ahmet F.; Ozcan, Aydogan

2010-01-01

We demonstrate lensfree holographic microscopy on a chip to achieve ~0.6 µm spatial resolution corresponding to a numerical aperture of ~0.5 over a large field-of-view of ~24 mm2. By using partially coherent illumination from a large aperture (~50 µm), we acquire lower resolution lensfree in-line holograms of the objects with unit fringe magnification. For each lensfree hologram, the pixel size at the sensor chip limits the spatial resolution of the reconstructed image. To circumvent this limitation, we implement a sub-pixel shifting based super-resolution algorithm to effectively recover much higher resolution digital holograms of the objects, permitting sub-micron spatial resolution to be achieved across the entire sensor chip active area, which is also equivalent to the imaging field-of-view (24 mm2) due to unit magnification. We demonstrate the success of this pixel super-resolution approach by imaging patterned transparent substrates, blood smear samples, as well as Caenoharbditis Elegans. PMID:20588977

Fine structure in the m/z 121 mass chromatogram of Paraho shale oil

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

Gallegos, E.J.

1984-04-01

High-resolution gas chromatography/high-resolution mass spectrometry/computer (HRGC/HRMS/C) techniques are reported here in the provisional identification of several homologous series of alkylpuridines, phenols, terpenes, and terpanes analytically isolated from Paraho shale oil. HRGC/HRMS/C techniques were also used to follow the hydrodenitrification, HDN, procedure for the removal of the heterocompounds, as well as to monitor the effect of hydrogenation on alkenes.

A comb-sampling method for enhanced mass analysis in linear electrostatic ion traps.

PubMed

Greenwood, J B; Kelly, O; Calvert, C R; Duffy, M J; King, R B; Belshaw, L; Graham, L; Alexander, J D; Williams, I D; Bryan, W A; Turcu, I C E; Cacho, C M; Springate, E

2011-04-01

In this paper an algorithm for extracting spectral information from signals containing a series of narrow periodic impulses is presented. Such signals can typically be acquired by pickup detectors from the image-charge of ion bunches oscillating in a linear electrostatic ion trap, where frequency analysis provides a scheme for high-resolution mass spectrometry. To provide an improved technique for such frequency analysis, we introduce the CHIMERA algorithm (Comb-sampling for High-resolution IMpulse-train frequency ExtRAaction). This algorithm utilizes a comb function to generate frequency coefficients, rather than using sinusoids via a Fourier transform, since the comb provides a superior match to the data. This new technique is developed theoretically, applied to synthetic data, and then used to perform high resolution mass spectrometry on real data from an ion trap. If the ions are generated at a localized point in time and space, and the data is simultaneously acquired with multiple pickup rings, the method is shown to be a significant improvement on Fourier analysis. The mass spectra generated typically have an order of magnitude higher resolution compared with that obtained from fundamental Fourier frequencies, and are absent of large contributions from harmonic frequency components. © 2011 American Institute of Physics

Observations of VOC Emissions and Photochemical Products over US Oil- and Gas-Producing Regions Using High-Resolution H3O+ CIMS (PTR-ToF-MS)

NASA Technical Reports Server (NTRS)

Koss, Abigail; Yuan, Bin; Warneke, Carsten; Gilman, Jessica B.; Lerner, Brian M.; Veres, Patrick R.; Peischl, Jeff; Eilerman, Scott; Wild, Rob; Brown, Steven S.;

Application of ultra-high pressure liquid chromatography linear ion-trap orbitrap to qualitative and quantitative assessment of pesticide residues.

PubMed

Farré, M; Picó, Y; Barceló, D

2014-02-07

The analysis of pesticides residues using a last generation high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometer (LTQ-Orbitrap-MS) was explored. Pesticides were extracted from fruits, fish, bees and sediments by QuEChERS and from water by solid-phase with Oasis HLB cartridges. Ultra-high pressure liquid chromatography (UHPLC)-LTQ-Orbitrap mass spectrometer acquired full scan MS data for quantification, and data dependent (dd) MS(2) and MS(3) product ion spectra for identification and/or confirmation. The regression coefficients (r(2)) for the calibration curves (two order of magnitude up to the lowest calibration level) in the study were ≥0.99. The LODs for 54 validated compounds were ≤2ngmL(-1) (analytical standards). The relative standard deviation (RSD), which was used to estimate precision, was always lower than 22%. The recovery of extraction and matrix effects ranged from 58 to 120% and from -92 to 52%, respectively. Mass accuracy was always ≤4ppm, corresponding to a maximum mass error of 1.6millimass units (mmu). This procedure was then successfully applied to pesticide residues in a set of the above-mentioned food and environmental samples. In addition to target analytes, this method enables the simultaneous detection/identification of non-target pesticides, pharmaceuticals, drugs of abuse, mycotoxins, and their metabolites. Copyright © 2013 Elsevier B.V. All rights reserved.

Detection of reactive metabolites using isotope-labeled glutathione trapping and simultaneous neutral loss and precursor ion scanning with ultra-high-pressure liquid chromatography triple quadruple mass spectrometry.

PubMed

Huang, Ke; Huang, Lingyi; van Breemen, Richard B

2015-04-07

Metabolic activation of drugs to electrophilic species is responsible for over 60% of black box warnings and drug withdrawals from the market place in the United States. Reactive metabolite trapping using glutathione (GSH) and analysis using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) or HPLC with high resolution mass spectrometry (mass defect filtering) have enabled screening for metabolic activation to become routine during drug development. However, current MS-based approaches cannot detect all GSH conjugates present in complex mixtures, especially those present in extracts of botanical dietary supplements. To overcome these limitations, a fast triple quadrupole mass spectrometer-based approach was developed that can detect positively and negatively charged GSH conjugates in a single analysis without the need for advanced knowledge of the elemental compositions of potential conjugates and while avoiding false positives. This approach utilized UHPLC instead of HPLC to shorten separation time and enhance sensitivity, incorporated stable-isotope labeled GSH to avoid false positives, and used fast polarity switching electrospray MS/MS to detect GSH conjugates that form positive and/or negative ions. The general new method was then used to test the licorice dietary supplement Glycyrrhiza glabra, which was found to form multiple GSH conjugates upon metabolic activation. Among the GSH conjugates found in the licorice assay were conjugates with isoliquiritigenin and glabridin, which is an irreversible inhibitor of cytochrome P450 enzymes.

Isotope ratio analysis by Orbitrap mass spectrometry

NASA Astrophysics Data System (ADS)

Eiler, J. M.; Chimiak, L. M.; Dallas, B.; Griep-Raming, J.; Juchelka, D.; Makarov, A.; Schwieters, J. B.

2016-12-01

Several technologies are being developed to examine the intramolecular isotopic structures of molecules (i.e., site-specific and multiple substitution), but various limitations in sample size and type or (for IRMS) resolution have so far prevented the creation of a truly general technique. We will discuss the initial findings of a technique based on Fourier transform mass spectrometry, using the Thermo Scientific Q Exactive GC — an instrument that contains an Orbitrap mass analyzer. Fourier transform mass spectrometry is marked by exceptionally high mass resolutions (the Orbitrap reaches M/ΔM in the range 250,000-1M in the mass range of greatest interest, 50-200 amu). This allows for resolution of a large range of nearly isobaric interferences for isotopologues of volatile and semi-volatile compounds (i.e., involving isotopes of H, C, N, O and S). It also provides potential to solve very challenging mass resolution problems for isotopic analysis of other, heavier elements. Both internal and external experimental reproducibilities of isotope ratio analyses using the Orbitrap typically conform to shot-noise limits down to levels of 0.2 ‰ (1SE), and routinely in the range 0.5-1.0 ‰, with similar accuracy when standardized to concurrently run reference materials. Such measurements can be made without modifications to the ion optics of the Q Exactive GC, but do require specially designed sample introduction devices to permit sample/standard comparison and long integration times. The sensitivity of the Q Exactive GC permits analysis of sub-nanomolar samples and quantification of multiply-substituted species. The site-specific capability of this instrument arises from the fact that mass spectra of molecular analytes commonly contain diverse fragment ion species, each of which samples a specific sub-set of molecular sites. We will present applications of this technique to the biological and abiological chemistry of amino acids, forensic identification of hydrocarbon environmental pollutants, and study of the origins of isotope anomalies in meteoritic organics.

Identification of low-abundance cancer biomarker candidate TIMP1 from serum with lectin fractionation and peptide affinity enrichment by ultrahigh-resolution mass spectrometry.

PubMed

Ahn, Yeong Hee; Kim, Kwang Hoe; Shin, Park Min; Ji, Eun Sun; Kim, Hoguen; Yoo, Jong Shin

2012-02-07

As investigating a proteolytic target peptide originating from the tissue inhibitor of metalloproteinase 1 (TIMP1) known to be aberrantly glycosylated in patients with colorectal cancer (CRC), we first confirmed that TIMP1 is to be a CRC biomarker candidate in human serum. For this, we utilized matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS) showing ultrahigh-resolution and high mass accuracy. This investigation used phytohemagglutinin-L(4) (L-PHA) lectin, which shows binding affinity to the β-1,6-N-acetylglucosamine moiety of N-linked glycan on a protein, to compare fractionated aberrant protein glycoforms from both noncancerous control and CRC serum. Each lectin-captured fraction containing aberrant glycoforms of TIMP1 was digested by trypsin, resulting in the tryptic target peptide, representative of the serum glycoprotein TIMP1. The resulting target peptide was enriched using a stable isotope standard and capture by the antipeptide antibody (SISCAPA) technique and analyzed by a 15 T MALDI FTICR mass spectrometer with high mass accuracy (Δ < 0.5 ppm to the theoretical mass value of the target peptide). Since exact measurement of multiplex isotopic peaks of the target peptide could be accomplished by virtue of high mass resolution (Rs > 400,000), robust identification of the target peptide is only achievable with 15 T FTICR MS. Also, MALDI data obtained in this study showed that the L-PHA-captured glycoforms of TIMP1 were measured in the pooled CRC serum with about 5 times higher abundance than that in the noncancerous serum, and were further proved by MRM mass analysis. These results confirm that TIMP1 in human serum is a potent CRC biomarker candidate, demonstrating that ultrahigh-resolution MS can be a powerful tool toward identifying and verifying potential protein biomarker candidates. © 2011 American Chemical Society

Multi-Pass Quadrupole Mass Analyzer

NASA Technical Reports Server (NTRS)

Prestage, John D.

2013-01-01

Analysis of the composition of planetary atmospheres is one of the most important and fundamental measurements in planetary robotic exploration. Quadrupole mass analyzers (QMAs) are the primary tool used to execute these investigations, but reductions in size of these instruments has sacrificed mass resolving power so that the best present-day QMA devices are still large, expensive, and do not deliver performance of laboratory instruments. An ultra-high-resolution QMA was developed to resolve N2 +/CO+ by trapping ions in a linear trap quadrupole filter. Because N2 and CO are resolved, gas chromatography columns used to separate species before analysis are eliminated, greatly simplifying gas analysis instrumentation. For highest performance, the ion trap mode is used. High-resolution (or narrow-band) mass selection is carried out in the central region, but near the DC electrodes at each end, RF/DC field settings are adjusted to allow broadband ion passage. This is to prevent ion loss during ion reflection at each end. Ions are created inside the trap so that low-energy particles are selected by low-voltage settings on the end electrodes. This is beneficial to good mass resolution since low-energy particles traverse many cycles of the RF filtering fields. Through Monte Carlo simulations, it is shown that ions are reflected at each end many tens of times, each time being sent back through the central section of the quadrupole where ultrahigh mass filtering is carried out. An analyzer was produced with electrical length orders of magnitude longer than its physical length. Since the selector fields are sized as in conventional devices, the loss of sensitivity inherent in miniaturizing quadrupole instruments is avoided. The no-loss, multi-pass QMA architecture will improve mass resolution of planetary QMA instruments while reducing demands on the RF electronics for high-voltage/high-frequency production since ion transit time is no longer limited to a single pass. The QMA-based instrument will thus give way to substantial reductions of the mass of flight instruments.

Efficient methods for implementation of multi-level nonrigid mass-preserving image registration on GPUs and multi-threaded CPUs.

PubMed

Ellingwood, Nathan D; Yin, Youbing; Smith, Matthew; Lin, Ching-Long

2016-04-01

Faster and more accurate methods for registration of images are important for research involved in conducting population-based studies that utilize medical imaging, as well as improvements for use in clinical applications. We present a novel computation- and memory-efficient multi-level method on graphics processing units (GPU) for performing registration of two computed tomography (CT) volumetric lung images. We developed a computation- and memory-efficient Diffeomorphic Multi-level B-Spline Transform Composite (DMTC) method to implement nonrigid mass-preserving registration of two CT lung images on GPU. The framework consists of a hierarchy of B-Spline control grids of increasing resolution. A similarity criterion known as the sum of squared tissue volume difference (SSTVD) was adopted to preserve lung tissue mass. The use of SSTVD consists of the calculation of the tissue volume, the Jacobian, and their derivatives, which makes its implementation on GPU challenging due to memory constraints. The use of the DMTC method enabled reduced computation and memory storage of variables with minimal communication between GPU and Central Processing Unit (CPU) due to ability to pre-compute values. The method was assessed on six healthy human subjects. Resultant GPU-generated displacement fields were compared against the previously validated CPU counterpart fields, showing good agreement with an average normalized root mean square error (nRMS) of 0.044±0.015. Runtime and performance speedup are compared between single-threaded CPU, multi-threaded CPU, and GPU algorithms. Best performance speedup occurs at the highest resolution in the GPU implementation for the SSTVD cost and cost gradient computations, with a speedup of 112 times that of the single-threaded CPU version and 11 times over the twelve-threaded version when considering average time per iteration using a Nvidia Tesla K20X GPU. The proposed GPU-based DMTC method outperforms its multi-threaded CPU version in terms of runtime. Total registration time reduced runtime to 2.9min on the GPU version, compared to 12.8min on twelve-threaded CPU version and 112.5min on a single-threaded CPU. Furthermore, the GPU implementation discussed in this work can be adapted for use of other cost functions that require calculation of the first derivatives. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

40 CFR 75.73 - Recordkeeping and reporting.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) CONTINUOUS EMISSION MONITORING NOX Mass Emissions Provisions § 75.73 Recordkeeping and reporting... for units using the low mass emissions unit provisions of § 75.19). (3) For each hour when the unit is operating, NOX mass emissions, calculated in accordance with section 8.1 of appendix F to this part. (4...

Determining neutrino mass from the cosmic microwave background alone.

PubMed

Kaplinghat, Manoj; Knox, Lloyd; Song, Yong-Seon

2003-12-12

Distortions of cosmic microwave background temperature and polarization maps caused by gravitational lensing, observable with high angular resolution and high sensitivity, can be used to measure the neutrino mass. Assuming two massless species and one with mass m(nu), we forecast sigma(m(nu))=0.15 eV from the Planck satellite and sigma(m(nu))=0.04 eV from observations with twice the angular resolution and approximately 20 times the sensitivity. A detection is likely at this higher sensitivity since the observation of atmospheric neutrino oscillations requires Deltam(2)(nu) greater, similar (0.04 eV)(2).

Structural Characterisation of Acetogenins from Annona muricata by Supercritical Fluid Chromatography Coupled to High-Resolution Tandem Mass Spectrometry.

PubMed

Laboureur, Laurent; Bonneau, Natacha; Champy, Pierre; Brunelle, Alain; Touboul, David

2017-11-01

Acetogenins are plant polyketides known to be cytotoxic and proposed as antitumor candidates. They are also suspected to be alimentary neurotoxins. Their occurrence as complex mixtures renders their dereplication and structural identification difficult using liquid chromatography coupled to tandem mass spectrometry and efforts are required to improve the methodology. To develop a supercritical fluid chromatography (SFC) high-resolution tandem mass spectrometry method, involving lithium post-column cationisation, for the structural characterisation of Annonaceous acetogenins in crude extracts. The seeds of Annona muricata L. were extracted with methanol. Supercritical fluid chromatography of the extract, using a 2-ethylpyridine stationary phase column, was monitored using a high-resolution quadrupole time-of-flight mass spectrometer. Lithium iodide was added post-column in the make-up solvent. For comparison, the same extract was analysed using high-pressure liquid chromatography coupled to the same mass spectrometer, with a column based on solid core particles. Sensitivity was similar for both HPLC and SFC approaches. Retention behaviour and fragmentation pathways of three different isomer groups are described. A previously unknown group of acetogenins was also evidenced for the first time. The use of SFC-MS/MS allows the reduction of the time of analysis, of environmental impact and an increase in the chromatographic resolution, compared to liquid chromatography. This new methodology enlightened a new group of acetogenins, isomers of montanacin-D. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

MALDI mass spectrometry imaging of bioactive lipids in mouse brain with a Synapt G2-S mass spectrometer operated at elevated pressure: improving the analytical sensitivity and the lateral resolution to ten micrometers.

PubMed

Kettling, Hans; Vens-Cappell, Simeon; Soltwisch, Jens; Pirkl, Alexander; Haier, Jörg; Müthing, Johannes; Dreisewerd, Klaus

2014-08-05

Mass spectrometers from the Synapt-G1/G2 family (Waters) are widely employed for matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). A lateral resolution of about 50 μm is typically achieved with these instruments, that is, however, below the often desired cellular resolution. Here, we show the first MALDI-MSI examples demonstrating a lateral resolution of about ten micrometers obtained with a Synapt G2-S HDMS mass spectrometer without oversampling. This improvement became possible by laser beam shaping using a 4:1 beam expander and a circular aperture for spatial mode filtering and by replacement of the default focusing lens. We used dithranol as an effective matrix for imaging of acidic lipids such as sulfatides, gangliosides, and phosphatidylinositols in the negative ion mode. At the same time, the matrix enables MS imaging of more basic lipids in the positive ion mode. Uniform matrix coatings with crystals having average dimensions between 0.5 and 3 μm were obtained upon spraying a chloroform/methanol matrix solution. Increasing the cooling gas pressure in the MALDI ion source after adding an additional gas line was furthermore found to increase the ion abundances of labile lipids such as gangliosides. The combined characteristics are demonstrated with the MALDI-MSI analysis of fine structures in coronal mouse brain slices.

The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins.

PubMed

Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

2016-03-24

It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks ("seeds") for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn's largest moon, Titan.

The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins

PubMed Central

Somogyi, Árpád; Thissen, Roland; Orthous-Daunay, Francois-Régis; Vuitton, Véronique

2016-01-01

It is an important but also a challenging analytical problem to understand the chemical composition and structure of prebiotic organic matter that is present in extraterrestrial materials. Its formation, evolution and content in the building blocks (“seeds”) for more complex molecules, such as proteins and DNA, are key questions in the field of exobiology. Ultrahigh resolution mass spectrometry is one of the best analytical techniques that can be applied because it provides reliable information on the chemical composition and structure of individual components of complex organic mixtures. Prebiotic organic material is delivered to Earth by meteorites or generated in laboratories in simulation (model) experiments that mimic space or atmospheric conditions. Recent representative examples for ultrahigh resolution mass spectrometry studies using Fourier-transform (FT) mass spectrometers such as Orbitrap and ion cyclotron resonance (ICR) mass spectrometers are shown and discussed in the present article, including: (i) the analysis of organic matter of meteorites; (ii) modeling atmospheric processes in ICR cells; and (iii) the structural analysis of laboratory made tholins that might be present in the atmosphere and surface of Saturn’s largest moon, Titan. PMID:27023520

Biodegradation of carbamazepine and clarithromycin by Trichoderma harzianum and Pleurotus ostreatus investigated by liquid chromatography - high-resolution tandem mass spectrometry (FTICR MS-IRMPD).

PubMed

Buchicchio, Alessandro; Bianco, Giuliana; Sofo, Adriano; Masi, Salvatore; Caniani, Donatella

2016-07-01

In this study, the capability of pharmaceutical biodegradation of fungus Trichoderma harzianum was evaluated through the comparison with the well-known biodegradation capability of white-rot fungus Pleurotus ostreatus. The study was performed in aqueous phase under aerobic conditions, using two of the most frequently detected drugs in water bodies: carbamazepine and clarithromycin, with concentrations commonly found in treated wastewater (4μg/l and 0.03μg/l respectively). For the first time, we demonstrated that T. harzianum is able to remove carbamazepine and clarithromycin. The analyses were performed by reversed-phase liquid chromatography/mass spectrometry, using high-resolution Fourier-transform ion cyclotron resonance mass spectrometry upon electrospray ionization in positive ion mode. The high selectivity and mass accuracy provided by high-resolution mass spectrometry, allowed us to identify some unknown metabolites. On the basis of our study, the major metabolites detected in liquid culture treated by T. harzianum were: 14-hydroxy-descladinosyl- and descladinosyl-clarithromycin, which are pharmacologically inactive products not dangerous for the environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of a new screening method for the detection of antibiotic residues in muscle tissues using liquid chromatography and high resolution mass spectrometry with a LC-LTQ-Orbitrap instrument.

PubMed

Hurtaud-Pessel, D; Jagadeshwar-Reddy, T; Verdon, E

2011-10-01

A liquid chromatography-high resolution mass spectrometry (LC-HRMS) method was developed for screening meat for a wide range of antibiotics used in veterinary medicine. Full-scan mode under high resolution mass spectral conditions using an LTQ-Orbitrap mass spectrometer with resolving power 60,000 full width at half maximum (FWHM) was applied for analysis of the samples. Samples were prepared using two extraction protocols prior to LC-HRMS analysis. The scope of the method focuses on screening the following main families of antibacterial veterinary drugs: penicillins, cephalosporins, sulfonamides, macrolides, tetracyclines, aminoglucosides and quinolones. Compounds were successfully identified in spiked samples from their accurate mass and LC retention times from the acquired full-scan chromatogram. Automated data processing using ToxId software allowed rapid treatment of the data. Analyses of muscle tissues from real samples collected from antibiotic-treated animals was carried out using the above methodology and antibiotic residues were identified unambiguously. Further analysis of the data for real samples allowed the identification of the targeted antibiotic residues but also non-targeted compounds, such as some of their metabolites.

Development of high-spatial and high-mass resolution mass spectrometric imaging (MSI) and its application to the study of small metabolites and endogenous molecules of plants

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

Jun, Ji Hyun

High-spatial and high-mass resolution laser desorption ionization (LDI) mass spectrometric (MS) imaging technology was developed for the attainment of MS images of higher quality containing more information on the relevant cellular and molecular biology in unprecedented depth. The distribution of plant metabolites is asymmetric throughout the cells and tissues, and therefore the increase in the spatial resolution was pursued to reveal the localization of plant metabolites at the cellular level by MS imaging. For achieving high-spatial resolution, the laser beam size was reduced by utilizing an optical fiber with small core diameter (25 μm) in a vacuum matrix-assisted laser desorptionmore » ionization-linear ion trap (vMALDI-LTQ) mass spectrometer. Matrix application was greatly improved using oscillating capillary nebulizer. As a result, single cell level spatial resolution of ~ 12 μm was achieved. MS imaging at this high spatial resolution was directly applied to a whole Arabidopsis flower and the substructures of an anther and single pollen grains at the stigma and anther were successfully visualized. MS imaging of high spatial resolution was also demonstrated to the secondary roots of Arabidopsis thaliana and a high degree of localization of detected metabolites was successfully unveiled. This was the first MS imaging on the root for molecular species. MS imaging with high mass resolution was also achieved by utilizing the LTQ-Orbitrap mass spectrometer for the direct identification of the surface metabolites on the Arabidopsis stem and root and differentiation of isobaric ions having the same nominal mass with no need of tandem mass spectrometry (MS/MS). MS imaging at high-spatial and high-mass resolution was also applied to cer1 mutant of the model system Arabidopsis thaliana to demonstrate its usefulness in biological studies and reveal associated metabolite changes in terms of spatial distribution and/or abundances compared to those of wild-type. The spatial distribution of targeted metabolites, mainly waxes and flavonoids, was systematically explored on various organs, including flowers, leaves, stems, and roots at high spatial resolution of ~ 12-50 μm and the changes in the abundance level of these metabolites were monitored on the cer1 mutant with respect to the wild-type. This study revealed the metabolic biology of CER1 gene on each individual organ level with very detailed high spatial resolution. The separate MS images of isobaric metabolites, i.e. C29 alkane vs. C28 aldehyde could be constructed on both genotypes from MS imaging at high mass resolution. This allows tracking of abundance changes for those compounds along with the genetic mutation, which is not achievable with low mass resolution mass spectrometry. This study supported previous hypothesis of molecular function of CER1 gene as aldehyde decarbonylase, especially by displaying hyper accumulation of aldehydes and C30 fatty acid and decrease in abundance of alkanes and ketones in several plant organs of cer1 mutant. The scope of analytes was further directed toward internal cell metabolites from the surface metabolites of the plant. MS profiling and imaging of internal cell metabolites were performed on the vibratome section of Arabidopsis leaf. Vibratome sectioning of the leaf was first conducted to remove the surface cuticle layer and it was followed by enzymatic treatment of the section to induce the digestion of primary cell walls, middle lamella, and expose the internal cells underneath to the surface for detection with the laser by LDI-MS. The subsequent MS imaging onto the enzymatically treated vibratome section allowed us to map the distribution of the metabolites in the internal cell layers, linolenic acid (C18:3 FA) and linoleic acid (C18:2 FA). The development of an assay for relative quantification of analytes at the single subcellular/organelle level by LDI-MS imaging was attempted and both plausibility and significant obstacles were seen. As a test system, native plant organelle, chloroplasts isolated from the spinach leaves were used and the localization of isolated chloroplasts dispersed on the target plate in low density was monitored by detecting the ion signal of chlorophyll a (Chl a) degradation products such as pheophytin a and pheophobide a by LDI-MS imaging in combination with fluorescence microscopy. The number of chloroplasts and their localization visualized in the MS image exactly matched those in the fluorescence image especially at low density, which first shows the plausibility of single-organelle level quantification of analytes by LDI-MS. The accumulation level of Chl a within a single chloroplast detected by LDI-MS was compared to the fluorescence signal on a pixel-to-pixel basis to further confirm the correlations of the accumulation levels measured by two methods. The proportional correlation was observed only for the chloroplasts which do not show the significant leakage of chlorophyll indicated by MS ion signal of Chl a degradation products and fluorescence signal, which was presumably caused by the prior fluorescence measurement before MS imaging. Further investigation is necessary to make this method more complete and develop LDI-MS imaging as an effective analytical tool to evaluate a relative accumulation of analytes of interest at the single subcellular/organelle level.« less

Mass Profile Decomposition of the Frontier Fields Cluster MACS J0416-2403: Insights on the Dark-matter Inner Profile

NASA Astrophysics Data System (ADS)

Annunziatella, M.; Bonamigo, M.; Grillo, C.; Mercurio, A.; Rosati, P.; Caminha, G.; Biviano, A.; Girardi, M.; Gobat, R.; Lombardi, M.; Munari, E.

2017-12-01

We present a high-resolution dissection of the two-dimensional total mass distribution in the core of the Hubble Frontier Fields galaxy cluster MACS J0416.1‑2403, at z = 0.396. We exploit HST/WFC3 near-IR (F160W) imaging, VLT/Multi Unit Spectroscopic Explorer spectroscopy, and Chandra data to separate the stellar, hot gas, and dark-matter mass components in the inner 300 kpc of the cluster. We combine the recent results of our refined strong lensing analysis, which includes the contribution of the intracluster gas, with the modeling of the surface brightness and stellar mass distributions of 193 cluster members, of which 144 are spectroscopically confirmed. We find that, moving from 10 to 300 kpc from the cluster center, the stellar to total mass fraction decreases from 12% to 1% and the hot gas to total mass fraction increases from 3% to 9%, resulting in a baryon fraction of approximatively 10% at the outermost radius. We measure that the stellar component represents ∼30%, near the cluster center, and 15%, at larger clustercentric distances, of the total mass in the cluster substructures. We subtract the baryonic mass component from the total mass distribution and conclude that within 30 kpc (∼3 times the effective radius of the brightest cluster galaxy) from the cluster center the surface mass density profile of the total mass and global (cluster plus substructures) dark-matter are steeper and that of the diffuse (cluster) dark-matter is shallower than an NFW profile. Our current analysis does not point to a significant offset between the cluster stellar and dark-matter components. This detailed and robust reconstruction of the inner dark-matter distribution in a larger sample of galaxy clusters will set a new benchmark for different structure formation scenarios.

In-depth study of in-trap high-resolution mass separation by transversal ion ejection from a multi-reflection time-of-flight device.

PubMed

Fischer, Paul; Knauer, Stefan; Marx, Gerrit; Schweikhard, Lutz

2018-01-01

The recently introduced method of ion separation by transversal ejection of unwanted species in electrostatic ion-beam traps and multi-reflection time-of-flight devices has been further studied in detail. As this separation is performed during the ion storage itself, there is no need for additional external devices such as ion gates or traps for either pre- or postselection of the ions of interest. The ejection of unwanted contaminant ions is performed by appropriate pulses of the potentials of deflector electrodes. These segmented ring electrodes are located off-center in the trap, i.e., between one of the two ion mirrors and the central drift tube, which also serves as a potential lift for capturing incoming ions and axially ejecting ions of interest after their selection. The various parameters affecting the selection effectivity and resolving power are illustrated with tin-cluster measurements, where isotopologue ion species provide mass differences down to a single atomic mass unit at ion masses of several hundred. Symmetric deflection voltages of only 10 V were found sufficient for the transversal ejection of ion species with as few as three deflection pulses. The duty cycle, i.e., the pulse duration with respect to the period of ion revolution, has been varied, resulting in resolving powers of up to several tens of thousands for this selection technique.

In-depth study of in-trap high-resolution mass separation by transversal ion ejection from a multi-reflection time-of-flight device

NASA Astrophysics Data System (ADS)

Fischer, Paul; Knauer, Stefan; Marx, Gerrit; Schweikhard, Lutz

2018-01-01

The recently introduced method of ion separation by transversal ejection of unwanted species in electrostatic ion-beam traps and multi-reflection time-of-flight devices has been further studied in detail. As this separation is performed during the ion storage itself, there is no need for additional external devices such as ion gates or traps for either pre- or postselection of the ions of interest. The ejection of unwanted contaminant ions is performed by appropriate pulses of the potentials of deflector electrodes. These segmented ring electrodes are located off-center in the trap, i.e., between one of the two ion mirrors and the central drift tube, which also serves as a potential lift for capturing incoming ions and axially ejecting ions of interest after their selection. The various parameters affecting the selection effectivity and resolving power are illustrated with tin-cluster measurements, where isotopologue ion species provide mass differences down to a single atomic mass unit at ion masses of several hundred. Symmetric deflection voltages of only 10 V were found sufficient for the transversal ejection of ion species with as few as three deflection pulses. The duty cycle, i.e., the pulse duration with respect to the period of ion revolution, has been varied, resulting in resolving powers of up to several tens of thousands for this selection technique.

Comparison of secondary ion mass spectrometry and micromilling/continuous flow isotope ratio mass spectrometry techniques used to acquire intra-otolith delta18O values of wild Atlantic salmon (Salmo salar).

PubMed

Hanson, N N; Wurster, C M; Todd, C D

2010-09-15

The chemical signals in the sequential layers of fish otoliths have the potential to provide fisheries biologists with temporal and spatial details of migration which are difficult to obtain without expensive tracking methods. Signal resolution depends, however, on the extraction technique used. We compared the use of mechanical micromilling and continuous flow isotope ratio mass spectrometry (CF-IRMS) methods with secondary ion mass spectrometry (SIMS) to obtain delta(18)O profiles from otoliths of wild Atlantic salmon (Salmo salar) and used these to corroborate the time of freshwater emigration of the juvenile with macroscopic patterns within the otolith. Both techniques showed the transition occurring at the same visible feature on the otolith, allowing future analyses to easily identify the juvenile (freshwater) versus adult (marine) life-stages. However, SIMS showed a rapid and abrupt transition whereas micromilling provided a less distinct signal. The number of samples that could be obtained per unit area sampled using SIMS was 2 to 3 times greater than that when using micromilling/CF-IRMS although the delta(18)O values and analytical precisions (approximately 0.2 per thousand) of the two methods were comparable. In addition, SIMS delta(18)O results were used to compare otolith aragonite values with predicted values calculated using various isotope fractionation equations. Copyright 2010 John Wiley & Sons, Ltd.

A 16-year time series of 1 km AVHRR satellite data of the conterminous United States and Alaska

USGS Publications Warehouse

Eidenshink, Jeff

2006-01-01

The U.S. Geological Survey (USGS) has developed a 16-year time series of vegetation condition information for the conterminous United States and Alaska using 1 km Advanced Very High Resolution Radiometer (AVHRR) data. The AVHRR data have been processed using consistent methods that account for radiometric variability due to calibration uncertainty, the effects of the atmosphere on surface radiometric measurements obtained from wide field-of-view observations, and the geometric registration accuracy. The conterminous United States and Alaska data sets have an atmospheric correction for water vapor, ozone, and Rayleigh scattering and include a cloud mask derived using the Clouds from AVHRR (CLAVR) algorithm. In comparison with other AVHRR time series data sets, the conterminous United States and Alaska data are processed using similar techniques. The primary difference is that the conterminous United States and Alaska data are at 1 km resolution, while others are at 8 km resolution. The time series consists of weekly and biweekly maximum normalized difference vegetation index (NDVI) composites.

A NEW MASS SPECTROMETRIC TECHNIQUE FOR IDENTIFYING TRACE-LEVEL ORGANIC COMPOUNDS IN COMPLEX MIXTURES

EPA Science Inventory

Most organic compounds are not found in mass spectral libraries and cannot be easily identified from low resolution mass spectra. Ion Composition Elucidation (ICE) utilizes selected ion recording with a double focusing mass spectrometer in a new way to determine exact mas...

Uncovering mass segregation with galaxy analogues in dark-matter simulations

NASA Astrophysics Data System (ADS)

Joshi, Gandhali D.; Parker, Laura C.; Wadsley, James

2016-10-01

We investigate mass segregation in group and cluster environments by identifying galaxy analogues in high-resolution dark-matter simulations. Subhaloes identified by the Amiga's Halo Finder (AHF) and ROCKSTAR halo finders have similar mass functions, independent of resolution, but different radial distributions due to significantly different subhalo hierarchies. We propose a simple way to classify subhaloes as galaxy analogues. The radial distributions of galaxy analogues agree well at large halocentric radii for both AHF and ROCKSTAR but disagree near parent halo centres where the phase-space information used by ROCKSTAR is essential. We see clear mass segregation at small radii (within 0.5 rvir) with average galaxy analogue mass decreasing with radius. Beyond the virial radius, we find a mild trend where the average galaxy analogue mass increases with radius. These mass segregation trends are strongest in small groups and dominated by the segregation of low-mass analogues. The lack of mass segregation in massive galaxy analogues suggests that the observed trends are driven by the complex accretion histories of the parent haloes rather than dynamical friction.

A compact E × B filter: A multi-collector cycloidal focusing mass spectrometer

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

Blase, Ryan C., E-mail: rblase@swri.edu; Miller, Greg; Brockwell, Tim

2015-10-15

A compact E × B mass spectrometer is presented. The mass spectrometer presented is termed a “perfect focus” mass spectrometer as the resolution of the device is independent of both the initial direction and energy of the ions (spatial and energy independent). The mass spectrometer is small in size (∼10.7 in.{sup 3}) and weight (∼2 kg), making it an attractive candidate for portability when using small, permanent magnets. A multi-collector Faraday cup design allows for the detection of multiple ion beams in discrete collectors simultaneously; providing the opportunity for isotope ratio monitoring. The mass resolution of the device is aroundmore » 400 through narrow collector slits and the sensitivity of the device follows expected theoretical calculations of the ion current produced in the electron impact ion source. Example mass spectra obtained from the cycloidal focusing mass spectrometer are presented as well as information on mass discrimination based on instrumental parameters and isotope ratio monitoring of certain ion signals in separate Faraday cups.« less

Very high resolution surface mass balance over Greenland modeled by the regional climate model MAR with a downscaling technique

NASA Astrophysics Data System (ADS)

Kittel, Christoph; Lang, Charlotte; Agosta, Cécile; Prignon, Maxime; Fettweis, Xavier; Erpicum, Michel

2016-04-01

This study presents surface mass balance (SMB) results at 5 km resolution with the regional climate MAR model over the Greenland ice sheet. Here, we use the last MAR version (v3.6) where the land-ice module (SISVAT) using a high resolution grid (5km) for surface variables is fully coupled while the MAR atmospheric module running at a lower resolution of 10km. This online downscaling technique enables to correct near-surface temperature and humidity from MAR by a gradient based on elevation before forcing SISVAT. The 10 km precipitation is not corrected. Corrections are stronger over the ablation zone where topography presents more variations. The model has been force by ERA-Interim between 1979 and 2014. We will show the advantages of using an online SMB downscaling technique in respect to an offline downscaling extrapolation based on local SMB vertical gradients. Results at 5 km show a better agreement with the PROMICE surface mass balance data base than the extrapolated 10 km MAR SMB results.

The Planck Constant, the International System of Units, and the 2012 North American Watt Balance Absolute Gravity Comparison

NASA Astrophysics Data System (ADS)

Newell, D. B.

2012-12-01

As outlined in Resolution 1 of the 24th Meeting of the General Conference on Weights and Measures (CGPM) on the future revision of the International System of Units (SI) [1], the current four SI base units the kilogram, the ampere, the kelvin and the mole, will be redefined in terms of invariants of nature. The new definitions will be based on fixed numerical values of the Planck constant (h), the elementary charge (e), the Boltzmann constant (k), and the Avogadro constant (NA), respectively. While significant progress has been made towards providing the necessary experimental results for the redefinition, some disagreement among the relevant data remain. Among the set of discrepant data towards the redefinition of the SI are the determinations of the Planck constant from the National Institute of Standards and Technology (NIST) watt balance [2] and the recent result from the National Research Council Canada (NRC) watt balance [3], with the discrepancy of roughly 2.5 parts in 107 being significantly outside the reported uncertainties. Of major concern is that the watt balance experiment is seen as a key component of a mise en pratique for the new kilogram definition, once such a redefinition takes place. The basic operational principle of a watt balance relates the Planck constant to mass, length, and time through h = mgvC, where m is the mass of an artifact mass standard, g is the local acceleration of gravity, v is a velocity, and C is a combination of frequencies and scalar constants. With the total uncertainty goal for the watt balance on the order of a few parts in 108, g needs to be determined at the location of the mass standard to parts in 109 such that its uncertainty is negligible in the final watt balance result. NIST and NRC have formed a collaborative effort to reconcile the relevant discrepant data and provide further progress towards preparing and testing a mise en pratique for the new kilogram definition. As an initial step, direct comparisons of key standards are being performed and similar components used in the operation of the watt balances are being jointly verified. To this end, a comparison between the gravitational measurement systems used in conjunction with the NIST and NRC watt balances was carried out in early 2012. The results of the comparison provide verification of the gravity values used in the recently published Planck constant determinations that play a vital role in the redefinition effort of the SI. [1] Resolution 1 of the 24th Meeting of the General Conference on Weights and Measures (CGPM) 2011 On the possible future revision of the International System of Units, Bureau International des Poids et Mesures, Paris, http://www.bipm.org/en/si/new_si/ [2] Steiner R L, Williams E R, Liu R, and Newell D B 2007 Uncertainty Improvements of the NIST Electronic Kilogram, IEEE Trans. Instrum. Meas., 56 2 592-596 [3] Steele A G, Meija J, Sanchez C A, Yang L, Wood B M, Sturgeon R E, Mester Z and Inglis A D 2012 Reconciling Planck constant determinations via watt balance and enriched-silicon measurements at NRC Canada Metrologia 49 1 L8-L10

Usability of small impact craters on small surface areas in crater count dating: Analysing examples from the Harmakhis Vallis outflow channel, Mars

NASA Astrophysics Data System (ADS)

Kukkonen, S.; Kostama, V.-P.

2018-05-01

The availability of very high-resolution images has made it possible to extend crater size-frequency distribution studies to small, deca/hectometer-scale craters. This has enabled the dating of small and young surface units, as well as recent, short-time and small-scale geologic processes that have occurred on the units. Usually, however, the higher the spatial resolution of space images is, the smaller area is covered by the images. Thus the use of single, very high-resolution images in crater count age determination may be debatable if the images do not cover the studied region entirely. Here we compare the crater count results for the floor of the Harmakhis Vallis outflow channel obtained from the images of the ConTeXt camera (CTX) and High Resolution Imaging Science Experiment (HiRISE) aboard the Mars Reconnaissance Orbiter (MRO). The CTX images enable crater counts for entire units on the Harmakhis Vallis main valley, whereas the coverage of the higher-resolution HiRISE images is limited and thus the images can only be used to date small parts of the units. Our case study shows that the crater count data based on small impact craters and small surface areas mainly correspond with the crater count data based on larger craters and more extensive counting areas on the same unit. If differences between the results were founded, they could usually be explained by the regional geology. Usually, these differences appeared when at least one cratering model age is missing from either of the crater datasets. On the other hand, we found only a few cases in which the cratering model ages were completely different. We conclude that the crater counts using small impact craters on small counting areas provide useful information about the geological processes which have modified the surface. However, it is important to remember that all the crater counts results obtained from a specific counting area always primarily represent the results from the counting area-not the whole unit. On the other hand, together with crater count results from extensive counting areas and lower-resolution images, crater counts on small counting areas but by using very high-resolution images is a very valuable tool for obtaining unique additional information about the local processes on the surface units.

The Characterization of Laser Ablation Patterns and a New Definition of Resolution in Matrix Assisted Laser Desorption Ionization Imaging Mass Spectrometry (MALDI-IMS).

PubMed

O'Rourke, Matthew B; Raymond, Benjamin B A; Padula, Matthew P

2017-05-01

Matrix assisted laser desorption ionization imaging mass spectrometry (MALDI-IMS) is a technique that has seen a sharp rise in both use and development. Despite this rapid adoption, there have been few thorough investigations into the actual physical mechanisms that underlie the acquisition of IMS images. We therefore set out to characterize the effect of IMS laser ablation patterns on the surface of a sample. We also concluded that the governing factors that control spatial resolution have not been correctly defined and therefore propose a new definition of resolution. Graphical Abstract ᅟ.

Electron source for a mini ion trap mass spectrometer

DOEpatents

Dietrich, D.D.; Keville, R.F.

1995-12-19

An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

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

Hill, N.C.; Limbach, P.A.; Shomo, R.E. II

The coupling of an autoneutralizing SF{sup {minus}}{sub 6} fast ion-beam gun to a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer is described. The fast neutral beam provides for secondary-ion-type FT/ICR mass analysis (e.g., production of abundant pseudomolecular (M+H){sup +} ions) of involatile samples without the need for external ion injection, since ions are formed at the entrance to the ICR ion trap. The design, construction, and testing of the hybrid instrument are described. The feasibility of the experiment (for both broadband and high-resolution FT/ICR positive-ion mass spectra) is demonstrated with {ital tetra}-butylammonium bromide and a Tylenol{sup ( )} sample.more » The ability to analyze high molecular weight polymers with high mass resolution is demonstrated for Teflon{sup ( )}. All of the advantages of the fast neutral beam ion source previously demonstrated with quadrupole mass analysis are preserved, and the additional advantages of FT/ICR mass analysis (e.g., high mass resolving power, ion trapping) are retained.« less

40 CFR 96.374 - Recordkeeping and reporting.

Code of Federal Regulations, 2010 CFR

2010-07-01

... entire year and shall report the NOX mass emissions data and heat input data for such unit, in an... monitoring of NOX mass emissions) for such unit for the entire year and report the NOX mass emissions data and heat input data for such unit in accordance with paragraph (d)(1) of this section; or (ii) Meet...

40 CFR 62.15250 - May I conduct stack testing less often?

Code of Federal Regulations, 2012 CFR

2012-07-01

... 15 nanograms per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter (total mass) for Class II units, for 2 consecutive years. In this case, you may choose... per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic...

40 CFR 62.15250 - May I conduct stack testing less often?

Code of Federal Regulations, 2014 CFR

2014-07-01

... 15 nanograms per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter (total mass) for Class II units, for 2 consecutive years. In this case, you may choose... per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic...

40 CFR 62.15250 - May I conduct stack testing less often?

Code of Federal Regulations, 2013 CFR

2013-07-01

... 15 nanograms per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic meter (total mass) for Class II units, for 2 consecutive years. In this case, you may choose... per dry standard cubic meter (total mass) for Class I units, or 30 nanograms per dry standard cubic...

Isobar Separation in a Multiple-Reflection Time-of-Flight Mass Spectrometer by Mass-Selective Re-Trapping.

PubMed

Dickel, Timo; Plaß, Wolfgang R; Lippert, Wayne; Lang, Johannes; Yavor, Mikhail I; Geissel, Hans; Scheidenberger, Christoph

2017-06-01

A novel method for (ultra-)high-resolution spatial mass separation in time-of-flight mass spectrometers is presented. Ions are injected into a time-of-flight analyzer from a radio frequency (rf) trap, dispersed in time-of-flight according to their mass-to-charge ratios and then re-trapped dynamically in the same rf trap. This re-trapping technique is highly mass-selective and after sufficiently long flight times can provide even isobaric separation. A theoretical treatment of the method is presented and the conditions for optimum performance of the method are derived. The method has been implemented in a multiple-reflection time-of-flight mass spectrometer and mass separation powers (FWHM) in excess of 70,000, and re-trapping efficiencies of up to 35% have been obtained for the protonated molecular ion of caffeine. The isobars glutamine and lysine (relative mass difference of 1/4000) have been separated after a flight time of 0.2 ms only. Higher mass separation powers can be achieved using longer flight times. The method will have important applications, including isobar separation in nuclear physics and (ultra-)high-resolution precursor ion selection in multiple-stage tandem mass spectrometry. Graphical Abstract ᅟ.

Isobar Separation in a Multiple-Reflection Time-of-Flight Mass Spectrometer by Mass-Selective Re-Trapping

NASA Astrophysics Data System (ADS)

Dickel, Timo; Plaß, Wolfgang R.; Lippert, Wayne; Lang, Johannes; Yavor, Mikhail I.; Geissel, Hans; Scheidenberger, Christoph

2017-06-01

A novel method for (ultra-)high-resolution spatial mass separation in time-of-flight mass spectrometers is presented. Ions are injected into a time-of-flight analyzer from a radio frequency (rf) trap, dispersed in time-of-flight according to their mass-to-charge ratios and then re-trapped dynamically in the same rf trap. This re-trapping technique is highly mass-selective and after sufficiently long flight times can provide even isobaric separation. A theoretical treatment of the method is presented and the conditions for optimum performance of the method are derived. The method has been implemented in a multiple-reflection time-of-flight mass spectrometer and mass separation powers (FWHM) in excess of 70,000, and re-trapping efficiencies of up to 35% have been obtained for the protonated molecular ion of caffeine. The isobars glutamine and lysine (relative mass difference of 1/4000) have been separated after a flight time of 0.2 ms only. Higher mass separation powers can be achieved using longer flight times. The method will have important applications, including isobar separation in nuclear physics and (ultra-)high-resolution precursor ion selection in multiple-stage tandem mass spectrometry. [Figure not available: see fulltext.

Structural elucidation of fucosylated chondroitin sulfates from sea cucumber using FTICR-MS/MS.

PubMed

Agyekum, Isaac; Pepi, Lauren; Yu, Yanlei; Li, Junhui; Yan, Lufeng; Linhardt, Robert J; Chen, Shiguo; Amster, I Jonathan

2018-02-01

Fucosylated chondroitin sulfates are complex polysaccharides extracted from sea cucumber. They have been extensively studied for their anticoagulant properties and have been implicated in other biological activities. While nuclear magnetic resonance spectroscopy has been used to extensively characterize fucosylated chondroitin sulfate oligomers, we herein report the first detailed mass characterization of fucosylated chondroitin sulfate using high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The two species of fucosylated chondroitin sulfates considered for this work include Pearsonothuria graeffei (FCS-Pg) and Isostichopus badionotus (FCS-Ib). Fucosylated chondroitin sulfate oligosaccharides were prepared by N-deacetylation-deaminative cleavage of the two fucosylated chondroitin sulfates and purified by repeated gel filtration. Accurate mass measurements obtained from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry measurements confirmed the oligomeric nature of these two fucosylated chondroitin sulfate oligosaccharides with each trisaccharide repeating unit averaging four sulfates per trisaccharide. Collision-induced dissociation of efficiently deprotonated molecular ions through Na/H + exchange proved useful in providing structurally relevant glycosidic and cross-ring product ions, capable of assigning the sulfate modifications on the fucosylated chondroitin sulfate oligomers. Careful examination of the tandem mass spectrometry of both species deferring in the positions of sulfate groups on the fucose residue (FCS-Pg-3,4- OS) and (FCS-Ib-2,4- OS) revealed cross-ring products 0,2 A αf and 2,4 X 2αf which were diagnostic for (FCS-Pg-3,4- OS) and 0,2 X 2αf diagnostic for (FCS-Ib-2,4- OS). Mass spectrometry and tandem mass spectrometry data acquired for both species varying in oligomer length (dp3-dp15) are presented.

Ubiquitous influence of wildfire emissions and secondary organic aerosol on summertime atmospheric aerosol in the forested Great Lakes region

NASA Astrophysics Data System (ADS)

Gunsch, Matthew J.; May, Nathaniel W.; Wen, Miao; Bottenus, Courtney L. H.; Gardner, Daniel J.; VanReken, Timothy M.; Bertman, Steven B.; Hopke, Philip K.; Ault, Andrew P.; Pratt, Kerri A.

2018-03-01

Long-range aerosol transport affects locations hundreds of kilometers from the point of emission, leading to distant particle sources influencing rural environments that have few major local sources. Source apportionment was conducted using real-time aerosol chemistry measurements made in July 2014 at the forested University of Michigan Biological Station near Pellston, Michigan, a site representative of the remote forested Great Lakes region. Size-resolved chemical composition of individual 0.5-2.0 µm particles was measured using an aerosol time-of-flight mass spectrometer (ATOFMS), and non-refractory aerosol mass less than 1 µm (PM1) was measured with a high-resolution aerosol mass spectrometer (HR-AMS). The field site was influenced by air masses transporting Canadian wildfire emissions and urban pollution from Milwaukee and Chicago. During wildfire-influenced periods, 0.5-2.0 µm particles were primarily aged biomass burning particles (88 % by number). These particles were heavily coated with secondary organic aerosol (SOA) formed during transport, with organics (average O/C ratio of 0.8) contributing 89 % of the PM1 mass. During urban-influenced periods, organic carbon, elemental carbon-organic carbon, and aged biomass burning particles were identified, with inorganic secondary species (ammonium, sulfate, and nitrate) contributing 41 % of the PM1 mass, indicative of atmospheric processing. With current models underpredicting organic carbon in this region and biomass burning being the largest combustion contributor to SOA by mass, these results highlight the importance for regional chemical transport models to accurately predict the impact of long-range transported particles on air quality in the upper Midwest, United States, particularly considering increasing intensity and frequency of Canadian wildfires.

Quadrupole mass filter: design and performance for operation in stability zone 3.

PubMed

Syed, Sarfaraz U A H; Hogan, Thomas J; Antony Joseph, Mariya J; Maher, Simon; Taylor, Stephen

2013-10-01

The predicted performance of a quadrupole mass filter (QMF) operating in Mathieu stability zone 3 is described in detail using computer simulations. The investigation considers the factors that limit the ultimate maximum resolution (Rmax) and percentage transmission (%Tx), which can be obtained for a given QMF for a particular scan line of operation. The performance curve (i.e., the resolution (R) versus number (N) of radio frequency (rf) cycles experienced by the ions in the mass filter) has been modeled for the upper and lower tip of stability zone 3. The saturation behavior of the performance curve observed in practice for zone 3 is explained. Furthermore, new design equations are presented by examining the intersection of the scan line with stability zone 3. Resolution versus transmission characteristics of stability zones 1 and 3 are compared and the dependence of performance for zones 1 and 3 is related to particular instrument operating parameters.

The technical consideration of multi-beam mask writer for production

NASA Astrophysics Data System (ADS)

Lee, Sang Hee; Ahn, Byung-Sup; Choi, Jin; Shin, In Kyun; Tamamushi, Shuichi; Jeon, Chan-Uk

2016-10-01

Multi-beam mask writer is under development to solve the throughput and patterning resolution problems in VSB mask writer. Theoretically, the writing time is appropriate for future design node and the resolution is improved with multi-beam mask writer. Many previous studies show the feasible results of resolution, CD control and registration. Although such technical results of development tool seem to be enough for mass production, there are still many unexpected problems for real mass production. In this report, the technical challenges of multi-beam mask writer are discussed in terms of production and application. The problems and issues are defined based on the performance of current development tool compared with the requirements of mask quality. Using the simulation and experiment, we analyze the specific characteristics of electron beam in multi-beam mask writer scheme. Consequently, we suggest necessary specifications for mass production with multi-beam mask writer in the future.

Development of high resolution simulations of the atmospheric environment using the MASS model

NASA Technical Reports Server (NTRS)

Kaplan, Michael L.; Zack, John W.; Karyampudi, V. Mohan

1989-01-01

Numerical simulations were performed with a very high resolution (7.25 km) version of the MASS model (Version 4.0) in an effort to diagnose the vertical wind shear and static stability structure during the Shuttle Challenger disaster which occurred on 28 January 1986. These meso-beta scale simulations reveal that the strongest vertical wind shears were concentrated in the 200 to 150 mb layer at 1630 GMT, i.e., at about the time of the disaster. These simulated vertical shears were the result of two primary dynamical processes. The juxtaposition of both of these processes produced a shallow (30 mb deep) region of strong vertical wind shear, and hence, low Richardson number values during the launch time period. Comparisons with the Cape Canaveral (XMR) rawinsonde indicates that the high resolution MASS 4.0 simulation more closely emulated nature than did previous simulations of the same event with the GMASS model.

Determination of the Isotopic Enrichment of 13C- and 2H-Labeled Tracers of Glucose Using High-Resolution Mass Spectrometry: Application to Dual- and Triple-Tracer Studies.

PubMed

Trötzmüller, Martin; Triebl, Alexander; Ajsic, Amra; Hartler, Jürgen; Köfeler, Harald; Regittnig, Werner

2017-11-21

Multiple-tracer approaches for investigating glucose metabolism in humans usually involve the administration of stable and radioactive glucose tracers and the subsequent determination of tracer enrichments in sampled blood. When using conventional, low-resolution mass spectrometry (LRMS), the number of spectral interferences rises rapidly with the number of stable tracers employed. Thus, in LRMS, both computational effort and statistical uncertainties associated with the correction for spectral interferences limit the number of stable tracers that can be simultaneously employed (usually two). Here we show that these limitations can be overcome by applying high-resolution mass spectrometry (HRMS). The HRMS method presented is based on the use of an Orbitrap mass spectrometer operated at a mass resolution of 100 000 to allow electrospray-generated ions of the deprotonated glucose molecules to be monitored at their exact masses. The tracer enrichment determination in blood plasma is demonstrated for several triple combinations of 13 C- and 2 H-labeled glucose tracers (e.g., [1- 2 H 1 ]-, [6,6- 2 H 2 ]-, [1,6- 13 C 2 ]glucose). For each combination it is shown that ions arising from 2 H-labeled tracers are completely differentiated from those arising from 13 C-labeled tracers, thereby allowing the enrichment of a tracer to be simply calculated from the observed ion intensities using a standard curve with curve parameters unaffected by the presence of other tracers. For each tracer, the HRMS method exhibits low limits of detection and good repeatability in the tested 0.1-15.0% enrichment range. Additionally, due to short sample preparation and analysis times, the method is well-suited for high-throughput determination of multiple glucose tracer enrichments in plasma samples.

Structure Annotation and Quantification of Wheat Seed Oxidized Lipids by High-Resolution LC-MS/MS.

PubMed

Riewe, David; Wiebach, Janine; Altmann, Thomas

2017-10-01

Lipid oxidation is a process ubiquitous in life, but the direct and comprehensive analysis of oxidized lipids has been limited by available analytical methods. We applied high-resolution liquid chromatography-mass spectrometry (LC-MS) and tandem mass spectrometry (MS/MS) to quantify oxidized lipids (glycerides, fatty acids, phospholipids, lysophospholipids, and galactolipids) and implemented a platform-independent high-throughput-amenable analysis pipeline for the high-confidence annotation and acyl composition analysis of oxidized lipids. Lipid contents of 90 different naturally aged wheat ( Triticum aestivum ) seed stocks were quantified in an untargeted high-resolution LC-MS experiment, resulting in 18,556 quantitative mass-to-charge ratio features. In a posthoc liquid chromatography-tandem mass spectrometry experiment, high-resolution MS/MS spectra (5 mD accuracy) were recorded for 8,957 out of 12,080 putatively monoisotopic features of the LC-MS data set. A total of 353 nonoxidized and 559 oxidized lipids with up to four additional oxygen atoms were annotated based on the accurate mass recordings (1.5 ppm tolerance) of the LC-MS data set and filtering procedures. MS/MS spectra available for 828 of these annotations were analyzed by translating experimentally known fragmentation rules of lipids into the fragmentation of oxidized lipids. This led to the identification of 259 nonoxidized and 365 oxidized lipids by both accurate mass and MS/MS spectra and to the determination of acyl compositions for 221 nonoxidized and 295 oxidized lipids. Analysis of 15-year aged wheat seeds revealed increased lipid oxidation and hydrolysis in seeds stored in ambient versus cold conditions. © 2017 The author(s). All Rights Reserved.

High-Resolution Infrared Imaging and Polarimetry plus Spectroscopy of Evolved Red and Yellow Supergiants

NASA Astrophysics Data System (ADS)

Gordon, Michael Scott; Humphreys, Roberta; Jones, Terry J.; Gehrz, Robert D.

2018-01-01

To what extent mass loss and periods of enhanced stellar outflow can influence the terminal state of the most massive stars remains an outstanding question in the fields of stellar physics, chemical enrichment of the Local Universe, andsupernova research. For my dissertation, I focus on characterizing the stellar ejecta around supergiants through a combination of observing techniques. Using the LBT, MMT, IRTF, VLT, and SOFIA observatories, I have performed high-resolution imaging, spectroscopy, and polarimetry—methods that provide us with keen insight on mass-loss histories and 3D morphology of the Local Group's most fascinating stars.Based on spectroscopic evidence for mass loss in the optical and the presence ofcircumstellar (CS) dust in infrared SEDs, we find that 30%–40% of observed yellow supergiants in M31 and M33 are likely in a post-RSG state. We also presentnear-IR spectra from IRTF/SPeX of optically-obscured RSGs in M33. These IR-bright sources likely have some of the highest mass-loss rates and are self-obscured in the optical by their own CS ejecta. For Galactic red supergiants (RSGs), we are able to observe the gas and CS dust ejecta both close in to the central star and at larger distances. The resulting radial profiles are valuable probes on timescale for the ejecta when combined with radiative-transfer models. We find evidence for both variable/high mass-loss events and constant mass loss over the last few thousand years. Finally, we discuss the use of high-resolution imaging polarimetry with VLT/NACO of two co-eval RSG clusters toward the Galactic center. The resulting polarized intensity images in the near-infrared provide unprecedented spatial and contrast resolution of the scattered light from extended nebular material.

Mass selectivity of dipolar resonant excitation in a linear quadrupole ion trap.

PubMed

Douglas, D J; Konenkov, N V

2014-03-15

For mass analysis, linear quadrupole ion traps operate with dipolar excitation of ions for either axial or radial ejection. There have been comparatively few computer simulations of this process. We introduce a new concept, the excitation contour, S(q), the fraction of the excited ions that reach the trap electrodes when trapped at q values near that corresponding to the excitation frequency. Ion trajectory calculations are used to calculate S(q). Ions are given Gaussian distributions of initial positions in x and y, and thermal initial velocity distributions. To model gas damping, a drag force is added to the equations of motion. The effects of the initial conditions, ejection Mathieu parameter q, scan speed, excitation voltage and collisional damping, are modeled. We find that, with no buffer gas, the mass resolution is mostly determined by the excitation time and is given by R~dβ/dq qn, where β(q) determines the oscillation frequency, and n is the number of cycles of the trapping radio frequency during the excitation or ejection time. The highest resolution at a given scan speed is reached with the lowest excitation amplitude that gives ejection. The addition of a buffer gas can increase the mass resolution. The simulation results are in broad agreement with experiments. The excitation contour, S(q), introduced here, is a useful tool for studying the ejection process. The excitation strength, excitation time and buffer gas pressure interact in a complex way but, when set properly, a mass resolution R0.5 of at least 10,000 can be obtained at a mass-to-charge ratio of 609. Copyright © 2014 John Wiley & Sons, Ltd.

Matrix vapor deposition/recrystallization and dedicated spray preparation for high-resolution scanning microprobe matrix-assisted laser desorption/ionization imaging mass spectrometry (SMALDI-MS) of tissue and single cells.

PubMed

Bouschen, Werner; Schulz, Oliver; Eikel, Daniel; Spengler, Bernhard

2010-02-01

Matrix preparation techniques such as air spraying or vapor deposition were investigated with respect to lateral migration, integration of analyte into matrix crystals and achievable lateral resolution for the purpose of high-resolution biological imaging. The accessible mass range was found to be beyond 5000 u with sufficient analytical sensitivity. Gas-assisted spraying methods (using oxygen-free gases) provide a good compromise between crystal integration of analyte and analyte migration within the sample. Controlling preparational parameters with this method, however, is difficult. Separation of the preparation procedure into two steps, instead, leads to an improved control of migration and incorporation. The first step is a dry vapor deposition of matrix onto the investigated sample. In a second step, incorporation of analyte into the matrix crystal is enhanced by a controlled recrystallization of matrix in a saturated water atmosphere. With this latter method an effective analytical resolution of 2 microm in the x and y direction was achieved for scanning microprobe matrix-assisted laser desorption/ionization imaging mass spectrometry (SMALDI-MS). Cultured A-498 cells of human renal carcinoma were successfully investigated by high-resolution MALDI imaging using the new preparation techniques. Copyright 2010 John Wiley & Sons, Ltd.

Late-Quaternary glacial to postglacial sedimentation in three adjacent fjord-lakes of the Québec North Shore (eastern Canadian Shield)

NASA Astrophysics Data System (ADS)

Poiré, Antoine G.; Lajeunesse, Patrick; Normandeau, Alexandre; Francus, Pierre; St-Onge, Guillaume; Nzekwe, Obinna P.

2018-04-01

High-resolution swath bathymetry imagery allowed mapping in great detail the sublacustrine geomorphology of lakes Pentecôte, Walker and Pasteur, three deep adjacent fjord-lakes of the Québec North Shore (eastern Canada). These sedimentary basins have been glacio-isostatically uplifted to form deep steep-sided elongated lakes. Their key geographical position and limnogeological characteristics typical of fjords suggest exceptional potential for long-term high-resolution paleoenvironmental reconstitutions. Acoustic subbottom profiles acquired using a bi-frequency Chirp echosounder (3.5 & 12 kHz), together with cm- and m-long sediment core data, reveal the presence of four acoustic stratigraphic units. The acoustic basement (Unit 1) represents the structural bedrock and/or the ice-contact sediments of the Laurentide Ice Sheet and reveals V-shaped bedrock valleys at the bottom of the lakes occupied by ice-loaded sediments in a basin-fill geometry (Unit 2). Moraines observed at the bottom of lakes and in their structural valleys indicate a deglaciation punctuated by short-term ice margin stabilizations. Following ice retreat and their isolation, the fjord-lakes were filled by a thick draping sequence of rhythmically laminated silts and clays (Unit 3) deposited during glaciomarine and/or glaciolacustrine settings. These sediments were episodically disturbed by mass-movements during deglaciation due to glacial-isostatic rebound. AMS 14C dating reveal that the transition between deglaciation of the lakes Pentecôte and Walker watersheds and the development of para- and post-glacial conditions occurred around 8000 cal BP. The development of the lake-head river delta plain during the Holocene provided a constant source of fluvial sediment supply to the lakes and the formation of turbidity current bedforms on the sublacustrine delta slopes. The upper sediment succession (i.e., ∼4-∼6.5 m) consists of a continuous para-to post-glacial sediment drape (Unit 4) that contains laminated and massive sediment and series of Rapidly Deposited Layers. These results allow establishing a conceptual model of how a glaciated coastal fjord evolves during and after deglaciation in a context of rapid glacio-isostatically induced forced regression.

Seismic responses and controlling factors of Miocene deepwater gravity-flow deposits in Block A, Lower Congo Basin

NASA Astrophysics Data System (ADS)

Wang, Linlin; Wang, Zhenqi; Yu, Shui; Ngia, Ngong Roger

2016-08-01

The Miocene deepwater gravity-flow sedimentary system in Block A of the southwestern part of the Lower Congo Basin was identified and interpreted using high-resolution 3-D seismic, drilling and logging data to reveal development characteristics and main controlling factors. Five types of deepwater gravity-flow sedimentary units have been identified in the Miocene section of Block A, including mass transport, deepwater channel, levee, abandoned channel and sedimentary lobe deposits. Each type of sedimentary unit has distinct external features, internal structures and lateral characteristics in seismic profiles. Mass transport deposits (MTDs) in particular correspond to chaotic low-amplitude reflections in contact with mutants on both sides. The cross section of deepwater channel deposits in the seismic profile is in U- or V-shape. The channel deposits change in ascending order from low-amplitude, poor-continuity, chaotic filling reflections at the bottom, to high-amplitude, moderate to poor continuity, chaotic or sub-parallel reflections in the middle section and to moderate-weak amplitude, good continuity, parallel or sub-parallel reflections in the upper section. The sedimentary lobes are laterally lobate, which corresponds to high-amplitude, good-continuity, moundy reflection signatures in the seismic profile. Due to sediment flux, faults, and inherited terrain, few mass transport deposits occur in the northeastern part of the study area. The front of MTDs is mainly composed of channel-levee complex deposits, while abandoned-channel and lobe-deposits are usually developed in high-curvature channel sections and the channel terminals, respectively. The distribution of deepwater channel, levee, abandoned channel and sedimentary lobe deposits is predominantly controlled by relative sea level fluctuations and to a lesser extent by tectonism and inherited terrain.

Fine resolution probabilistic land cover classification of landscapes in the southeastern United States

Treesearch

Joseph St. Peter; John Hogland; Nathaniel Anderson; Jason Drake; Paul Medley

2018-01-01

Land cover classification provides valuable information for prioritizing management and conservation operations across large landscapes. Current regional scale land cover geospatial products within the United States have a spatial resolution that is too coarse to provide the necessary information for operations at the local and project scales. This paper describes a...

A resolution honoring Admiral Thad Allen of the United States Coast Guard (Ret.) for his lifetime of selfless commitment and exemplary service to the United States.

THOMAS, 112th Congress

Sen. Cochran, Thad [R-MS

2011-05-05

Senate - 06/30/2011 Resolution agreed to in Senate without amendment and with a preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

A resolution recognizing Hispanic Heritage Month and celebrating the heritage and culture of Latinos in the United States and the immense contributions of Latinos to the United States.

THOMAS, 113th Congress

Sen. Menendez, Robert [D-NJ

2014-09-15

Senate - 09/17/2014 Resolution agreed to in Senate without amendment and with a preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

Explorer of Enceladus and Titan (E2T): Investigating ocean worlds' evolution and habitability in the solar system

NASA Astrophysics Data System (ADS)

Mitri, Giuseppe; Postberg, Frank; Soderblom, Jason M.; Wurz, Peter; Tortora, Paolo; Abel, Bernd; Barnes, Jason W.; Berga, Marco; Carrasco, Nathalie; Coustenis, Athena; Paul de Vera, Jean Pierre; D'Ottavio, Andrea; Ferri, Francesca; Hayes, Alexander G.; Hayne, Paul O.; Hillier, Jon K.; Kempf, Sascha; Lebreton, Jean-Pierre; Lorenz, Ralph D.; Martelli, Andrea; Orosei, Roberto; Petropoulos, Anastassios E.; Reh, Kim; Schmidt, Juergen; Sotin, Christophe; Srama, Ralf; Tobie, Gabriel; Vorburger, Audrey; Vuitton, Véronique; Wong, Andre; Zannoni, Marco

2018-06-01

Titan, with its organically rich and dynamic atmosphere and geology, and Enceladus, with its active plume, both harbouring global subsurface oceans, are prime environments in which to investigate the habitability of ocean worlds and the conditions for the emergence of life. We present a space mission concept, the Explorer of Enceladus and Titan (E2T), which is dedicated to investigating the evolution and habitability of these Saturnian satellites. E2T is proposed as a medium-class mission led by ESA in collaboration with NASA in response to ESA's M5 Cosmic Vision Call. E2T proposes a focused payload that would provide in-situ composition investigations and high-resolution imaging during multiple flybys of Enceladus and Titan using a solar-electric powered spacecraft in orbit around Saturn. The E2T mission would provide high-resolution mass spectrometry of the plume currently emanating from Enceladus' south polar terrain and of Titan's changing upper atmosphere. In addition, high-resolution infrared (IR) imaging would detail Titan's geomorphology at 50-100 m resolution and the temperature of the fractures on Enceladus' south polar terrain at meter resolution. These combined measurements of both Titan and Enceladus would enable the E2T mission scenario to achieve two major scientific goals: 1) Study the origin and evolution of volatile-rich ocean worlds; and 2) Explore the habitability and potential for life in ocean worlds. E2T's two high-resolution time-of-flight mass spectrometers would enable resolution of the ambiguities in chemical analysis left by the NASA/ESA/ASI Cassini-Huygens mission regarding the identification of low-mass organic species, detect high-mass organic species for the first time, further constrain trace species such as the noble gases, and clarify the evolution of solid and volatile species. The high-resolution IR camera would reveal the geology of Titan's surface and the energy dissipated by Enceladus' fractured south polar terrain and plume in detail unattainable by the Cassini mission.

Structural characterization and identification of iridoid glycosides, saponins, phenolic acids and flavonoids in Flos Lonicerae Japonicae by a fast liquid chromatography method with diode-array detection and time-of-flight mass spectrometry.

PubMed

Qi, Lian-Wen; Chen, Chun-Yun; Li, Ping

2009-10-01

A fast liquid chromatography method with diode-array detection (DAD) and time-of-flight mass spectrometry (TOF-MS) has been developed for analysis of constituents in Flos Lonicerae Japonicae (FLJ), a traditional Chinese medicine derived from the flower bud of Lonicera japonica. The chromatographic analytical time decreased to 25 min without sacrificing resolution using a column packed with 1.8-microm porous particles (4.6 x 50 mm), three times faster than the performance of conventional 5.0-microm columns (4.6 x 150 mm). Four major groups of compounds previously isolated from FLJ were structurally characterized by DAD-TOF-MS: iridoid glycosides showed maximum UV absorption at 240 nm; phenolic acids at 217, 242, and 326 nm; flavonoids at 255 and 355 nm; while saponins had no absorption. In electrospray ionization (ESI)-TOF-MS experiments, elimination of a glucose unit (162 Da), and successive losses of H(2)O, CH(3)OH and CO, were generally observed in iridoid glycosides; saponins were characterized by a series of identical aglycone ions; phenolic acids typically generated a base peak at [M-H-caffeoyl](-) by loss of a caffeic acid unit (162 Da) and several marked quinic acid moiety ions; cleavage of the glycosidic bond (loss of 162 or 308 Da), subsequent losses of H(2)O, CO, RDA and C-ring fragmentation were the most possible fragmentation pathways for flavonoids. By accurate mass measurements within 4 ppm error for each molecular ion and subsequent fragment ions, as well as the 'full mass spectral' information of TOF-MS, a total of 41 compounds including 13 iridoid glycosides, 11 phenolic acids, 7 saponins, and 10 flavonoids were identified in a methanolic extract of FLJ. Copyright (c) 2009 John Wiley & Sons, Ltd.

Localization accuracy of compact binary coalescences detected by the third-generation gravitational-wave detectors and implication for cosmology

NASA Astrophysics Data System (ADS)

Zhao, Wen; Wen, Linqing

2018-03-01

We use the Fisher information matrix to investigate the angular resolution and luminosity distance uncertainty for coalescing binary neutron stars (BNSs) and neutron star-black hole binaries (NSBHs) detected by the third-generation (3G) gravitational-wave (GW) detectors. Our study focuses on an individual 3G detector and a network of up to four 3G detectors at different locations including the United States, Europe, China, and Australia for the proposed Einstein Telescope (ET) and Cosmic Explorer (CE) detectors. In particular, we examine the effect of the Earth's rotation, as GW signals from BNS and low-mass NSBH systems could be hours long for 3G detectors. In this case, an individual detector can be effectively treated as a detector network with long baselines formed by the trajectory of the detector as it rotates with the Earth. Therefore, a single detector or two-detector networks could also be used to localize the GW sources effectively. We find that a time-dependent antenna beam-pattern function can help better localize BNS and NSBH sources, especially edge-on ones. The medium angular resolution for one ET-D detector is around 150 deg2 for BNSs at a redshift of z =0.1 , which improves rapidly with a decreasing low-frequency cutoff flow in sensitivity. The medium angular resolution for a network of two CE detectors in the United States and Europe, respectively, is around 20 deg2 at z =0.2 for the simulated BNS and NSBH samples. While for a network of two ET-D detectors, the similar angular resolution can be achieved at a much higher redshift of z =0.5 . The angular resolution of a network of three detectors is mainly determined by the baselines between detectors regardless of the CE or ET detector type. The medium angular resolution of BNS for a network of three detectors of the ET-D or CE type in the United States, Europe, and Australia is around 10 deg2 at z =2 . We discuss the implications of our results for multimessenger astronomy and, in particular, for using GW sources as independent tools to constrain the Hubble constant H0, the deceleration parameter q0, and the equation-of-state (EoS) of dark energy. We find that, in general, if 10 BNSs or NSBHs at z =0.1 with known redshifts are detected by 3G networks consisting of two ET-like detectors, H0 can be measured with an accuracy of 0.9%. If 1000 face-on BNSs at z <2 are detected with known redshifts, we are able to achieve Δ q0=0.002 for the deceleration parameter, or Δ w0=0.03 and Δ wa=0.2 for EoS of dark energy, respectively.

21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Greatly Expands Mass Spectrometry Toolbox

NASA Astrophysics Data System (ADS)

Shaw, Jared B.; Lin, Tzu-Yung; Leach, Franklin E.; Tolmachev, Aleksey V.; Tolić, Nikola; Robinson, Errol W.; Koppenaal, David W.; Paša-Tolić, Ljiljana

2016-12-01

We provide the initial performance evaluation of a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer operating at the Environmental Molecular Sciences Laboratory at the Pacific Northwest National Laboratory. The spectrometer constructed for the 21T system employs a commercial dual linear ion trap mass spectrometer coupled to a FTICR spectrometer designed and built in-house. Performance gains from moving to higher magnetic field strength are exemplified by the measurement of peptide isotopic fine structure, complex natural organic matter mixtures, and large proteins. Accurate determination of isotopic fine structure was demonstrated for doubly charged Substance P with minimal spectral averaging, and 8158 molecular formulas assigned to Suwannee River Fulvic Acid standard with root-mean-square (RMS) error of 10 ppb. We also demonstrated superior performance for intact proteins; namely, broadband isotopic resolution of the entire charge state distribution of apo-transferrin (78 kDa) and facile isotopic resolution of monoclonal antibody under a variety of acquisition parameters (e.g., 6 s time-domains with absorption mode processing yielded resolution of approximately 1 M at m/z = 2700).

21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Greatly Expands Mass Spectrometry Toolbox

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

Shaw, Jared B.; Lin, Tzu-Yung; Leach, Franklin E.

We provide the initial performance evaluation of a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer operating at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory. The spectrometer constructed for the 21T system employs a commercial dual linear ion trap mass spectrometer coupled to a FTICR spectrometer designed and built in-house. Performance gains from moving to higher magnetic field strength are exemplified by the measurement of peptide isotopic fine structure, complex natural organic matter mixtures, and large proteins. Accurate determination of isotopic fine structure was demonstrated for doubly charged substance P with minimal spectral averaging, and 8,158more » molecular formulas assigned to Suwannee River Fulvic Acid standard with RMS error of 10 ppb. We also demonstrated superior performance for intact proteins; namely, broadband isotopic resolution of the entire charge state distribution of apotransferrin (78 kDa) and facile isotopic resolution of monoclonal antibody under a variety of acquisition parameters (e.g. 6 s time-domains with absorption mode processing yielded resolution of approximately 1M at m/z =2,700).« less

Simulating Halos with the Caterpillar Project

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2016-04-01

The Caterpillar Project is a beautiful series of high-resolution cosmological simulations. The goal of this project is to examine the evolution of dark-matter halos like the Milky Ways, to learn about how galaxies like ours formed. This immense computational project is still in progress, but the Caterpillar team is already providing a look at some of its first results.Lessons from Dark-Matter HalosWhy simulate the dark-matter halos of galaxies? Observationally, the formation history of our galaxy is encoded in galactic fossil record clues, like the tidal debris from disrupted satellite galaxies in the outer reaches of our galaxy, or chemical abundance patterns throughout our galactic disk and stellar halo.But to interpret this information in a way that lets us learn about our galaxys history, we need to first test galaxy formation and evolution scenarios via cosmological simulations. Then we can compare the end result of these simulations to what we observe today.This figure illustrates the difference that mass resolution makes. In the left panel, the mass resolution is 1.5*10^7 solar masses per particle. In the right panel, the mass resolution is 3*10^4 solar masses per particle [Griffen et al. 2016]A Computational ChallengeDue to how computationally expensive such simulations are, previous N-body simulations of the growth of Milky-Way-like halos have consisted of only one or a few halos each. But in order to establish a statistical understanding of how galaxy halos form and find out whether the Milky Ways halo is typical or unusual! it is necessary to simulate a larger number of halos.In addition, in order to accurately follow the formation and evolution of substructure within the dark-matter halos, these simulations must be able to resolve the smallest dwarf galaxies, which are around a million solar masses. This requires an extremely high mass resolution, which adds to the computational expense of the simulation.First OutcomesThese are the challenges faced by the Caterpillar Project, detailed in a recently published paper led by Brendan Griffen (Massachusetts Institute of Technology). The Caterpillar Project was designed to simulate 70 Milky-Way-size halos (quadrupling the total number of halos that have been simulated in the past!) at a high mass resolution (10,000 solar masses per particle) and time resolution (5 Myr per snapshot). The project is extremely computationally intense, requiring 14 million CPU hours and 700 TB of data storage!Mass evolution of the first 24 Caterpillar halos (selected to be Milky-Way-size at z=0). The inset panel shows the mass evolution normalized by the halo mass at z=0, demonstrating the highly varied evolution these different halos undergo. [Griffen et al. 2016]In this first study, the Griffen and collaboratorsshow the end states for the first 24 halos of the project, evolved from a large redshift to today (z=0). They use these initialresults to demonstrate the integrity of their data and the utility of their methods, which include new halo-finding techniques that recover more substructure within each halo.The first results from the Caterpillar Project are already enough to show clear general trends, such as the highly variable paths the different halos take as they merge, accrete, and evolve, as well as how different their ends states can be. Statistically examining the evolution of these halos is an importantnext step in providinginsight intothe origin and evolution of the Milky Way, and helping us to understand how our galaxy differs from other galaxies of similar mass. Keep an eye out for future results from this project!BonusCheck out this video (make sure to watch in HD!) of how the first 24 Milky-Way-like halos from the Caterpillar simulations form. Seeingthese halos evolve simultaneously is an awesome way to identifythe similarities and differences between them.CitationBrendan F. Griffen et al 2016 ApJ 818 10. doi:10.3847/0004-637X/818/1/10

Assessing the Impact of Source-Zone Remediation Efforts at the Contaminant-Plume Scale Through Analysis of Contaminant Mass Discharge

PubMed Central

Brusseau, M. L.; Hatton, J.; DiGuiseppi, W.

2011-01-01

The long-term impact of source-zone remediation efforts was assessed for a large site contaminated by trichloroethene. The impact of the remediation efforts (soil vapor extraction and in-situ chemical oxidation) was assessed through analysis of plume-scale contaminant mass discharge, which was measured using a high-resolution data set obtained from 23 years of operation of a large pump-and-treat system. The initial contaminant mass discharge peaked at approximately 7 kg/d, and then declined to approximately 2 kg/d. This latter value was sustained for several years prior to the initiation of source-zone remediation efforts. The contaminant mass discharge in 2010, measured several years after completion of the two source-zone remediation actions, was approximately 0.2 kg/d, which is ten times lower than the value prior to source-zone remediation. The time-continuous contaminant mass discharge data can be used to evaluate the impact of the source-zone remediation efforts on reducing the time required to operate the pump-and-treat system, and to estimate the cost savings associated with the decreased operational period. While significant reductions have been achieved, it is evident that the remediation efforts have not completely eliminated contaminant mass discharge and associated risk. Remaining contaminant mass contributing to the current mass discharge is hypothesized to comprise poorly-accessible mass in the source zones, as well as aqueous (and sorbed) mass present in the extensive lower-permeability units located within and adjacent to the contaminant plume. The fate of these sources is an issue of critical import to the remediation of chlorinated-solvent contaminated sites, and development of methods to address these sources will be required to achieve successful long-term management of such sites and to ultimately transition them to closure. PMID:22115080

Does resolution of flow field observation influence apparent habitat use and energy expenditure in juvenile coho salmon?

USGS Publications Warehouse

Tullos, Desiree D.; Walter, Cara; Dunham, Jason B.

2016-01-01

This study investigated how the resolution of observation influences interpretation of how fish, juvenile Coho Salmon (Oncorhynchus kisutch), exploit the hydraulic environment in streams. Our objectives were to evaluate how spatial resolution of the flow field observation influenced: (1) the velocities considered to be representative of habitat units; (2) patterns of use of the hydraulic environment by fish; and (3) estimates of energy expenditure. We addressed these objectives using observations within a 1:1 scale physical model of a full-channel log jam in an outdoor experimental stream. Velocities were measured with Acoustic Doppler Velocimetry at a 10 cm grid spacing, whereas fish locations and tailbeat frequencies were documented over time using underwater videogrammetry. Results highlighted that resolution of observation did impact perceived habitat use and energy expenditure, as did the location of measurement within habitat units and the use of averaging to summarize velocities within a habitat unit. In this experiment, the range of velocities and energy expenditure estimates increased with coarsening resolution (grid spacing from 10 to 100 cm), reducing the likelihood of measuring the velocities locally experienced by fish. In addition, the coarser resolutions contributed to fish appearing to select velocities that were higher than what was measured at finer resolutions. These findings indicate the need for careful attention to and communication of resolution of observation in investigating the hydraulic environment and in determining the habitat needs and bioenergetics of aquatic biota.

Deployment of United Nations Peace Keeping Forces: The Nature of Transportation and Review of Current Methodologies.

DTIC Science & Technology

1980-06-06

cessation of hostilities in accordance hwith all the terms of UN Resolution 998 ( ES -l) of 3 November 1956" relating to the armistice line between Egypt and...passed a series of resolu- tions. The first (GA Res. 997 ( ES -l), 2 November 1956) called for a cease fire and a return of forces to the armistice...lines. The second resolution (GS Res. 998 ( ES -l), 4 November 1956) established a United Nations Emergency Force. (Resolutions relevant to UNEF are

Stochastic Models for Precipitable Water in Convection

NASA Astrophysics Data System (ADS)

Leung, Kimberly

Atmospheric precipitable water vapor (PWV) is the amount of water vapor in the atmosphere within a vertical column of unit cross-sectional area and is a critically important parameter of precipitation processes. However, accurate high-frequency and long-term observations of PWV in the sky were impossible until the availability of modern instruments such as radar. The United States Department of Energy (DOE)'s Atmospheric Radiation Measurement (ARM) Program facility made the first systematic and high-resolution observations of PWV at Darwin, Australia since 2002. At a resolution of 20 seconds, this time series allowed us to examine the volatility of PWV, including fractal behavior with dimension equal to 1.9, higher than the Brownian motion dimension of 1.5. Such strong fractal behavior calls for stochastic differential equation modeling in an attempt to address some of the difficulties of convective parameterization in various kinds of climate models, ranging from general circulation models (GCM) to weather research forecasting (WRF) models. This important observed data at high resolution can capture the fractal behavior of PWV and enables stochastic exploration into the next generation of climate models which considers scales from micrometers to thousands of kilometers. As a first step, this thesis explores a simple stochastic differential equation model of water mass balance for PWV and assesses accuracy, robustness, and sensitivity of the stochastic model. A 1000-day simulation allows for the determination of the best-fitting 25-day period as compared to data from the TWP-ICE field campaign conducted out of Darwin, Australia in early 2006. The observed data and this portion of the simulation had a correlation coefficient of 0.6513 and followed similar statistics and low-resolution temporal trends. Building on the point model foundation, a similar algorithm was applied to the National Center for Atmospheric Research (NCAR)'s existing single-column model as a test-of-concept for eventual inclusion in a general circulation model. The stochastic scheme was designed to be coupled with the deterministic single-column simulation by modifying results of the existing convective scheme (Zhang-McFarlane) and was able to produce a 20-second resolution time series that effectively simulated observed PWV, as measured by correlation coefficient (0.5510), fractal dimension (1.9), statistics, and visual examination of temporal trends.

Sensitivity of Hydrologic Extremes to Spatial Resolution of Meteorological Forcings: A Case Study of the Conterminous United States

NASA Astrophysics Data System (ADS)

Kao, S. C.; Naz, B. S.; Gangrade, S.; Ashfaq, M.; Rastogi, D.

2016-12-01

The magnitude and frequency of hydroclimate extremes are projected to increase in the conterminous United States (CONUS) with significant implications for future water resource planning and flood risk management. Nevertheless, apart from the change of natural environment, the choice of model spatial resolution could also artificially influence the features of simulated extremes. To better understand how the spatial resolution of meteorological forcings may affect hydroclimate projections, we test the runoff sensitivity using the Variable Infiltration Capacity (VIC) model that was calibrated for each CONUS 8-digit hydrologic unit (HUC8) at 1/24° ( 4km) grid resolution. The 1980-2012 gridded Daymet and PRISM meteorological observations are used to conduct the 1/24° resolution control simulation. Comparative simulations are achieved by smoothing the 1/24° forcing into 1/12° and 1/8° resolutions which are then used to drive the VIC model for the CONUS. In addition, we also test how the simulated high and low runoff conditions would react to change in precipitation (±10%) and temperature (+1°C). The results are further analyzed for various types of hydroclimate extremes across different watersheds in the CONUS. This work helps us understand the sensitivity of simulated runoff to different spatial resolutions of climate forcings and also its sensitivity to different watershed sizes and characteristics of extreme events in the future climate conditions.

Time-of-flight mass spectrographs—From ions to neutral atoms

NASA Astrophysics Data System (ADS)

Möbius, E.; Galvin, A. B.; Kistler, L. M.; Kucharek, H.; Popecki, M. A.

2016-12-01

After their introduction to space physics in the mid 1980s time-of-flight (TOF) spectrographs have become a main staple in spaceborne mass spectrometry. They have largely replaced magnetic spectrometers, except when extremely high mass resolution is required to identify complex molecules, for example, in the vicinity of comets or in planetary atmospheres. In combination with electrostatic analyzers and often solid state detectors, TOF spectrographs have become key instruments to diagnose space plasma velocity distributions, mass, and ionic charge composition. With a variety of implementation schemes that also include isochronous electric field configurations, TOF spectrographs can respond to diverse science requirements. This includes a wide range in mass resolution to allow the separation of medium heavy isotopes or to simply provide distributions of the major species, such as H, He, and O, to obtain information on source tracers or mass fluxes. With a top-hat analyzer at the front end, or in combination with deflectors for three-axis stabilized spacecraft, the distribution function of ions can be obtained with good time resolution. Most recently, the reach of TOF ion mass spectrographs has been extended to include energetic neutral atoms. After selecting the arrival direction with mechanical collimation, followed by conversion to ions, adapted TOF sensors form a new branch of the spectrograph family tree. We review the requirements, challenges, and implementation schemes for ion and neutral atom spectrographs, including potential directions for the future, while largely avoiding overlap with complementary contributions in this special issue.

A High-resolution Study of Presupernova Core Structure

NASA Astrophysics Data System (ADS)

Sukhbold, Tuguldur; Woosley, S. E.; Heger, Alexander

2018-06-01

The density structure surrounding the iron core of a massive star when it dies is known to have a major effect on whether or not the star explodes. Here we repeat previous surveys of presupernova evolution with some important corrections to code physics and four to 10 times better mass resolution in each star. The number of presupernova masses considered is also much larger. Over 4000 models are calculated in the range from 12 to 60 M ⊙ with varying mass loss rates. The core structure is not greatly affected by the increased spatial resolution. The qualitative patterns of compactness measures and their extrema are the same, but with the increased number of models, the scatter seen in previous studies is replaced by several localized branches. More physics-based analyses by Ertl et al. and Müller et al. show these branches with less scatter than the single-parameter characterization of O’Connor & Ott. These branches are particularly apparent for stars in the mass ranges 14–19 and 22–24 M ⊙. The multivalued solutions are a consequence of interference between several carbon- and oxygen-burning shells during the late stages of evolution. For a relevant range of masses, whether a star explodes or not may reflect the small, almost random differences in its late evolution more than its initial mass. The large number of models allows statistically meaningful statements about the radius, luminosity, and effective temperatures of presupernova stars, their core structures, and their remnant mass distributions.

Broad screening and identification of β-agonists in feed and animal body fluid and tissues using ultra-high performance liquid chromatography-quadrupole-orbitrap high resolution mass spectrometry combined with spectra library search.

PubMed

Li, Tingting; Cao, Jingjing; Li, Zhen; Wang, Xian; He, Pingli

2016-02-01

Broad screening and identification of β-agonists in feed, serum, urine, muscle and liver samples was achieved in a quick and highly sensitive manner using ultra high performance liquid chromatography-quadrupole-orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS) combined with a spectra library search. Solid-phase extraction technology was employed for sample purification and enrichment. After extraction and purification, the samples were analyzed using a Q-Orbitrap high-resolution mass spectrometer under full-scan and data-dependent MS/MS mode. The acquired mass spectra were compared with an in-house library (compound library and MS/MS mass spectral library) built with TraceFinder Software which contained the M/Z of the precursor ion, chemical formula, retention time, character fragment ions and the entire MS/MS spectra of 32 β-agonist standards. Screening was achieved by comparing 5 key mass spectral results and positive matches were marked. Using the developed method, the identification results from 10 spiked samples and 238 actual samples indicated that only 2% of acquired mass spectra produced false identities. The method validation results showed that the limit of detection ranged from 0.021-3.854 μg kg(-1)and 0.015-1.198 ng mL(-1) for solid and liquid samples, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Peptide Peak Detection for Low Resolution MALDI-TOF Mass Spectrometry.

PubMed

Yao, Jingwen; Utsunomiya, Shin-Ichi; Kajihara, Shigeki; Tabata, Tsuyoshi; Aoshima, Ken; Oda, Yoshiya; Tanaka, Koichi

2014-01-01

A new peak detection method has been developed for rapid selection of peptide and its fragment ion peaks for protein identification using tandem mass spectrometry. The algorithm applies classification of peak intensities present in the defined mass range to determine the noise level. A threshold is then given to select ion peaks according to the determined noise level in each mass range. This algorithm was initially designed for the peak detection of low resolution peptide mass spectra, such as matrix-assisted laser desorption/ionization Time-of-Flight (MALDI-TOF) mass spectra. But it can also be applied to other type of mass spectra. This method has demonstrated obtaining a good rate of number of real ions to noises for even poorly fragmented peptide spectra. The effect of using peak lists generated from this method produces improved protein scores in database search results. The reliability of the protein identifications is increased by finding more peptide identifications. This software tool is freely available at the Mass++ home page (http://www.first-ms3d.jp/english/achievement/software/).

Peptide Peak Detection for Low Resolution MALDI-TOF Mass Spectrometry

PubMed Central

Yao, Jingwen; Utsunomiya, Shin-ichi; Kajihara, Shigeki; Tabata, Tsuyoshi; Aoshima, Ken; Oda, Yoshiya; Tanaka, Koichi

2014-01-01

A new peak detection method has been developed for rapid selection of peptide and its fragment ion peaks for protein identification using tandem mass spectrometry. The algorithm applies classification of peak intensities present in the defined mass range to determine the noise level. A threshold is then given to select ion peaks according to the determined noise level in each mass range. This algorithm was initially designed for the peak detection of low resolution peptide mass spectra, such as matrix-assisted laser desorption/ionization Time-of-Flight (MALDI-TOF) mass spectra. But it can also be applied to other type of mass spectra. This method has demonstrated obtaining a good rate of number of real ions to noises for even poorly fragmented peptide spectra. The effect of using peak lists generated from this method produces improved protein scores in database search results. The reliability of the protein identifications is increased by finding more peptide identifications. This software tool is freely available at the Mass++ home page (http://www.first-ms3d.jp/english/achievement/software/). PMID:26819872

Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Marshall, Alan G.

1998-06-01

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

Comprehensive characterization of C-glycosyl flavones in wheat (Triticum aestivum L.) germ using UPLC-PDA-ESI/HRMSn and mass defect filtering

USDA-ARS?s Scientific Manuscript database

A comprehensive characterization of C-glycosyl flavones in wheat germ has been conducted using multi-stage high resolution mass spectrometry (HRMS) combined with mass defect filter (MDF). MDF performed the initial search of raw data with defined mass ranges and mass defect windows to generate the n...

Phonon-assisted field emission in silicon nanomembranes for time-of-flight mass spectrometry of proteins.

PubMed

Park, Jonghoo; Aksamija, Zlatan; Shin, Hyun-Cheol; Kim, Hyunseok; Blick, Robert H

2013-06-12

Time-of-flight (TOF) mass spectrometry has been considered as the method of choice for mass analysis of large intact biomolecules, which are ionized in low charge states by matrix-assisted-laser-desorption/ionization (MALDI). However, it remains predominantly restricted to the mass analysis of biomolecules with a mass below about 50,000 Da. This limitation mainly stems from the fact that the sensitivity of the standard detectors decreases with increasing ion mass. We describe here a new principle for ion detection in TOF mass spectrometry, which is based upon suspended silicon nanomembranes. Impinging ion packets on one side of the suspended silicon nanomembrane generate nonequilibrium phonons, which propagate quasi-diffusively and deliver thermal energy to electrons within the silicon nanomembrane. This enhances electron emission from the nanomembrane surface with an electric field applied to it. The nonequilibrium phonon-assisted field emission in the suspended nanomembrane connected to an effective cooling of the nanomembrane via field emission allows mass analysis of megadalton ions with high mass resolution at room temperature. The high resolution of the detector will give better insight into high mass proteins and their functions.

Design, Synthesis, and Biological Evaluations of Asymmetric Bow-Tie PAMAM Dendrimer-Based Conjugates for Tumor-Targeted Drug Delivery.

PubMed

Wang, Tao; Zhang, Yaozhong; Wei, Longfei; Teng, Yuhan G; Honda, Tadashi; Ojima, Iwao

2018-04-30

A unique asymmetric bow-tie poly(amidoamine) (PAMAM) dendrimer (ABTD) scaffold was designed and developed as a well-defined macromolecular carrier for tumor-targeted drug delivery. The ABTD scaffold in this study consists of a G3-half-dendron (G3-HD) unit and a G1-half-dendron (G1-HD) unit, bearing thiol moiety in each unit and a bis(maleimide) linker unit, which undergo sequential thiol-maleimide coupling to assemble the scaffold. This assembly methodology is applicable to all other combinations of different generations of PAMAM dendrimers. In the prototype ABTD in this study, 16 biotin moieties were tethered to the G3-HD unit and 4 payloads (new-generation taxoid) to the G1-HD via a self-immolative linker to form an ABTD-tumor-targeting conjugate (ABTD-TTC-1). Two other ABTD-TTCs were synthesized, wherein the G1-HD unit was tethered to a fluorescence-labeled taxoid or to a fluorescent probe. These three ABTD-TTCs were constructed by using a common key ABTD 6 bearing a terminal acetylene group in the G1-HD unit, which was fully characterized as a single molecule by high-resolution mass spectrometry and NMR despite its high molecular weight ( M w : 12 876). Then, the click reaction was employed to couple ABTD 6 with a small-molecule payload or fluorescence probe unit bearing a terminal azide moiety. ABTD-TTC-3, as a surrogate of ABTD-TTC-2, showed substantially enhanced internalization into two cancer cell lines via receptor-mediated endocytosis, attributed to multibinding effect. ABTD-TTC-1 exhibited a remarkable selectivity to cancer cells (1400-7500 times) compared to human normal cells, which demonstrates the salient feature and bright prospect of the ABTD-based tumor-targeted drug-delivery system.

Real-time dose computation: GPU-accelerated source modeling and superposition/convolution

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

Jacques, Robert; Wong, John; Taylor, Russell

Purpose: To accelerate dose calculation to interactive rates using highly parallel graphics processing units (GPUs). Methods: The authors have extended their prior work in GPU-accelerated superposition/convolution with a modern dual-source model and have enhanced performance. The primary source algorithm supports both focused leaf ends and asymmetric rounded leaf ends. The extra-focal algorithm uses a discretized, isotropic area source and models multileaf collimator leaf height effects. The spectral and attenuation effects of static beam modifiers were integrated into each source's spectral function. The authors introduce the concepts of arc superposition and delta superposition. Arc superposition utilizes separate angular sampling for themore » total energy released per unit mass (TERMA) and superposition computations to increase accuracy and performance. Delta superposition allows single beamlet changes to be computed efficiently. The authors extended their concept of multi-resolution superposition to include kernel tilting. Multi-resolution superposition approximates solid angle ray-tracing, improving performance and scalability with a minor loss in accuracy. Superposition/convolution was implemented using the inverse cumulative-cumulative kernel and exact radiological path ray-tracing. The accuracy analyses were performed using multiple kernel ray samplings, both with and without kernel tilting and multi-resolution superposition. Results: Source model performance was <9 ms (data dependent) for a high resolution (400{sup 2}) field using an NVIDIA (Santa Clara, CA) GeForce GTX 280. Computation of the physically correct multispectral TERMA attenuation was improved by a material centric approach, which increased performance by over 80%. Superposition performance was improved by {approx}24% to 0.058 and 0.94 s for 64{sup 3} and 128{sup 3} water phantoms; a speed-up of 101-144x over the highly optimized Pinnacle{sup 3} (Philips, Madison, WI) implementation. Pinnacle{sup 3} times were 8.3 and 94 s, respectively, on an AMD (Sunnyvale, CA) Opteron 254 (two cores, 2.8 GHz). Conclusions: The authors have completed a comprehensive, GPU-accelerated dose engine in order to provide a substantial performance gain over CPU based implementations. Real-time dose computation is feasible with the accuracy levels of the superposition/convolution algorithm.« less

Black hole mass measurement using molecular gas kinematics: what ALMA can do

NASA Astrophysics Data System (ADS)

Yoon, Ilsang

2017-04-01

We study the limits of the spatial and velocity resolution of radio interferometry to infer the mass of supermassive black holes (SMBHs) in galactic centres using the kinematics of circum-nuclear molecular gas, by considering the shapes of the galaxy surface brightness profile, signal-to-noise ratios (S/Ns) of the position-velocity diagram (PVD) and systematic errors due to the spatial and velocity structure of the molecular gas. We argue that for fixed galaxy stellar mass and SMBH mass, the spatial and velocity scales that need to be resolved increase and decrease, respectively, with decreasing Sérsic index of the galaxy surface brightness profile. We validate our arguments using simulated PVDs for varying beam size and velocity channel width. Furthermore, we consider the systematic effects on the inference of the SMBH mass by simulating PVDs including the spatial and velocity structure of the molecular gas, which demonstrates that their impacts are not significant for a PVD with good S/N unless the spatial and velocity scale associated with the systematic effects are comparable to or larger than the angular resolution and velocity channel width of the PVD from pure circular motion. Also, we caution that a bias in a galaxy surface brightness profile owing to the poor resolution of a galaxy photometric image can largely bias the SMBH mass by an order of magnitude. This study shows the promise and the limits of ALMA observations for measuring SMBH mass using molecular gas kinematics and provides a useful technical justification for an ALMA proposal with the science goal of measuring SMBH mass.

Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

PubMed Central

2015-01-01

Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. Using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. Speculation about how to successfully resolve these issues is a key part of the discussion. PMID:25458665

Early Activity of Cometary Species from ROSINA/DFMS at 67P/ Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Hässig, Myrtha; Fuselier, Stephen A.; Altwegg, Kathrin; Balsiger, Hans; Berthelier, Jean-Jacques; Bieler, André; Calmonte, Ursina; Dhooghe, Frederik; Fiethe, Björn; Gasc, Sébastien; Gombosi, Tamas I.; Jäckel, Annette; Korth, Axel; Le Roy, Léna; Rème, Henri; Rubin, Martin; Tzou, Chia-Yu; Wurz, Peter

2014-11-01

The European Space Agency’s Rosetta spacecraft arrived after a journey of more than 10 years at comet 67P/Churyumov-Gerasimenko. ROSINA is an instrument package on board Rosetta. It consists of two mass spectrometers and a COmetary Pressure Sensor (COPS). The two mass spectrometers, the Double Focusing Mass Spectrometer (DFMS) and the Reflectron Time of Flight (RTOF) complement each other with high mass resolution (e.g to resolve 13C from CH), high dynamic range (to detect low abundant isotopes and species), high mass range (to detect organics), and high time resolution. ROSINA is designed to measure the neutral gas and plasma composition in the coma of 67P/Churyumov-Gerasimenko in addition to the physical properties of the neutral component of the coma. For the first time, a comet can be observed in situ from its early activity towards and after perihelion. Little is known about what drives initial cometary activity very far from the Sun. Remote sensing observations to date are highly constrained to a limited number of a few bright comets (e.g. Hale-Bopp) and a limited number of species. Rosetta provides the first measurements of the early activity of a comet in situ and detected the first cometary molecules early August. We will focus on early activity of cometary species from the high resolution mass spectrometer ROSINA/DFMS.

MASS SPECTROMETRIC ANALYSIS AND CHARACTERIZATION OF KEPONE IN ENVIRONMENTAL AND HUMAN SAMPLES

EPA Science Inventory

A specific portion of our environment has been contaminated with Kepone, or chlordecone. Additionally, some specific human exposures to high concentrations of Kepone have been confirmed. Gas chromatography mass spectrometry involving chemical ionization and high resolution mass s...

Mass Defect from Nuclear Physics to Mass Spectral Analysis.

PubMed

Pourshahian, Soheil

2017-09-01

Mass defect is associated with the binding energy of the nucleus. It is a fundamental property of the nucleus and the principle behind nuclear energy. Mass defect has also entered into the mass spectrometry terminology with the availability of high resolution mass spectrometry and has found application in mass spectral analysis. In this application, isobaric masses are differentiated and identified by their mass defect. What is the relationship between nuclear mass defect and mass defect used in mass spectral analysis, and are they the same? Graphical Abstract ᅟ.

Bayesian Peptide Peak Detection for High Resolution TOF Mass Spectrometry.

PubMed

Zhang, Jianqiu; Zhou, Xiaobo; Wang, Honghui; Suffredini, Anthony; Zhang, Lin; Huang, Yufei; Wong, Stephen

2010-11-01

In this paper, we address the issue of peptide ion peak detection for high resolution time-of-flight (TOF) mass spectrometry (MS) data. A novel Bayesian peptide ion peak detection method is proposed for TOF data with resolution of 10 000-15 000 full width at half-maximum (FWHW). MS spectra exhibit distinct characteristics at this resolution, which are captured in a novel parametric model. Based on the proposed parametric model, a Bayesian peak detection algorithm based on Markov chain Monte Carlo (MCMC) sampling is developed. The proposed algorithm is tested on both simulated and real datasets. The results show a significant improvement in detection performance over a commonly employed method. The results also agree with expert's visual inspection. Moreover, better detection consistency is achieved across MS datasets from patients with identical pathological condition.

Bayesian Peptide Peak Detection for High Resolution TOF Mass Spectrometry

PubMed Central

Zhang, Jianqiu; Zhou, Xiaobo; Wang, Honghui; Suffredini, Anthony; Zhang, Lin; Huang, Yufei; Wong, Stephen

2011-01-01

In this paper, we address the issue of peptide ion peak detection for high resolution time-of-flight (TOF) mass spectrometry (MS) data. A novel Bayesian peptide ion peak detection method is proposed for TOF data with resolution of 10 000–15 000 full width at half-maximum (FWHW). MS spectra exhibit distinct characteristics at this resolution, which are captured in a novel parametric model. Based on the proposed parametric model, a Bayesian peak detection algorithm based on Markov chain Monte Carlo (MCMC) sampling is developed. The proposed algorithm is tested on both simulated and real datasets. The results show a significant improvement in detection performance over a commonly employed method. The results also agree with expert’s visual inspection. Moreover, better detection consistency is achieved across MS datasets from patients with identical pathological condition. PMID:21544266

Prospects for Measuring Supermassive Black Hole Masses with Future Extremely Large Telescopes

NASA Astrophysics Data System (ADS)

Do, Tuan; Wright, S. A.; Barton, E. J.; Barth, A. J.; Simard, L.; Larkin, J. E.; Moore, A.

2013-01-01

The next generation of giant-segmented mirror telescopes (> 20 m) will enable us to observe galactic nuclei at much higher angular resolution and sensitivity than ever before. These capabilities will introduce a revolutionary shift in our understanding of the origin and evolution of supermassive black holes by enabling more precise black hole mass measurements in a mass range that is unreachable today. We present simulations and predictions of the observations of nuclei that will be made with the Thirty Meter Telescope (TMT) and the adaptive optics assisted integral-field spectrograph IRIS. These simulations, for the first time, use realistic values for the sky, telescope, adaptive optics system, and instrument, to determine the expected signal-to-noise of a range of possible targets spanning intermediate mass black holes of ~10^4 M⊙ to the most massive black holes known today of >10^10 M⊙. We find that future integral-field spectrographs will be able to observe Milky Way-mass black holes out the distance of the Virgo cluster, and will allow us to observe many more brightest-cluster galaxies where the most massive black holes are thought to reside. We also evaluate how well the kinematic moments of the velocity distributions can be constrained at different spectral resolutions and plate scales. We find that a spectral resolution of ~8000 will be necessary to measure the masses of IMBHs. We find by using the SDSS DR7 catalog of galaxies that over 4000 massive black holes will be observable at distances between 0.005 < z < 0.3 with the estimated sensitivity and angular resolution of TMT. These observations will provide the most accurate dynamical mass measurements of black holes to enable the study of their demography, address the origin of the M_bh-σ and M_bh - L relationships, and the origins and evolution of black holes through cosmic time.

Co-Registered In Situ Secondary Electron and Mass Spectral Imaging on the Helium Ion Microscope Demonstrated Using Lithium Titanate and Magnesium Oxide Nanoparticles.

PubMed

Dowsett, D; Wirtz, T

2017-09-05

The development of a high resolution elemental imaging platform combining coregistered secondary ion mass spectrometry and high resolution secondary electron imaging is reported. The basic instrument setup and operation are discussed and in situ image correlation is demonstrated on a lithium titanate and magnesium oxide nanoparticle mixture. The instrument uses both helium and neon ion beams generated by a gas field ion source to irradiate the sample. Both secondary electrons and secondary ions may be detected. Secondary ion mass spectrometry (SIMS) is performed using an in-house developed double focusing magnetic sector spectrometer with parallel detection. Spatial resolutions of 10 nm have been obtained in SIMS mode. Both the secondary electron and SIMS image data are very surface sensitive and have approximately the same information depth. While the spatial resolutions are approximately a factor of 10 different, switching between the different images modes may be done in situ and extremely rapidly, allowing for simple imaging of the same region of interest and excellent coregistration of data sets. The ability to correlate mass spectral images on the 10 nm scale with secondary electron images on the nanometer scale in situ has the potential to provide a step change in our understanding of nanoscale phenomena in fields from materials science to life science.

New design for a time-of-flight mass spectrometer with a liquid beam laser desorption ion source for the analysis of biomolecules

NASA Astrophysics Data System (ADS)

Charvat, A.; Lugovoj, E.; Faubel, M.; Abel, B.

2004-05-01

We describe a novel liquid beam mass spectrometer, based on a recently discovered nanosecond laser desorption phenomenon, [W. Kleinekofort, J. Avdiev, and B. Brutschy, Int. J. Mass Ion. Processes 152, 135 (1996)] which allows the liquid-to-vacuum transfer, and subsequent mass analysis of pre-existing ions and ionic associates from liquid microjets of aqueous solutions. The goal of our novel technical approach is to establish a system with good mass resolution that implements improvements on critical components that make the system more reliable and easier to operate. For laser desorption pulsed dye-laser difference frequency mixing is used that provides tunable infrared light near the absorption maximum of liquid water around 3 μm. Different types of liquid beam glass nozzles (convergent capillary and aperture plate nozzles) are investigated and characterized. Starting from theoretical considerations of hydrodynamic drag forces on micrometer size droplets in supersonic rarefied gas flows we succeeded in capturing efficiently the liquid beam in a liquid beam recycling trap operating at the vapor pressure of liquid water. For improving the pollution resistance, the liquid jet high vacuum ion source region is spatially separated from the reflectron time-of-flight mass spectrometer (TOF-MS) working behind a gate valve in an ultrahigh vacuum environment. A simple (simulation optimized) ion optics is employed for the ion transfer from the source to the high vacuum region. This new feature is also mostly responsible for the improved mass resolution. With the present tandem-TOF-MS setup a resolution of m/Δm≈1800 for the low and m/Δm≈700 in the high mass region has been obtained for several biomolecules of different mass and complexity (amino acids, insulin, and cytochrome c).

Counting individual sulfur atoms in a protein by ultrahighresolution Fourier transform ion cyclotron resonance mass spectrometry: Experimental resolution of isotopic fine structure in proteins

PubMed Central

Shi, Stone D.-H.; Hendrickson, Christopher L.; Marshall, Alan G.

1998-01-01

A typical molecular ion mass spectrum consists of a sum of signals from species of various possible isotopic compositions. Only the monoisotopic peak (e.g., all carbons are 12C; all nitrogens are 14N, etc.) has a unique elemental composition. Every other isotope peak at approximately integer multiples of ∼1 Da higher in nominal mass represents a sum of contributions from isotope combinations differing by a few mDa (e.g., two 13C vs. two 15N vs. one 13C and one 15N vs. 34S, vs. 18O, etc., at ∼2 Da higher in mass than the monoisotopic mass). At sufficiently high mass resolving power, each of these nominal-mass peaks resolves into its isotopic fine structure. Here, we report resolution of the isotopic fine structure of proteins up to 15.8 kDa (isotopic 13C,15N doubly depleted tumor suppressor protein, p16), made possible by electrospray ionization followed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass analysis at 9.4 tesla. Further, a resolving power of m/Δm50% ≈8,000,000 has been achieved on bovine ubiquitin (8.6 kDa). These results represent a 10-fold increase in the highest mass at which isotopic fine structure previously had been observed. Finally, because isotopic fine structure reveals elemental composition directly, it can be used to confirm or determine molecular formula. For p16, for example, we were able to determine (5.1 ± 0.3) the correct number (five) of sulfur atoms solely from the abundance ratio of the resolved 34S peak to the monoisotopic peak. PMID:9751700

Filamentary structure and Keplerian rotation in the high-mass star-forming region G35.03+0.35 imaged with ALMA

NASA Astrophysics Data System (ADS)

Beltrán, M. T.; Sánchez-Monge, Á.; Cesaroni, R.; Kumar, M. S. N.; Galli, D.; Walmsley, C. M.; Etoka, S.; Furuya, R. S.; Moscadelli, L.; Stanke, T.; van der Tak, F. F. S.; Vig, S.; Wang, K.-S.; Zinnecker, H.; Elia, D.; Schisano, E.

2014-11-01

Context. Theoretical scenarios propose that high-mass stars are formed by disk-mediated accretion. Aims: To test the theoretical predictions on the formation of massive stars, we wish to make a thorough study at high-angular resolution of the structure and kinematics of the dust and gas emission toward the high-mass star-forming region G35.03+0.35, which harbors a disk candidate around a B-type (proto)star. Methods: We carried out ALMA Cycle 0 observations at 870 μm of dust of typical high-density, molecular outflow, and cloud tracers with resolutions of < 0''&dotbelow;5. Complementary Subaru COMICS 25 μm observations were carried out to trace the mid-infrared emission toward this star-forming region. Results: The submillimeter continuum emission has revealed a filamentary structure fragmented into six cores, called A-F. The filament could be in quasi-equilibrium taking into account that the mass per unit length of the filament, 200-375 M⊙/pc, is similar to the critical mass of a thermally and turbulently supported infinite cylinder, ~335 M⊙/pc. The cores, which are on average separated by ~0.02 pc, have deconvolved sizes of 1300-3400 AU, temperatures of 35-240 K, H2 densities >107 cm -3, and masses in the range 1-5 M⊙, and they are subcritical. Core A, which is associated with a hypercompact Hii region and could be the driving source of the molecular outflow observed in the region, is the most chemically rich source in G35.03+0.35 with strong emission of typical hot core tracers such as CH3CN. Tracers of high density and excitation show a clear velocity gradient along the major axis of the core, which is consistent with a disk rotating about the axis of the associated outflow. The PV plots along the SE-NW direction of the velocity gradient show clear signatures of Keplerian rotation, although infall could also be present, and they are consistent with the pattern of an edge-on Keplerian disk rotating about a star with a mass in the range 5-13 M⊙. The high tff/trot ratio for core A suggests that the structure rotates fast and that the accreting material has time to settle into a centrifugally supported disk. Conclusions: G35.03+0.35 is one of the most convincing examples of Keplerian disks rotating about high-mass (proto)stars. This supports theoretical scenarios according to which high-mass stars, at least B-type stars, would form through disk-mediated accretion. Appendices are available in electronic form at http://www.aanda.org

Insights into Aqueous-phase processing through Comparison of the Organic Chemical Composition of Atmospheric Particles and Cloud Water in the Southeast United States

NASA Astrophysics Data System (ADS)

Boone, E.; Laskin, J.; Laskin, A.; Wirth, C.; Shepson, P. B.; Stirm, B. H.; Pratt, K.

2014-12-01

Organic compounds comprise a significant mass fraction of submicron atmospheric particles with considerable contribution from secondary organic aerosol (SOA), a large fraction of which is formed from the oxidation of biogenic volatile organic compounds. Aqueous-phase reactions in particles and cloud droplets are suggested to increase SOA mass and change the chemical composition the particles following cloud evaporation. Aqueous-phase processing may also explain discrepancies between measurements and models. To gain a better understanding of these processes, cloud water and below-cloud atmospheric particles were collected onboard a research aircraft during the Southeast Oxidants and Aerosol Study (SOAS) over Alabama in June 2013. Nanospray desorption electrospray ionization (nano-DESI) and direct electrospray ionization (ESI) coupled with high resolution mass spectrometry were utilized to compare the organic molecular composition of the particle and cloud water samples, respectively. Several hundred unique compounds have been identified in the particle and cloud water samples, allowing possible aqueous-phase reactions to be examined. Hydrolysis of organosulfate compounds, aqueous-phase formation of nitrogen-containing compounds, and possible fragmentation of oligomeric compounds will be discussed, with comparisons to previous laboratory studies. This study provides insights into aqueous-phase reactions in ambient cloud droplets.

An Upper Limit on the Mass of a Central Black Hole in the Large Magellanic Cloud from the Stellar Rotation Field

NASA Astrophysics Data System (ADS)

Boyce, H.; Lützgendorf, N.; van der Marel, R. P.; Baumgardt, H.; Kissler-Patig, M.; Neumayer, N.; de Zeeuw, P. T.

2017-09-01

We constrain the possible presence of a central black hole (BH) in the center of the Large Magellanic Cloud. This requires spectroscopic measurements over an area of the order of a square degree, due to the poorly known position of the kinematic center. Such measurements are now possible with the impressive field of view of the Multi Unit Spectroscopic Explorer (MUSE) on the ESO Very Large Telescope. We used the Calcium Triplet (˜850 nm) spectral lines in many short-exposure MUSE pointings to create a two-dimensional integrated-light line-of-sight velocity map from the ˜ {10}8 individual spectra, taking care to identify and remove Galactic foreground populations. The data reveal a clear velocity gradient at an unprecedented spatial resolution of 1 arcmin2. We fit kinematic models to arrive at a 3σ upper-mass limit of {10}7.1 {M}⊙ for any central BH—consistent with the known scaling relations for supermassive black holes and their host systems. This adds to the growing body of knowledge on the presence of BHs in low-mass and dwarf galaxies, and their scaling relations with host-galaxy properties, which can shed light on theories of BH growth and host system interaction.

Trace-Level Volatile Quantitation by Direct Analysis in Real Time Mass Spectrometry following Headspace Extraction: Optimization and Validation in Grapes.

PubMed

Jastrzembski, Jillian A; Bee, Madeleine Y; Sacks, Gavin L

2017-10-25

Ambient ionization mass spectrometric (AI-MS) techniques like direct analysis in real time (DART) offer the potential for rapid quantitative analyses of trace volatiles in food matrices, but performance is generally limited by the lack of preconcentration and extraction steps. The sensitivity and selectivity of AI-MS approaches can be improved through solid-phase microextraction (SPME) with appropriate thin-film geometries, for example, solid-phase mesh-enhanced sorption from headspace (SPMESH). This work improves the SPMESH-DART-MS approach for use in food analyses and validates the approach for trace volatile analysis for two compounds in real samples (grape macerates). SPMESH units prepared with different sorbent coatings were evaluated for their ability to extract a range of odor-active volatiles, with poly(dimethylsiloxane)/divinylbenzene giving the most satisfactory results. In combination with high-resolution mass spectrometry (HRMS), detection limits for SPMESH-DART-MS under 4 ng/L in less than 30 s acquisition times could be achieved for some volatiles [3-isobutyl-2-methoxypyrazine (IBMP) and β-damascenone]. A comparison of SPMESH-DART-MS and SPME-GC-MS quantitation of linalool and IBMP demonstrates excellent agreement between the two methods for real grape samples (r 2 ≥ 0.90), although linalool measurements appeared to also include isobaric interference.

Advanced Mass Spectrometric Methods for the Rapid and Quantitative Characterization of Proteomes

DOE PAGES

Smith, Richard D.

2002-01-01

Progress is reviewedmore » towards the development of a global strategy that aims to extend the sensitivity, dynamic range, comprehensiveness and throughput of proteomic measurements based upon the use of high performance separations and mass spectrometry. The approach uses high accuracy mass measurements from Fourier transform ion cyclotron resonance mass spectrometry (FTICR) to validate peptide ‘accurate mass tags’ (AMTs) produced by global protein enzymatic digestions for a specific organism, tissue or cell type from ‘potential mass tags’ tentatively identified using conventional tandem mass spectrometry (MS/MS). This provides the basis for subsequent measurements without the need for MS/ MS. High resolution capillary liquid chromatography separations combined with high sensitivity, and high resolution accurate FTICR measurements are shown to be capable of characterizing peptide mixtures of more than 10 5 components. The strategy has been initially demonstrated using the microorganisms Saccharomyces cerevisiae and Deinococcus radiodurans. Advantages of the approach include the high confidence of protein identification, its broad proteome coverage, high sensitivity, and the capability for stableisotope labeling methods for precise relative protein abundance measurements. Abbreviations : LC, liquid chromatography; FTICR, Fourier transform ion cyclotron resonance; AMT, accurate mass tag; PMT, potential mass tag; MMA, mass measurement accuracy; MS, mass spectrometry; MS/MS, tandem mass spectrometry; ppm, parts per million.« less

Smooth seaward-dipping horizons - An important factor in sea-floor stability?

USGS Publications Warehouse

McGregor, B.A.

1981-01-01

Mass movement has influenced in varying degrees the morphology of the United States east coast continental margin seaward of the Baltimore Canyon trough as revealed by detailed geophysical studies using high-resolution 3.5-kHz, and seismic reflection data. Each of three areas studied is along the slope within a distance of 225 km, and is seaward of a nonglaciated shelf but near major land drainage systems. Thick sequences of material believed to be Pleistocene were deposited on the slope in all three areas. Sediment failure in the form of large block movement involving block thicknesses of more than 100 m, however, has taken place in only two of the areas. A factor common to the two areas where failure took place, but absent in the area where no failure took place, is smooth seaward-dipping sub-bottom horizons. Whatever the triggering mechanism, a smooth slip surface that has a seward slope may contribute to mass movement by reducing the internal friction. This may be one of several factors that should be considered in assessing slope stability. ?? 1981.

Progesterone potentially degrades to potent androgens in surface waters.

PubMed

Ojoghoro, Jasper O; Chaudhary, Abdul J; Campo, Pablo; Sumpter, John P; Scrimshaw, Mark D

2017-02-01

Progesterone is a natural hormone, excreted in higher concentrations than estrogens, and has been detected in the aqueous environment. As with other compounds, it is transformed during wastewater treatment processes and in the environment. However, minor modifications to the structure may result in transformation products which still exhibit biological activity, so understanding what transformation products are formed is of importance. The current study was undertaken to identify putative transformation products resulting from spiking river water with progesterone in a laboratory-based degradation study and hence to follow the metabolic breakdown pathways. On the basis of literature reports and predictions from the EAWAG Biocatalysis/biodegradation database, target putative transformation products were initially monitored under unit resolution mass spectrometry. The identity of these transformation products was confirmed by using accurate-mass quadrupole time-of-flight. The study results highlight that transformation of progesterone can potentially create other classes of steroids, some of which may still be potent, and possess other types of biological activity. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

High mass resolution isochronous time-of-flight spectrograph for three-dimensional space plasma measurements

NASA Technical Reports Server (NTRS)

Moebius, E.; Bochsler, P.; Ghielmetti, A. G.; Hamilton, D. C.

1990-01-01

By combining a toroidal electrostatic analyzer with a novel cylindrically symmetric isochronous time-of-flight mass spectrometer, an instrument was developed that simultaneously determines the three-dimensional distribution function of ions and differentiates species. The ion mass is determined to high resolution (M/Delta-M greater than 50) from the time of flight within a harmonic field configuration defined by hyperboloid equipotential surfaces. A second conventional time-of-flight channel makes use of particles leaving the thin entrance foil as neutrals. An additional solid state detector in which the neutrals are stopped allows the total energy and thereby the ionic charge of the incident ions to be determined as well. Information from the neutral and the ion channels can be combined to determine the total mass of an incident molecular ion and the mass of one atomic fragment.

Estimation and Validation of Oceanic Mass Circulation from the GRACE Mission

NASA Technical Reports Server (NTRS)

Boy, J.-P.; Rowlands, D. D.; Sabaka, T. J.; Luthcke, S. B.; Lemoine, F. G.

2011-01-01

Since the launch of the Gravity Recovery And Climate Experiment (GRACE) in March 2002, the Earth's surface mass variations have been monitored with unprecedented accuracy and resolution. Compared to the classical spherical harmonic solutions, global high-resolution mascon solutions allows the retrieval of mass variations with higher spatial and temporal sampling (2 degrees and 10 days). We present here the validation of the GRACE global mascon solutions by comparing mass estimates to a set of about 100 ocean bottom pressure (OSP) records, and show that the forward modelling of continental hydrology prior to the inversion of the K-band range rate data allows better estimates of ocean mass variations. We also validate our GRACE results to OSP variations modelled by different state-of-the-art ocean general circulation models, including ECCO (Estimating the Circulation and Climate of the Ocean) and operational and reanalysis from the MERCATOR project.

On optical imaging through aircraft turbulent boundary layers

NASA Technical Reports Server (NTRS)

Sutton, G. W.

1980-01-01

Optical resolution quality as affected by aircraft turbulent boundary layers is analyzed. Wind-tunnel data was analyzed to obtained the variation of boundary layer turbulence scale length and mass density rms fluctuations with Mach number. The data gave good agreement with a mass density fluctuation turbulence spectrum that is either isotropic of orthogonally anisotropic. The data did not match an isotropic turbulence velocity spectrum which causes an anisotropic non-orthogonal mass density fluctuation spectrum. The results indicate that the average mass density rms fluctuation is about 10% of the maximum mass density across the boundary layer and that the transverse turbulence scale size is about 10% of the boundary layer thickness. The results indicate that the effect of the turbulent boundary layer is large angle scattering which decreases contrast but not resolution. Using extinction as a criteria the range of acceptable aircraft operating conditions are given.

Automated quantification of pancreatic β-cell mass

PubMed Central

Golson, Maria L.; Bush, William S.

2014-01-01

β-Cell mass is a parameter commonly measured in studies of islet biology and diabetes. However, the rigorous quantification of pancreatic β-cell mass using conventional histological methods is a time-consuming process. Rapidly evolving virtual slide technology with high-resolution slide scanners and newly developed image analysis tools has the potential to transform β-cell mass measurement. To test the effectiveness and accuracy of this new approach, we assessed pancreata from normal C57Bl/6J mice and from mouse models of β-cell ablation (streptozotocin-treated mice) and β-cell hyperplasia (leptin-deficient mice), using a standardized systematic sampling of pancreatic specimens. Our data indicate that automated analysis of virtual pancreatic slides is highly reliable and yields results consistent with those obtained by conventional morphometric analysis. This new methodology will allow investigators to dramatically reduce the time required for β-cell mass measurement by automating high-resolution image capture and analysis of entire pancreatic sections. PMID:24760991

A resolution recognizing the 100th anniversary of the Veterans of Foreign Wars of the United States and commending its members for their courage and sacrifice in service to the United States.

THOMAS, 113th Congress

Sen. Toomey, Pat [R-PA

2014-07-30

Senate - 09/18/2014 Resolution agreed to in Senate without amendment and with a preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

A resolution recognizing the 40th anniversary of the withdrawal of United States combat troops from the Vietnam War and expressing renewed support for United States veterans of that conflict.

THOMAS, 113th Congress

Sen. Thune, John [R-SD

2013-10-31

Senate - 11/07/2013 Resolution agreed to in Senate without amendment and with a preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

High-resolution seismic-reflection profiles collected by the R/V James M. Gilliss, cruise GS 7903-4, in the Baltimore Canyon outer continental shelf area, offshore New Jersey

USGS Publications Warehouse

Robb, James M.

1980-01-01

High-resolution seismic-reflection profiles were collected by the U.S. Geological Survey (USGS) aboard R/V JAMES M. GILLIS (cruise GS 7903-4) from 27 June to 11 July 1979 over the Continental Slope of the Eastern United States between Lindenkohl and Hudson Canyons. These data were acquired as part of a study to determine potential geologic hazards to petroleum development of the Baltimore Canyon trough area. On this cruise, the Continental Slope between Carteret and South Toms Canyons was surveyed along lines spaced one-half nautical mile apart to study the size and distribution of mass-wasting features as a guide to assess the importance of mass-wasting processes on the Continental Slope. The seimsic-reflection profiles were placed to complement other data gathered previously by the USGS and to continue a survey grid begun in 1978 aboard the R/V COLUMBUS !SELIN, cruise CI 7807-1.Track-line distances totaled 1,555 km of 40-in3 air-gun (with wave shaper) profiles, 1, 750 km of 800-J sparker data, and 1,780 km of 3 .5-kHz data. All data are of high quality. A side-scan sonar system was operated briefly along the uppermost Continental Slope to acquire data over 70 km of ship's track. In addition, experimental profiling data were collected from a hydrophone towed at depth over the midslope on the end of the side-scan cable; the surface-towed sparker was used as a sound source. High-resolution profiles were collected by this method over 105 km of track.Navigation was by Loran-C (5-minute fix interval) and satellite.The original data may be inspected at the offices of the U.S. Geological Survey in Woods Hole, Massachusetts 02543. Microfilm copies of the data from this cruise are available for purchase from the National Geophysical and Solar-Terrestrial Data Center (NGSDC), Boulder, Colorado 80303.

Mass balance of Mars' residual south polar cap from CTX images and other data

NASA Astrophysics Data System (ADS)

Thomas, P. C.; Calvin, W.; Cantor, B.; Haberle, R.; James, P. B.; Lee, S. W.

2016-04-01

Erosion of pits in the residual south polar cap (RSPC) of Mars concurrent with deposition and fluctuating cap boundaries raises questions about the mass balance and long term stability of the cap. Determining a mass balance by measurement of a net gain or loss of atmospheric CO2 by direct pressure measurements (Haberle, R.M. et al. [2014]. Secular climate change on Mars: An update using one Mars year of MSL pressure data. American Geophysical Union (Fall). Abstract 3947), although perhaps the most direct method, has so far given ambiguous results. Estimating volume changes from imaging data faces challenges, and has previously been attempted only in isolated areas of the cap. In this study we use 6 m/pixel Context Imager (CTX) data from Mars year 31 to map all the morphologic units of the RSPC, expand the measurement record of pit erosion rates, and use high resolution images to place limits on vertical changes in the surface of the residual cap. We find the mass balance in Mars years 9-31 to be -6 to +4 km3/♂y, or roughly -0.039% to +0.026% of the mean atmospheric CO2 mass/♂y. The indeterminate sign results chiefly from uncertainty in the amounts of deposition or erosion on the upper surfaces of deposits (as opposed to scarp retreat). Erosion and net deposition in this period appear to be controlled by summertime planetary scale dust events, the largest occurring in MY 9, another, smaller one in MY 28. The rates of erosion and the deposition observed since MY 9 appear to be consistent with the types of deposits and erosional behavior found in most of the residual cap. However, small areas (<10%) of the cap are distinguished by their greater thickness, polygonal troughs, and embayed contacts with thinner units. These deposits may require extended periods (>100 ♂y) of depositional and/or erosional conditions different from those occurring in the period since MY 9, although these environmental differences could be subtle.

The AstroSat Production Line: From AstroSat 100 to AstroSat 1000

NASA Astrophysics Data System (ADS)

Maliet, E.; Pawlak, D.; Koeck, C.; Beaufumé, E.

2008-08-01

From the late 90s onward, Astrium Satellites has developed and improved several classes of high resolution optical Earth Observation satellites. The resulting product line ranges from micro-satellites (about 120 kg) type to the large satellites (in the range of 1 200 kg). They all make uses of state of the art technologies for optical payloads, as well as for avionics. Several classes of platforms have thus been defined and standardised: AstroSat 100 for satellites up to 150 kg, allowing affordable but fully operational missions, AstroSat 500 for satellites up to 800 kg, allowing complex high resolution missions, and AstroSat 1000 for satellites up to 1 200 kg, providing very high resolution and outstanding imaging and agility capabilities. A new class, AstroSat 250, has been developed by Astrium Satellites, and is now proposed, offering a state-of-the-art 3-axis agile platform for high- resolution missions, with a launch mass below 550 kg. The Astrosat platforms rely on a centralised architecture avionics based on an innovative AOCS hybridising of measurements from GPS, stellar sensors and inertial reference unit. Operational safety has been emphasised through thruster free safe modes. All optical payloads make use of all Silicon Carbide (SiC) telescopes. High performance and low consumption linear CCD arrays provide state of the art images. The satellites are designed for simple flight operations, large data collection capability, and large versatility of payload and missions. They are adaptable to a large range of performances. Astrium satellites have already been selected by various customers worldwide.

Morphometric attributes to understand palaeogeomorphological controls on mass-transport deposits offshore Brazil

NASA Astrophysics Data System (ADS)

Piedade, Aldina; Alves, Tiago; Luís Zêzere, José

2017-04-01

Mass-transport deposits form a significant part of the stratigraphic record of ancient and modern deep-water basins worldwide. Three-dimensional (3D) seismic data is used to analyse two different types of buried mass-transport deposits offshore Espírito Santo Basin (SE Brazil. Both types are developed within Early Miocene to Holocene stratigraphic units composed of sandstones, calcarenites, turbidite sands and marls. The high resolution images provided by the interpreted 3D seismic data allowed a detailed analysis of the seismic stratigraphy and internal structure of mass-transport deposits. In addition, improvements in visualisation techniques were used to compute simple morphometric attributes of buried mass-transport deposits in continental slopes. This study classifies the interpreted mass-transport deposits in two different types according to the relationship between the morphology of mass-transport deposits and the surrounding topography. Locally confined mass-transport deposits are laterally constrained by non-deformed strata that surrounds the mass-transport deposit and by the local topography of the depositional surface. Their dimensions are relatively small (area of 5.251 km2). Unconfined mass-transport deposits show a much larger volume compared to the previously type ( 87.180 km2), and local topography does not have control on their geometry. The analysis proves that local topography and geometry of the depositional surface are key controlling factors on the spatial distribution and dimensions of the two types of mass-transport deposits. However, the two types differ in size, geomorphological expression, local structural controls and run-out distance. This work importance is relate variations in the character of the depositional surface with the morphology mass-transport deposits and run-out distance. As a result of the methodology used, two different styles of mass-transport run-out are identified and local factors controlling their morphology are addressed, such as roughness and local morphology of the depositional surface. Separating these two styles, or types, of mass-transport deposits it is of critical importance to understand their mechanisms of gliding, downslope spreading and emplacement.

High mass resolution, high angular acceptance time-of-flight mass spectroscopy for planetary missions under the Planetary Instrument Definition and Development Program (PIDDP)

NASA Technical Reports Server (NTRS)

Young, David T.

1991-01-01

This final report covers three years and several phases of work in which instrumentation for the Planetary Instrument Definition and Development Program (PIDDP) were successfully developed. There were two main thrusts to this research: (1) to develop and test methods for electrostatically scanning detector field-of-views, and (2) to improve the mass resolution of plasma mass spectrometers to M/delta M approximately 25, their field-of-view (FOV) to 360 degrees, and their E-range to cover approximately 1 eV to 50 keV. Prototypes of two different approaches to electrostatic scanning were built and tested. The Isochronous time-of-flight (TOF) and the linear electric field 3D TOF devices were examined.

Identifying Ca2+-Binding Sites in Proteins by Liquid Chromatography-Mass Spectrometry Using Ca2+-Directed Dissociations

PubMed Central

Jamalian, Azadeh; Sneekes, Evert-Jan; Wienk, Hans; Dekker, Lennard J. M.; Ruttink, Paul J. A.; Ursem, Mario; Luider, Theo M.; Burgers, Peter C.

2014-01-01

Here we describe a new method to identify calcium-binding sites in proteins using high-resolution liquid chromatography-mass spectrometry in concert with calcium-directed collision-induced dissociations. Our method does not require any modifications to the liquid chromatography-mass spectrometry apparatus, uses standard digestion protocols, and can be applied to existing high-resolution MS data files. In contrast to NMR, our method is applicable to very small amounts of complex protein mixtures (femtomole level). Calcium-bound peptides can be identified using three criteria: (1) the calculated exact mass of the calcium containing peptide; (2) specific dissociations of the calcium-containing peptide from threonine and serine residues; and (3) the very similar retention times of the calcium-containing peptide and the free peptide. PMID:25023127

Isolation and characterisation of the biological repeating unit of cepacian, the exopolysaccharide produced by bacteria of the Burkholderia cepacia complex.

PubMed

Cescutti, Paola; Foschiatti, Michela; Furlanis, Linda; Lagatolla, Cristina; Rizzo, Roberto

2010-07-02

The repeating unit of cepacian, the exopolysaccharide produced by the majority of the microorganisms belonging to the Burkholderia cepacia complex, was isolated from inner bacterial membranes and investigated by mass spectrometry, with and without prior derivatisation. Interpretation of the mass spectra led to the determination of the biological repeating unit primary structure, thus disclosing the nature of the oligosaccharide produced in vivo. Moreover, mass spectra recorded on the native sample revealed that acetyl substitution was very variable, producing a mixture of repeating units containing zero to four acyl groups. At the same time, finding acetylated oligosaccharides showed that binding of these substituents occurred in the cellular periplasmic space, before the polymerisation process took place. In the chromatographic peak containing the repeating unit, oligosaccharides shorter than the repeating unit co-eluted. Mass spectrometric analysis showed that they were biosynthetic intermediates of the repeating unit and further investigation revealed the biosynthetic sequence of cepacian building block. Copyright 2010 Elsevier Ltd. All rights reserved.

High spatial resolution free-breathing 3D late gadolinium enhancement cardiac magnetic resonance imaging in ischaemic and non-ischaemic cardiomyopathy: quantitative assessment of scar mass and image quality.

PubMed

Bizino, Maurice B; Tao, Qian; Amersfoort, Jacob; Siebelink, Hans-Marc J; van den Bogaard, Pieter J; van der Geest, Rob J; Lamb, Hildo J

2018-04-06

To compare breath-hold (BH) with navigated free-breathing (FB) 3D late gadolinium enhancement cardiac MRI (LGE-CMR) MATERIALS AND METHODS: Fifty-one patients were retrospectively included (34 ischaemic cardiomyopathy, 14 non-ischaemic cardiomyopathy, three discarded). BH and FB 3D phase sensitive inversion recovery sequences were performed at 3T. FB datasets were reformatted into normal resolution (FB-NR, 1.46x1.46x10mm) and high resolution (FB-HR, isotropic 0.91-mm voxels). Scar mass, scar edge sharpness (SES), SNR and CNR were compared using paired-samples t-test, Pearson correlation and Bland-Altman analysis. Scar mass was similar in BH and FB-NR (mean ± SD: 15.5±18.0 g vs. 15.5±16.9 g, p=0.997), with good correlation (r=0.953), and no bias (mean difference ± SD: 0.00±5.47 g). FB-NR significantly overestimated scar mass compared with FB-HR (15.5±16.9 g vs 14.4±15.6 g; p=0.007). FB-NR and FB-HR correlated well (r=0.988), but Bland-Altman demonstrated systematic bias (1.15±2.84 g). SES was similar in BH and FB-NR (p=0.947), but significantly higher in FB-HR than FB-NR (p<0.01). SNR and CNR were lower in BH than FB-NR (p<0.01), and lower in FB-HR than FB-NR (p<0.01). Navigated free-breathing 3D LGE-CMR allows reliable scar mass quantification comparable to breath-hold. During free-breathing, spatial resolution can be increased resulting in improved sharpness and reduced scar mass. • Navigated free-breathing 3D late gadolinium enhancement is reliable for myocardial scar quantification. • High-resolution 3D late gadolinium enhancement increases scar sharpness • Ischaemic and non-ischaemic cardiomyopathy patients can be imaged using free-breathing LGE CMR.

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

PubMed

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

2018-01-18

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

A Broadband X-Ray Imaging Spectroscopy with High-Angular Resolution: the FORCE Mission

NASA Technical Reports Server (NTRS)

Mori, Koji; Tsuru, Takeshi Go; Nakazawac, Kazuhiro; Ueda, Yoshihiro; Okajima, Takashi; Murakami, Hiroshi; Awaki, Hisamitsu; Matsumoto, Hironori; Fukazawai, Yasushi; Tsunemi, Hiroshi;

Ozone-induced dissociation on a traveling wave high-resolution mass spectrometer for determination of double-bond position in lipids.

PubMed

Vu, Ngoc; Brown, Jeffery; Giles, Kevin; Zhang, Qibin

2017-09-15

The position of C=C within fatty acyl chains affects the biological function of lipids. Ozone-induced dissociation mass spectrometry (OzID-MS) has great potential in determination of lipid double-bond position, but has generally been implemented on low-resolution ion trap mass spectrometers. In addition, most of the OzID-MS experiments carried out so far were focused on the sodiated adducts of lipids; fragmentation of the most commonly observed protonated ions generated in LC/MS-based lipidomics workflow has been less explored. Ozone generated in line from an ozone generator was connected to the trap and transfer gas supply line of a Synapt G2 high-resolution mass spectrometer. Protonated ions of different phosphatidylcholines (PC) were generated by electrospray ionization through direct infusion. Different parameters, including traveling wave height and velocity, trap entrance and DC potential, were adjusted to maximize the OzID efficiency. sn-positional isomers and cis/trans isomers of lipids were compared for their reactivity with ozone. Traveling wave height and velocity were tuned to prolong the encounter time between lipid ions and ozone, and resulted in improved OzID efficiency, as did increasing trapping region DC and entrance potential. Under optimized settings, at least 1000 times enhancement in OzID efficiency was achieved compared to that under default settings for monounsaturated PC standards. Monounsaturated C=C in the sn-2 PC isomer reacted faster with ozone than the sn-1 isomer. Similarly, the C=C in trans PC reacted faster than in cis PC. This is the first implementation of OzID in the trap and transfer region of a traveling wave enabled high-resolution mass spectrometer. The OzID reaction efficiency is significantly improved by slowing down ions in the trap region for their prolonged interaction with ozone. This will facilitate application of high-resolution OzID-MS in lipidomics. Copyright © 2017 John Wiley & Sons, Ltd.

Aquatic plant-derived changes in oil sands naphthenic acid signatures determined by low-, high- and ultrahigh-resolution mass spectrometry.

PubMed

Headley, John V; Peru, Kerry M; Armstrong, Sarah A; Han, Xiumei; Martin, Jonathan W; Mapolelo, Mmilili M; Smith, Donald F; Rogers, Ryan P; Marshall, Alan G

2009-02-01

Mass spectrometry is a common tool for studying the fate of complex organic compound mixtures in oil sands processed water (OSPW), but a comparison of low-, high- ( approximately 10 000), and ultrahigh-resolution ( approximately 400 000) instrumentation for this purpose has not previously been made. High-resolution quadrupole time-of-flight mass spectrometry (QTOF MS) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), with negative-ion electrospray ionization, provided evidence for the selective dissipation of components in OSPW. Dissipation of oil sands naphthenic acids (NAs with general formula C(n)H(2n+z)O(2) where n is the number of carbon atoms, and Z is zero or a negative even number describing the number of rings) was masked (by components such as fatty acids, O(3), O(5), O(6), O(7), SO(2), SO(3), SO(4), SO(5), SO(6), and NO(4) species) at low resolution (1000) when using a triple quadrupole mass spectrometer. Changes observed in the relative composition of components in OSPW appear to be due primarily to the presence of plants, specifically cattails (Typha latifolia) and their associated microorganisms. The observed dissipation included a range of heteratomic species containing O(2), O(3), O(4), and O(5), present in Athabasca oil sands acid extracts. For the heteratomic O(2) species, namely naphthenic acids, an interesting structural relationship suggests that low and high carbon number NAs are dissipated by the plants preferentially, with a minimum around C(14)/C(15). Other heteratomic species containing O(6), O(7), SO(2), SO(3), SO(4), SO(5), SO(6), and NO(4) appear to be relatively recalcitrant to the cattails and were not dissipated to the same extent in planted systems. Copyright 2009 John Wiley & Sons, Ltd.

Opto-mechanical design of a new cross dispersion unit for the CRIRES+ high resolution spectrograph for the VLT

NASA Astrophysics Data System (ADS)

Lizon, Jean Louis; Klein, Barbara; Oliva, Ernesto; Löwinger, Tom; Anglada Escude, Guillem; Baade, Dietrich; Bristow, Paul; Dorn, Reinhold J.; Follert, Roman; Grunhut, Jason; Hatzes, Artie; Heiter, Ulrike; Ives, Derek; Jung, Yves; Kerber, Florian; Lockhart, Matt; Marquart, Thomas; Origlia, Livia; Pasquini, Luca; Paufique, Jerome; Piskunov, N.; Pozna, Eszter; Reiners, Ansgar; Smette, Alain; Smoker, Jonathan; Seemann, Ulf; Stempels, Eric; Valenti, Elena

2014-07-01

CRIRES is one of the few IR (0.92-5.2 μm) high-resolution spectrographs in operation at the VLT since 2006. Despite good performance it suffers a limitation that significantly hampers its ability: a small spectral coverage per exposure. The CRIRES upgrade (CRIRES+) proposes to transform CRIRES into a cross-dispersed spectrograph while maintaining the high resolution (100000) and increasing the wavelength coverage by a factor 10 compared to the current capabilities. A major part of the upgrade is the exchange of the actual cryogenic pre-disperser module by a new cross disperser unit. In addition to a completely new optical design, a number of important changes are required on key components and functions like the slit unit and detectors units. We will outline the design of these new units fitting inside a predefined and restricted space. The mechanical design of the new functions including a description and analysis will be presented. Finally we will present the strategy for the implementation of the changes.

Linear electric field mass spectrometry

DOEpatents

McComas, David J.; Nordholt, Jane E.

1992-01-01

A mass spectrometer and methods for mass spectrometry. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field.

Permian U-Pb (CA-TIMS) zircon ages from Australia and China: Constraining the time scale of environmental and biotic change

NASA Astrophysics Data System (ADS)

Denyszyn, S. W.; Mundil, R.; Metcalfe, I.; He, B.

2010-12-01

In eastern Australia, the interconnected Bowen and Sydney Basins are filled with terrestrial sediments of late Paleozoic to early Mesozoic age. These sedimentary units record significant evolutionary events of eastern Gondwana during the time interval between two major mass extinctions (end Middle Permian and Permian-Triassic), and also provide lithological evidence for the Carboniferous-Permian Late Paleozoic Ice Age of southern Pangea, considered to be divisible into up to seven discrete glaciation events in Australia [e.g., 1]. These glaciations are currently assigned ages that indicate that the last of the glaciations predate the end Middle Permian mass extinction at ca. 260 Ma. However, the estimates for the time and durations are largely based on biostratigraphy and lithostratigraphy that, in the absence of robust and precise radioisotopic ages, are unacceptably fragile for providing an accurate high-resolution framework. Interbedded with the sediments are numerous tuff layers that contain zircon, many of which are associated with extensive coal measures in the Sydney and Bowen Basins. Published SHRIMP U-Pb zircon ages [2, 3] have been shown to be less precise and inaccurate when compared to ages applying the CA-TIMS method to the same horizons. Also within the late Middle Permian, the eruption of the Emeishan flood basalts in SW China has been proposed to have caused the end Middle Permian mass extinction [e.g., 4], though a causal link between these events demands a rigorous test that can only be provided by high-resolution geochronology. We present new U-Pb (CA-TIMS) zircon ages on tuff layers from the Sydney and Bowen Basins, with the purpose of generating a timescale for the Upper Permian of Australia to allow correlation with different parts of the world. Initial results, with permil precision, date a tuff layer within the uppermost Bandanna Fm. to ca. 252 Ma, a tuff within the Moranbah Coal Measures to ca. 256 Ma, and a tuff within the Ingelara Fm. to ca. 257 Ma, the latter two units lying stratigraphically below the latest identified glacial deposits. U-Pb (CA-TIMS) results on zircons from the Emeishan flood basalts and related volcanic products confirm the end-Guadalupian age (ca. 260 Ma) of the magmatism, and based on present data, place the Emeishan volcanic event (and its possibly associated mass extinction) within the occurrence of the Late Paleozoic Ice Age. This study’s primary goal is the establishment of a chronostratigraphic framework that would allow the integration of calibrated records from both terrestrial and marine units from different parts of the world in order to constrain the timing and rates of extinctions and recoveries in different locations and physical environments. [1] Fielding et al. (2008), J. Geol Soc. Lon., v. 165, pp. 129-140 [2] Michaelsen et al. (2001), Aus. J. Earth Sci., v. 48, pp. 183-192 [3] Roberts et al. (1996), Aus. J. Earth Sci., v. 43, pp. 401-421 [4] He et al. (2007), EPSL, v. 255, pp. 306-323

Ultrahigh pressure fast size exclusion chromatography for top-down proteomics.

PubMed

Chen, Xin; Ge, Ying

2013-09-01

Top-down MS-based proteomics has gained a solid growth over the past few years but still faces significant challenges in the LC separation of intact proteins. In top-down proteomics, it is essential to separate the high mass proteins from the low mass species due to the exponential decay in S/N as a function of increasing molecular mass. SEC is a favored LC method for size-based separation of proteins but suffers from notoriously low resolution and detrimental dilution. Herein, we reported the use of ultrahigh pressure (UHP) SEC for rapid and high-resolution separation of intact proteins for top-down proteomics. Fast separation of intact proteins (6-669 kDa) was achieved in < 7 min with high resolution and high efficiency. More importantly, we have shown that this UHP-SEC provides high-resolution separation of intact proteins using a MS-friendly volatile solvent system, allowing the direct top-down MS analysis of SEC-eluted proteins without an additional desalting step. Taken together, we have demonstrated that UHP-SEC is an attractive LC strategy for the size separation of proteins with great potential for top-down proteomics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Model for mapping settlements

DOEpatents

Vatsavai, Ranga Raju; Graesser, Jordan B.; Bhaduri, Budhendra L.

2016-07-05

A programmable media includes a graphical processing unit in communication with a memory element. The graphical processing unit is configured to detect one or more settlement regions from a high resolution remote sensed image based on the execution of programming code. The graphical processing unit identifies one or more settlements through the execution of the programming code that executes a multi-instance learning algorithm that models portions of the high resolution remote sensed image. The identification is based on spectral bands transmitted by a satellite and on selected designations of the image patches.

Mapping Monthly Water Scarcity in Global Transboundary Basins at Country-Basin Mesh Based Spatial Resolution.

PubMed

Degefu, Dagmawi Mulugeta; Weijun, He; Zaiyi, Liao; Liang, Yuan; Zhengwei, Huang; Min, An

2018-02-01

Currently fresh water scarcity is an issue with huge socio-economic and environmental impacts. Transboundary river and lake basins are among the sources of fresh water facing this challenge. Previous studies measured blue water scarcity at different spatial and temporal resolutions. But there is no global water availability and footprint assessment done at country-basin mesh based spatial and monthly temporal resolutions. In this study we assessed water scarcity at these spatial and temporal resolutions. Our results showed that around 1.6 billion people living within the 328 country-basin units out of the 560 we assessed in this study endures severe water scarcity at least for a month within the year. In addition, 175 country-basin units goes through severe water scarcity for 3-12 months in the year. These sub-basins include nearly a billion people. Generally, the results of this study provide insights regarding the number of people and country-basin units experiencing low, moderate, significant and severe water scarcity at a monthly temporal resolution. These insights might help these basins' sharing countries to design and implement sustainable water management and sharing schemes.

IDENTIFICATION OF POLLUTANTS IN A MUNICIPAL WELL USING HIGH RESOLUTION MASS SPECTROMETRY

EPA Science Inventory

An elevated incidence of childhood cancer was observed near a contaminated site. Trace amounts of several isomeric compounds were detected by gas chromatography/mass spectrometry (GC/MS) in a concentrated extract of municipal well water. No matching library mass spectra were foun...

Confirmation of Pinnatoxins and Spirolides in Shellfish and Passive Samplers from Catalonia (Spain) by Liquid Chromatography Coupled with Triple Quadrupole and High-Resolution Hybrid Tandem Mass Spectrometry

PubMed Central

García-Altares, María; Casanova, Alexis; Bane, Vaishali; Diogène, Jorge; Furey, Ambrose; de la Iglesia, Pablo

2014-01-01

Cyclic imines are lipophilic marine toxins that bioaccumulate in seafood. Their structure comprises a cyclic-imino moiety, responsible for acute neurotoxicity in mice. Cyclic imines have not been linked yet to human poisonings and are not regulated in Europe, although the European Food Safety Authority requires more data to perform a conclusive risk assessment for consumers. This work presents the first detection of pinnatoxin G (PnTX-G) in Spain and 13-desmethyl spirolide C (SPX-1) in shellfish from Catalonia (Spain, NW Mediterranean Sea). Cyclic imines were found at low concentrations (2 to 60 µg/kg) in 13 samples of mussels and oysters (22 samples analyzed). Pinnatoxin G has been also detected in 17 seawater samples (out of 34) using solid phase adsorption toxin tracking devices (0.3 to 0.9 µg/kg-resin). Pinnatoxin G and SPX-1 were confirmed with both low and high resolution (<2 ppm) mass spectrometry by comparison of the response with that from reference standards. For other analogs without reference standards, we applied a strategy combining low resolution MS with a triple quadrupole mass analyzer for a fast and reliable screening, and high resolution MS LTQ Orbitrap® for unambiguous confirmation. The advantages and limitations of using high resolution MS without reference standards were discussed. PMID:24960460

Accurate physical laws can permit new standard units: The two laws F→=ma→ and the proportionality of weight to mass

NASA Astrophysics Data System (ADS)

Saslow, Wayne M.

2014-04-01

Three common approaches to F→=ma→ are: (1) as an exactly true definition of force F→ in terms of measured inertial mass m and measured acceleration a→; (2) as an exactly true axiom relating measured values of a→, F→ and m; and (3) as an imperfect but accurately true physical law relating measured a→ to measured F→, with m an experimentally determined, matter-dependent constant, in the spirit of the resistance R in Ohm's law. In the third case, the natural units are those of a→ and F→, where a→ is normally specified using distance and time as standard units, and F→ from a spring scale as a standard unit; thus mass units are derived from force, distance, and time units such as newtons, meters, and seconds. The present work develops the third approach when one includes a second physical law (again, imperfect but accurate)—that balance-scale weight W is proportional to m—and the fact that balance-scale measurements of relative weight are more accurate than those of absolute force. When distance and time also are more accurately measurable than absolute force, this second physical law permits a shift to standards of mass, distance, and time units, such as kilograms, meters, and seconds, with the unit of force—the newton—a derived unit. However, were force and distance more accurately measurable than time (e.g., time measured with an hourglass), this second physical law would permit a shift to standards of force, mass, and distance units such as newtons, kilograms, and meters, with the unit of time—the second—a derived unit. Therefore, the choice of the most accurate standard units depends both on what is most accurately measurable and on the accuracy of physical law.

A Combined Photochemical and Multicomponent Reaction Approach to Precision Oligomers.

PubMed

Konrad, Waldemar; Bloesser, Fabian R; Wetzel, Katharina S; Boukis, Andreas C; Meier, Michael A R; Barner-Kowollik, Christopher

2018-03-07

We introduce the convergent synthesis of linear monodisperse sequence-defined oligomers through a unique approach, combining the Passerini three-component reaction (P-3CR) and a Diels-Alder (DA) reaction based on photocaged dienes. A set of oligomers is prepared resting on a Passerini linker unit carrying an isocyano group for chain extension by P-3CR and a maleimide moiety for photoenol conjugation enabling a modular approach for chain growth. Monodisperse oligomers are accessible in a stepwise fashion by switching between both reaction types. Employing sebacic acid as a core unit allows the synthesis of a library of symmetric sequence-defined oligomers. The oligomers consist of alternating P-3CR and photoblocks with molecular weights up to 3532.16 g mol -1 , demonstrating the successful switching from P-3CR to photoenol conjugation. In-depth characterization was carried out including size-exclusion chromatography (SEC), high-resolution electrospray ionization mass spectrometry (ESI-MS) and NMR spectroscopy, evidencing the monodisperse nature of the precision oligomers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative targeted and retrospective data analysis of relevant pesticides, antibiotics and mycotoxins in bakery products by liquid chromatography-single-stage Orbitrap mass spectrometry.

PubMed

De Dominicis, Emiliano; Commissati, Italo; Gritti, Elisa; Catellani, Dante; Suman, Michele

2015-01-01

In addition to 'traditional' multi-residue and multi-contaminant multiple reaction monitoring (MRM) mass spectrometric techniques devoted to quantifying a list of targeted compounds, the global food industry requires non-targeted methods capable of detecting other possible potentially hazardous compounds. Ultra-high-performance liquid chromatography combined with a single-stage Orbitrap high-resolution mass spectrometer (UHPLC-HRMS Exactive™-Orbitrap Technology) was successfully exploited for the complete selective and quantitative determination of 33 target compounds within three major cross categories (pesticides, antibiotics and mycotoxins) in bakery matrices (specifically milk, wheat flour and mini-cakes). Resolution was set at 50 000 full width at half maximum (FWHM) to achieve the right compromise between an adequate scan speed and selectivity, allowing for the limitations related to the necessary generic sample preparation approach. An exact mass with tolerance of 5 ppm and minimum peak threshold of 10 000 units were fixed as the main identification conditions, including retention time and isotopic pattern as additional criteria devoted to greatly reducing the risk of false-positive findings. The full validation for all the target analytes was performed: linearity, intermediate repeatability and recovery (28 analytes within 70-120%) were positively assessed; furthermore, limits of quantification between 5 and 100 µg kg(-1) (with most of the analytes having a limit of detection below 6 µg kg(-1)) indicate good performance, which is compatible with almost all the regulatory needs. Naturally contaminated and fortified mini-cakes, prepared through combined use of industrial and pilot plant production lines, were analysed at two different concentration levels, obtaining good overall quantitative results and providing preliminary indications of the potential of full-scan HRMS cluster analysis. The effectiveness of this analytical approach was also tested in terms of the formulation of hypotheses for the identification of other analytes not initially targeted which can have toxicological implications (e.g. 3-acetyl-deoxynivalenol and deoxynivalenol-3-glucoside), opening a window on retrospective investigation perspectives in food safety laboratories.

Controlled banked turns in coleopteran flight measured by a miniature wireless inertial measurement unit.

PubMed

Li, Yao; Cao, Feng; Thang Vo Doan, Tat; Sato, Hirotaka

2016-09-28

The mechanisms and principles of insect flight have long been investigated by researchers working on micro and nano air vehicles (MAVs/NAVs). However, studies of insect flight maneuvers require high speed filming and high spatial resolution in a small experimental space, or the tethering of the insect to a fixed place. Under such artificial conditions, the insects may deviate its flying behavior from that of regular flight. In this study, we mounted a tiny wireless system, or 'backpack', on live beetles (Mecynorrhina torquata; length 62 ± 8 mm; mass 7.4 ± 1.3 g) freely flying in a large laboratory space. The backpack contains a micro inertial measurement unit (IMU) that was especially designed and manufactured for this purpose. Owing to the small mass (∼1.30 g) and dimensions (∼2.3 cm 2 ) of the backpack and the high accuracy of the IMU, we could remotely record the beetle in free flight. The free flight data revealed a strong linear correlation between the roll angle and yaw angular velocity. The strength of the correlation was quantified by the correlation coefficients and mean values. The change in roll angle preceded the change in yaw angular velocity. Moreover, there were frequent fluctuations in the roll angular velocity, which were uncorrelated with the yaw angular velocity. Apart from the strong correlation, these findings imply that Mecynorrhina torquata actively manipulates its roll rotation without coupling to the yaw rotation.

A resolution congratulating the athletes from the State of Nevada and throughout the United States who participated in the 2012 Olympic and Paralympic Games as members of the United States Olympic and Paralympic Teams.

THOMAS, 112th Congress

Sen. Reid, Harry [D-NV

2012-09-13

Senate - 09/22/2012 Resolution agreed to in Senate without amendment and with a preamble by Unanimous Consent. (All Actions) Tracker: This bill has the status Agreed to in SenateHere are the steps for Status of Legislation:

3 CFR - Delegation of Responsibility Under the Senate Resolution of Advice and Consent to Ratification of...

Code of Federal Regulations, 2013 CFR

2013-01-01

... 3 The President 1 2013-01-01 2013-01-01 false Delegation of Responsibility Under the Senate Resolution of Advice and Consent to Ratification of the Treaty Between the Government of the United States of America and the Government of the United Kingdom of Great Britain and Northern Ireland Concerning Defense Trade Cooperation; and the Defense Trad...

[Uncertainty evaluation of the determination of toxic equivalent quantity of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil by isotope dilution high resolution gas chromatography and high resolution mass spectrometry].

PubMed

Du, Bing; Liu Aimin; Huang, Yeru

2014-09-01

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in soil samples were analyzed by isotope dilution method with high resolution gas chromatography and high resolution mass spectrometry (ID-HRGC/HRMS), and the toxic equivalent quantity (TEQ) were calculated. The impacts of major source of measurement uncertainty are discussed, and the combined relative standard uncertainties were calculated for each 2, 3, 7, 8 substituted con- gener. Furthermore, the concentration, combined uncertainty and expanded uncertainty for TEQ of PCDD/Fs in a soil sample in I-TEF, WHO-1998-TEF and WHO-2005-TEF schemes are provided as an example. I-TEF, WHO-1998-TEF and WHO-2005-TEF are the evaluation schemes of toxic equivalent factor (TEF), and are all currently used to describe 2,3,7,8 sub- stituted relative potencies.

Multiplexed Post-Experimental Monoisotopic Mass Refinement ( m PE-MMR) to Increase Sensitivity and Accuracy in Peptide Identifications from Tandem Mass Spectra of Cofragmentation

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

Madar, Inamul Hasan; Ko, Seung-Ik; Kim, Hokeun

Mass spectrometry (MS)-based proteomics, which uses high-resolution hybrid mass spectrometers such as the quadrupole-orbitrap mass spectrometer, can yield tens of thousands of tandem mass (MS/MS) spectra of high resolution during a routine bottom-up experiment. Despite being a fundamental and key step in MS-based proteomics, the accurate determination and assignment of precursor monoisotopic masses to the MS/MS spectra remains difficult. The difficulties stem from imperfect isotopic envelopes of precursor ions, inaccurate charge states for precursor ions, and cofragmentation. We describe a composite method of utilizing MS data to assign accurate monoisotopic masses to MS/MS spectra, including those subject to cofragmentation. Themore » method, “multiplexed post-experiment monoisotopic mass refinement” (mPE-MMR), consists of the following: multiplexing of precursor masses to assign multiple monoisotopic masses of cofragmented peptides to the corresponding multiplexed MS/MS spectra, multiplexing of charge states to assign correct charges to the precursor ions of MS/ MS spectra with no charge information, and mass correction for inaccurate monoisotopic peak picking. When combined with MS-GF+, a database search algorithm based on fragment mass difference, mPE-MMR effectively increases both sensitivity and accuracy in peptide identification from complex high-throughput proteomics data compared to conventional methods.« less

The National Map - Elevation

USGS Publications Warehouse

Gesch, Dean; Evans, Gayla; Mauck, James; Hutchinson, John; Carswell, William J.

2009-01-01

The National Elevation Dataset (NED) is the primary elevation data product produced and distributed by the USGS. The NED provides seamless raster elevation data of the conterminous United States, Alaska, Hawaii, and the island territories. The NED is derived from diverse source data sets that are processed to a specification with a consistent resolution, coordinate system, elevation units, and horizontal and vertical datums. The NED is the logical result of the maturation of the long-standing USGS elevation program, which for many years concentrated on production of topographic map quadrangle-based digital elevation models. The NED serves as the elevation layer of The National Map, and provides basic elevation information for earth science studies and mapping applications in the United States. The NED is a multi-resolution dataset that is updated bimonthly to integrate newly available, improved elevation source data. NED data are available nationally at grid spacings of 1 arc-second (approximately 30 meters) for the conterminous United States, and at 1/3 and 1/9 arc-seconds (approximately 10 and 3 meters, respectively) for parts of the United States. Most of the NED for Alaska is available at 2-arc-second (about 60 meters) grid spacing, where only lower resolution source data exist. Part of Alaska is available at the 1/3-arc-second resolution, and plans are in development for a significant upgrade in elevation data coverage of the State over the next 5 years. Specifications for the NED include the following: *Coordinate system: Geographic (decimal degrees of latitude and longitude), *Horizontal datum: North American Datum of 1983 (NAD 83), *Vertical datum: North American Vertical Datum of 1988 (NAVD 88) over the conterminous United States and varies in other areas, and *Elevation units: Decimal meters.

Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

DOE PAGES

Winograd, Nicholas

2014-12-02

Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. When, using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Some issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. One key part of this discussion involves speculation onmore » how best to resolve these issues.« less

Imaging Mass Spectrometry on the Nanoscale with Cluster Ion Beams

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

Winograd, Nicholas

Imaging with cluster secondary ion mass spectrometry (SIMS) is reaching a mature level of development. When, using a variety of molecular ion projectiles to stimulate desorption, 3-dimensional imaging with the selectivity of mass spectrometry can now be achieved with submicrometer spatial resolution and <10 nm depth resolution. In this Perspective, stock is taken regarding what it will require to routinely achieve these remarkable properties. Some issues include the chemical nature of the projectile, topography formation, differential erosion rates, and perhaps most importantly, ionization efficiency. Shortcomings of existing instrumentation are also noted. One key part of this discussion involves speculation onmore » how best to resolve these issues.« less

Detection of Gelatin Adulteration in Traditional Chinese Medicine: Analysis of Deer-Horn Glue by Rapid-Resolution Liquid Chromatography-Triple Quadrupole Mass Spectrometry

PubMed Central

Chen, Jia; Cheng, Xian-Long; Wei, Feng; Zhang, Qian-Qian; Li, Ming-Hua; Ma, Shuang-Cheng

2015-01-01

Simultaneous identification of donkey-hide gelatin and bovine-hide gelatin in deer-horn glue was established by rapid-resolution liquid chromatography-triple quadrupole mass spectrometry. Water containing 1% NH4HCO3 was used for sample dissolution and trypsin was used for hydrolysis of the gelatins. After separation by a SB-C18 reversed-phase analytical column, collagen marker peptides were detected by mass spectrometry in positive electrospray ionization mode with multiple reaction monitoring. The method was specific, precise and reliable, and suitable for detection of adulterants derived from donkey-hide gelatin and bovine-hide gelatin in deer-horn glue. PMID:26504613

Coupling of the recoil mass spectrometer CAMEL to the γ-ray spectrometer GASP

NASA Astrophysics Data System (ADS)

Spolaore, P.; Ackermann, D.; Bednarczyk, P.; De Angelis, G.; Napoli, D.; Rossi Alvarez, C.; Bazzacco, D.; Burch, R.; Müller, L.; Segato, G. F.; Scarlassara, F.

1995-02-01

A project has been realized to link the CAMEL recoil mass spectrometer to the GASP γ-spectrometer in order to perform high resolution and efficiency γ-recoil coincidence measurements. To preserve high flexibility and autonomy in the operation of the two complex apparatus a rough factor two of reduction in the overall heavy ion transmission was accepted in designing the optics of the particle transport from the GASP center to the CAMEL focal plane. The coupled configuration has been tested with the fusion reaction 58Ni (E = 212 MeV) + 64Ni, obtaining a mass resolution of {1}/{300} and efficiency between ˜ 11% and ˜ 15% for different evaporation products.

Time-Resolved Molecular Characterization of Limonene/Ozone Aerosol using High-Resolution Electrospray Ionization Mass Spectrometry

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

Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia

2009-09-09

Molecular composition of limonene/O3 secondary organic aerosol (SOA) was investigated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) as a function of reaction time. SOA was generated by ozonation of D-limonene in a reaction chamber and sampled at different time intervals using a cascade impactor. The SOA samples were extracted into acetonitrile and analyzed using a HR-ESI-MS instrument with a resolving power of 100,000 (m/Δm). The resulting mass spectra provided detailed information about the extent of oxidation inferred from the O:C ratios, double bond equivalency (DBE) factors, and aromaticity indexes (AI) in hundreds of identified individual SOA species.

An improved experimental scheme for simultaneous measurement of high-resolution zero electron kinetic energy (ZEKE) photoelectron and threshold photoion (MATI) spectra

NASA Astrophysics Data System (ADS)

Michels, François; Mazzoni, Federico; Becucci, Maurizio; Müller-Dethlefs, Klaus

2017-10-01

An improved detection scheme is presented for threshold ionization spectroscopy with simultaneous recording of the Zero Electron Kinetic Energy (ZEKE) and Mass Analysed Threshold Ionisation (MATI) signals. The objective is to obtain accurate dissociation energies for larger molecular clusters by simultaneously detecting the fragment and parent ion MATI signals with identical transmission. The scheme preserves an optimal ZEKE spectral resolution together with excellent separation of the spontaneous ion and MATI signals in the time-of-flight mass spectrum. The resulting improvement in sensitivity will allow for the determination of dissociation energies in clusters with substantial mass difference between parent and daughter ions.

Uncertainty estimates of a GRACE inversion modelling technique over Greenland using a simulation

NASA Astrophysics Data System (ADS)

Bonin, Jennifer; Chambers, Don

2013-07-01

The low spatial resolution of GRACE causes leakage, where signals in one location spread out into nearby regions. Because of this leakage, using simple techniques such as basin averages may result in an incorrect estimate of the true mass change in a region. A fairly simple least squares inversion technique can be used to more specifically localize mass changes into a pre-determined set of basins of uniform internal mass distribution. However, the accuracy of these higher resolution basin mass amplitudes has not been determined, nor is it known how the distribution of the chosen basins affects the results. We use a simple `truth' model over Greenland as an example case, to estimate the uncertainties of this inversion method and expose those design parameters which may result in an incorrect high-resolution mass distribution. We determine that an appropriate level of smoothing (300-400 km) and process noise (0.30 cm2 of water) gets the best results. The trends of the Greenland internal basins and Iceland can be reasonably estimated with this method, with average systematic errors of 3.5 cm yr-1 per basin. The largest mass losses found from GRACE RL04 occur in the coastal northwest (-19.9 and -33.0 cm yr-1) and southeast (-24.2 and -27.9 cm yr-1), with small mass gains (+1.4 to +7.7 cm yr-1) found across the northern interior. Acceleration of mass change is measurable at the 95 per cent confidence level in four northwestern basins, but not elsewhere in Greenland. Due to an insufficiently detailed distribution of basins across internal Canada, the trend estimates of Baffin and Ellesmere Islands are expected to be incorrect due to systematic errors caused by the inversion technique.

Primary and secondary organic aerosols in Fresno, California during wintertime: Results from high resolution aerosol mass spectrometry

NASA Astrophysics Data System (ADS)

Ge, Xinlei; Setyan, Ari; Sun, Yele; Zhang, Qi

2012-10-01

Organic aerosols (OA) were studied in Fresno, California, in winter 2010 with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). OA dominated the submicron aerosol mass (average = 67%) with an average concentration of 7.9μg m-3 and a nominal formula of C1H1.59N0.014O0.27S0.00008, which corresponds to an average organic mass-to-carbon ratio of 1.50. Three primary OA (POA) factors and one oxygenated OA factor (OOA) representative of secondary OA (SOA) were identified via Positive Matrix Factorization of the high-resolution mass spectra. The three POA factors, which include a traffic-related hydrocarbon-like OA (HOA), a cooking OA (COA), and a biomass burning OA (BBOA) released from residential heating, accounted for an average 57% of the OA mass and up to 80% between 6 - 9 P.M., during which enhanced emissions from evening rush hour traffic, dinner cooking, and residential wood burning were exacerbated by low mixed layer height. The mass-based size distributions of the OA factors were estimated based on multilinear analysis of the size-resolved mass spectra of organics. Both HOA and BBOA peaked at ˜140 nm in vacuum aerodynamic diameter (Dva) while OOA peaked at an accumulation mode of ˜460 nm. COA exhibited a unique size distribution with two size modes centering at ˜200 nm and 450 nm respectively. This study highlights the leading roles played by anthropogenic POA emissions, primarily from traffic, cooking and residential heating, in aerosol pollution in Fresno in wintertime.

Some characteristics of matrix-assisted UV laser desorption/ionization mass spectrometric analysis of large proteins

NASA Astrophysics Data System (ADS)

Perera, I. K.; Kantartzoglou, S.; Dyer, P. E.

1996-12-01

We have performed experiments to explore the characteristics of the matrix-assisted laser desorption/ionization (MALDI) process and to ascertain optimal operational conditions for observing intact molecular ions of large proteins. In this study, several methods have been adopted for the preparation of analyte samples. Of these, the samples prepared with the simple dried-droplet method were found to be the most suitable for the generation of the large molecular clusters, while the near-uniform spin-coated samples were observed to produce highly reproducible molecular ion signals of relatively high mass resolutions. A resulting mass spectrum which illustrates the formation of cluster ions up to the 26-mer [26M+H]+ of bovine insulin corresponding to a mass of about 150,000 Da, is presented. The effect of fluence on the extent of clustering of protein molecules has been studied, the results revealing the existence of an optimum fluence for detecting the large cluster ions. Investigations have also indicated that the use of polyethylene-coated metallic substrates as sample supports can considerably reduce the fragmentation of the matrix/analyte molecular ions and the desorption of "neat" MALDI matrices deposited on these polyethylene-coated sample probes enhance their aggregation, forming up to the heptamer [7M+H]+ of the matrix, ferulic acid. The dependence of the mass resolution on the applied acceleration voltage and the desorption fluence has been examined and the results obtained are discussed in terms of a simple analysis of the linear time-of-flight mass spectrometer. A spectrum of chicken egg lysozyme (M~14,306) displaying the high mass resolutions (M/[Delta]M~690) that can be attained when the mass spectrometer is operated in the reflectron mode is also presented.

Seasonal and developmental differences in blubber stores of beluga whales in Bristol Bay, Alaska using high-resolution ultrasound

PubMed Central

Cornick, Leslie A.; Quakenbush, Lori T.; Norman, Stephanie A.; Pasi, Coral; Maslyk, Pamela; Burek, Kathy A.; Goertz, Caroline E. C.; Hobbs, Roderick C.

2016-01-01

Abstract Diving mammals use blubber for a variety of structural and physiological functions, including buoyancy, streamlining, thermoregulation, and energy storage. Estimating blubber stores provides proxies for body condition, nutritional status, and health. Blubber stores may vary topographically within individuals, across seasons, and with age, sex, and reproductive status; therefore, a single full-depth blubber biopsy does not provide an accurate measure of blubber depth, and additional biopsies are limited because they result in open wounds. We examined high-resolution ultrasound as a noninvasive method for assessing blubber stores by sampling blubber depth at 11 locations on beluga whales in Alaska. Blubber mass was estimated as a proportion of body mass (40% from the literature) and compared to a function of volume calculated using ultrasound blubber depth measurements in a truncated cone. Blubber volume was converted to total and mass-specific blubber mass estimates based on the density of beluga blubber. There was no significant difference in mean total blubber mass between the 2 estimates (R2 = 0.88); however, body mass alone predicted only 68% of the variation in mass-specific blubber stores in juveniles, 7% for adults in the fall, and 33% for adults in the spring. Mass-specific blubber stores calculated from ultrasound measurements were highly variable. Adults had significantly greater blubber stores in the fall (0.48±0.02kg/kgMB) than in the spring (0.33±0.02kg/kgMB). There was no seasonal effect in juveniles. High-resolution ultrasound is a more powerful, noninvasive method for assessing blubber stores in wild belugas, allowing for precise measurements at multiple locations. PMID:29899579

A Model of Equilibrium Conditions of Roof Rock Mass Giving Consideration to the Yielding Capacity of Powered Supports

NASA Astrophysics Data System (ADS)

Jaszczuk, Marek; Pawlikowski, Arkadiusz

2017-12-01

The work presents the model of interactions between the powered roof support units and the rock mass, while giving consideration to the yielding capacity of the supports - a value used for the analysis of equilibrium conditions of roof rock mass strata in geological and mining conditions of a given longwall. In the model, the roof rock mass is kept in equilibrium by: support units, the seam, goafs, and caving rocks (Fig. 1). In the assumed model of external load on the powered roof support units it is a new development - in relation to the model applied in selection of supports based on the allowable deflection of roof theory - that the load bearing capacity is dependent on the increment of the inclination of the roof rock mass and on the properties of the working medium, while giving consideration to the air pockets in the hydraulic systems, the load of the caving rocks on the caving shield, introducing the RA support value of the roof rock mass by the coal seam as a closed-form expression and while giving consideration to the additional support provided by the rocks of the goaf as a horizontal component R01H of the goaf reaction. To determine the roof maintenance conditions it is necessary to know the characteristics linking the yielding capacity of the support units with the heading convergence, which may be measured as the inclination angle of the roof rock mass. In worldwide mining, Ground Reaction Curves are used, which allow to determine the required yielding capacity of support units based on the relation between the load exerted on the unit and the convergence of the heading ensuring the equilibrium of the roof rock mass. (Figs. 4 and 8). The equilibrium of the roof rock mass in given conditions is determined at the displacement of the rock mass by the α angle, which impacts the following values: yielding capacity of units FN, vertical component of goaf reaction R01V and the horizontal component of goaf reaction R01H. In the model of load on the support units giving consideration to the load of the caving shield, a model of support unit was used that allows for unequivocal determination of the yielding capacity of the support with consideration given to the height of the unit in use and the change in the inclination of the canopy resulting from the displacement of the roof of the longwall. The yielding capacity of the support unit and its point of application on the canopy was determined using the method of units which allows for the internal forces to be manifested. The weight of the rock mass depends on the geological and mining conditions, for which the shape and dimensions of the rock mass affecting the support unit are determined. The resultant force of the pressure of gob on the gob shield was calculated by assuming that the load may be understood as a pressure of ground on a wall. This required the specification of the volume of the fallen rocks that affect the unit of powered roof supports (Fig. 2). To determine the support of the roof rock mass by the coal seam, experience of the Australian mining industry was used. Experiments regarding the strength properties of coal have exhibited that vertical deformation, at which the highest seam reaction occurs while supporting the roof rock mass, amounts to 0.5% of the longwall's height. The measure of the width of the contact area between the rock mass and the seam is the width of the additional uncovering of the face roof due to spalling of seam topcorners da (Fig. 2). With the above parameters and the value of the modulus of elasticity of coal in mind, the value of the seam's reaction may be estimated using the dependence (2). The vertical component of the goafs' reaction may be determined based on the strength characteristics of the fallen roof, the contact area of the rock mass with the fallen roof and the mean strain of the fallen roof at the area of contact. In the work by Pawlikowski (2014), a research procedure was proposed which encompasses model tests and exploitation tests of the loads exerted on the support units, aimed at the determination of the vertical component of the goaf reaction (Fig. 5). Based on duty cycles of powered roof support units, a mean value of the indicator of contact stiffness between the roof rock mass and the rocks constituting the caving is determined, assuming the linear dependence between the horizontal reaction and the heading convergence. The parameter allows for the determination of the horizontal component of the goafs' reaction in the external loading model of support units and allows for the determination of the required yielding capacity of supports, required to ensure the equilibrium of the roof rock mass. The experimentally verified model of the external loading of the units was used to conduct simulations of interactions between the KOPEX-095/17-POz support unit and the rock mass in a face characterized by the height of 1.6 m. Based on the data obtained in experiment, the variability of the yielding capacity of the support units was analyzed. A yielding capacity inclination angle of the units was determined for the registered curves (Figs. 6 and 7). At the same time, the presentation of the lines corresponding to the required yielding capacity of units and characterizing the deformability of the support units, allows for the prediction of the yielding capacity of the powered supports and the convergence of the heading in the conditions of a given face (Fig. 9).

Primary and secondary aerosols in Beijing in winter: sources, variations and processes

NASA Astrophysics Data System (ADS)

Sun, Yele; Du, Wei; Fu, Pingqing; Wang, Qingqing; Li, Jie; Ge, Xinlei; Zhang, Qi; Zhu, Chunmao; Ren, Lujie; Xu, Weiqi; Zhao, Jian; Han, Tingting; Worsnop, Douglas R.; Wang, Zifa

2016-07-01

Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions as well as two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size distributions, oxidation states of OA and evolutionary processes of secondary aerosols.

Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

NASA Astrophysics Data System (ADS)

Kostenidou, Evangelia; Karnezi, Eleni; Hite, James R., Jr.; Bougiatioti, Aikaterini; Cerully, Kate; Xu, Lu; Ng, Nga L.; Nenes, Athanasios; Pandis, Spyros N.

2018-04-01

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol-1 for the LO-OOA, 89 ± 10 kJ mol-1 for the MO-OOA, 55 ± 11 kJ mol-1 for the BBOA, and 63 ± 15 kJ mol-1 for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O : C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties.

Particle Environment Package (PEP) for the ESA JUICE mission

NASA Astrophysics Data System (ADS)

Barabash, Stas; Brandt, Pontus; Wurz, Peter; PEP Team

2016-10-01

PEP is a suite of six (6) sensors arranged in 4 units to measure charged and neutral particles in the Jupiter magnetospheres and at the moons to answer four overarching science questions:1. How does the corotating magnetosphere of Jupiter interact with the complex and diverse environment of Ganymede?2. How does the rapidly rotating magnetosphere of Jupiter interact with the seemingly inert Callisto?3. What are the governing mechanisms and their global impacts of release of material into the Jovian magnetosphere from seemingly inert Europa and active Io?4. How do internal and solar wind drivers cause such energetic, time variable and multi-scale phenomena in the steadily rotating giant magnetosphere of Jupiter?PEP measures positive and negative ions, electrons, exospheric neutral gas, thermal plasma and energetic neutral atoms present in all domains of the Jupiter system over nine decades of energy from < 0.001 eV to > 1 MeV with full angular coverage.PEP provides instantaneous measurements of 3D flow of the ion plasma and composition to understand the magnetosphere and magnetosphere-moon interactions. It also measures instantaneously 3D electron plasma to investigate auroral processes at the moon and Jupiter. Measurements of the angular distributions of energetic electrons at sub-second resolution probe the acceleration mechanisms and magnetic field topology and boundaries.PEP combines global imaging via remote sensing using energetic neutral atoms (ENA) with in-situ measurements and performs global imaging of Europa/Io tori and magnetosphere combined with energetic ion measurements. Using low energy ENAs originating from the particle - surface interaction PEP investigate space weathering of the icy moons by precipitation particles. PEP will first-ever directly sample of the exospheres of Europa, Ganymede, and Callisto with extremely high mass resolution (M/ΔM > 1100).The PEP sensors are (1) an ion mass analyzer, (2) an electron spectrometer, (3) a low energy ENA imager, (4) a high energy ENA and energetic ions imager, (5) an energetic electron sensor, and (6) a neutral gas and ions mass spectrometer.

Review: LC coupled to low- and high-resolution mass spectrometry for new psychoactive substance screening in biological matrices - Where do we stand today?

PubMed

Meyer, Markus R; Maurer, Hans H

2016-07-13

The field of new psychoactive substances (NPS) is highly dynamic and the situation changes from year to year. Therefore, the current review provides a timely update about the latest developments to help analysts keep the pace with NPS distribution. It covers PubMed-listed studies published between January 2014 and January 2016 dealing with the application of liquid chromatography (LC) coupled low- and high-resolution mass spectrometry (MS) for broad screenings for NPS in clinical (CT) and forensic (FT) toxicology. Latest developments and applications are highlighted and selected papers critically discussed. Comprehensive tables summarizing all discussed articles complete the overview. Finally, an outlook on the future of LC coupled MS in CT and FT is provided and readers will learn why low-resolution mass spectrometry might remain the standard for the next couple of years at least for easy-to-use quantitative screening procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

Strategies for dereplication of natural compounds using high-resolution tandem mass spectrometry.

PubMed

Kind, Tobias; Fiehn, Oliver

2017-09-01

Complete structural elucidation of natural products is commonly performed by nuclear magnetic resonance spectroscopy (NMR), but annotating compounds to most likely structures using high-resolution tandem mass spectrometry is a faster and feasible first step. The CASMI contest 2016 (Critical Assessment of Small Molecule Identification) provided spectra of eighteen compounds for the best manual structure identification in the natural products category. High resolution precursor and tandem mass spectra (MS/MS) were available to characterize the compounds. We used the Seven Golden Rules, Sirius2 and MS-FINDER software for determination of molecular formulas, and then we queried the formulas in different natural product databases including DNP, UNPD, ChemSpider and REAXYS to obtain molecular structures. We used different in-silico fragmentation tools including CFM-ID, CSI:FingerID and MS-FINDER to rank these compounds. Additional neutral losses and product ion peaks were manually investigated. This manual and time consuming approach allowed for the correct dereplication of thirteen of the eighteen natural products.

Profiling of patterned metal layers by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

NASA Astrophysics Data System (ADS)

Bi, Melody; Ruiz, Antonio M.; Gornushkin, Igor; Smith, Ben W.; Winefordner, James D.

2000-02-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for profiling patterned thin metal layers on a polymer/silicon substrate. The parameters of the laser and ICP-MS operating conditions have been studied and optimized for this purpose. A new laser ablation chamber was designed and built to achieve the best spatial resolution. The results of the profiling by LA-ICP-MS were compared to those obtained from a laser ablation optical emission spectrometry (LA-OES) instrument, which measured the emission of the plasma at the sample surface, and thus, eliminated the time delay caused by the sample transport into the ICP-MS system. Emission spectra gave better spatial resolution than mass spectra. However, LA-ICP-MS provided much better sensitivity and was able to profile thin metal layers (on the order of a few nanometers) on the silicon surface. A lateral spatial resolution of 45 μm was achieved.

Combining targeted and nontargeted data analysis for liquid chromatography/high-resolution mass spectrometric analyses.

PubMed

Croley, Timothy R; White, Kevin D; Wong, Jon; Callahan, John H; Musser, Steven M; Antler, Margaret; Lashin, Vitaly; McGibbon, Graham A

2013-03-01

Increasing importation of food and the diversity of potential contaminants have necessitated more analytical testing of these foods. Historically, mass spectrometric methods for testing foods were confined to monitoring selected ions (SIM or MRM), achieving sensitivity by focusing on targeted ion signals. A limiting factor in this approach is that any contaminants not included on the target list are not typically identified and retrospective data mining is limited. A potential solution is to utilize high-resolution MS to acquire accurate mass full-scan data. Based on the instrumental resolution, these data can be correlated to the actual mass of a contaminant, which would allow for identification of both target compounds and compounds that are not on a target list (nontargets). The focus of this research was to develop software algorithms to provide rapid and accurate data processing of LC/MS data to identify both targeted and nontargeted analytes. Software from a commercial vendor was developed to process LC/MS data and the results were compared to an alternate, vendor-supplied solution. The commercial software performed well and demonstrated the potential for a fully automated processing solution. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Background correction in separation techniques hyphenated to high-resolution mass spectrometry - Thorough correction with mass spectrometry scans recorded as profile spectra.

PubMed

Erny, Guillaume L; Acunha, Tanize; Simó, Carolina; Cifuentes, Alejandro; Alves, Arminda

2017-04-07

Separation techniques hyphenated with high-resolution mass spectrometry have been a true revolution in analytical separation techniques. Such instruments not only provide unmatched resolution, but they also allow measuring the peaks accurate masses that permit identifying monoisotopic formulae. However, data files can be large, with a major contribution from background noise and background ions. Such unnecessary contribution to the overall signal can hide important features as well as decrease the accuracy of the centroid determination, especially with minor features. Thus, noise and baseline correction can be a valuable pre-processing step. The methodology that is described here, unlike any other approach, is used to correct the original dataset with the MS scans recorded as profiles spectrum. Using urine metabolic studies as examples, we demonstrate that this thorough correction reduces the data complexity by more than 90%. Such correction not only permits an improved visualisation of secondary peaks in the chromatographic domain, but it also facilitates the complete assignment of each MS scan which is invaluable to detect possible comigration/coeluting species. Copyright © 2017 Elsevier B.V. All rights reserved.

The Q continuum simulation: Harnessing the power of GPU accelerated supercomputers

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

Heitmann, Katrin; Frontiere, Nicholas; Sewell, Chris

2015-08-01

Modeling large-scale sky survey observations is a key driver for the continuing development of high-resolution, large-volume, cosmological simulations. We report the first results from the "Q Continuum" cosmological N-body simulation run carried out on the GPU-accelerated supercomputer Titan. The simulation encompasses a volume of (1300 Mpc)(3) and evolves more than half a trillion particles, leading to a particle mass resolution of m(p) similar or equal to 1.5 . 10(8) M-circle dot. At thismass resolution, the Q Continuum run is currently the largest cosmology simulation available. It enables the construction of detailed synthetic sky catalogs, encompassing different modeling methodologies, including semi-analyticmore » modeling and sub-halo abundance matching in a large, cosmological volume. Here we describe the simulation and outputs in detail and present first results for a range of cosmological statistics, such as mass power spectra, halo mass functions, and halo mass-concentration relations for different epochs. We also provide details on challenges connected to running a simulation on almost 90% of Titan, one of the fastest supercomputers in the world, including our usage of Titan's GPU accelerators.« less

High Resolution Chemical Study of ALH84001

NASA Technical Reports Server (NTRS)

Conrad, Pamela G.; Douglas, Susanne; Kuhlman, Kimberly R.

2001-01-01

We have studied the chemistry of a sample of the SNC meteorite ALH84001 using an environmental scanning electron microscope (ESEM) with an energy dispersive chemical analytical detector and a focused ion beam secondary ion mass spectrometer (FIB-SIMS). Here we present the chemical data, both spectra and images, from two techniques that do not require sample preparation with a conductive coating, thus eliminating the possibility of preparation-induced textural artifacts. The FIB-SIMS instrument includes a column optimized for SEM with a quadrupole type mass spectrometer. Its spatial and spectral resolution are 20 nm and 0.4 AMU, respectively. The spatial resolution of the ESEM for chemical analysis is about 100 nm. Limits of detection for both instruments are mass dependent. Both the ESEM and the FIB-SIMS instrument revealed contrasting surficial features; crumbled, weathered appearance of the matrix in some regions as well as a rather ubiquitous presence of euhedral halite crystals, often associated with cracks or holes in the surface of the rock. Other halogen elements present in the vicinity of the NaCl crystals include K and Br. In this report, elemental inventories are shown as mass spectra and as X-ray maps.

Application of a trap-free two-dimensional liquid chromatography combined with ion trap/time-of-flight mass spectrometry for separation and characterization of impurities and isomers in cefpiramide.

PubMed

Wang, Jian; Xu, Yu; Wen, Chunmei; Wang, Zhijian

2017-11-01

High-resolution mass spectrometry had been routinely used for structure identification of impurity. However, all LC-MS methods were based on a volatile mobile phase, and a non-volatile system is used in the official analytical method of United States Pharmacopoeia for cefpiramide which limited the use of mass spectrometry for structure characterization of the impurities. Here we presented the utilization of a trap-free two-dimensional liquid chromatography coupled to high resolution ion trap/time-of-flight mass spectrometry (2D LC-IT-TOF MS) with positive and negative modes of electrospray ionization for characterization of eight impurities in cefpiramide. Trap-free two-dimensional liquid chromatography and online desalting technique made it possible to characterize the impurity in cefpiramide in the condition of official standard, and the TIC chromatogram of LC-MS was in conformity with the LC chromatogram of the official analytical method in the peak sequence of impurities, which could further improve the method of official monographs in pharmacopoeias. Each peak separated by the non-volatile mobile phase was trapped by a 20 μL quantitative loop then transferred into a system with a volatile mobile phase connected to a MS detector. In the first dimension, the column was Kromasil C 8 analytical column (250 mm × 4.6 mm, 5 μm) with a non-volatile salt mobile phase at the flow rate of 0.8 mL min -1 . In the second dimension, the column was Shimadzu Shim-pack GISS C 18 (50 mm × 2.1 mm, 1.9 μm) with a volatile salt mobile phase at the flow rate of 0.3 mL min -1 . Through the multiple heart-cutting 2D-LC approach and online desalting technique, the problem of incompatibility between non-volatile salt mobile phase and mass spectrometry was solved completely. The fragmentation behavior of cefpiramide and its eight impurities were studied. The structures of eight impurities in cefpiramide drug substance were deduced based on the HPLC-MS n data, in which seven impurities were novel impurities. The forming mechanisms of degradation products in cefpiramide were also studied. Copyright © 2017 Elsevier B.V. All rights reserved.

Bondi or not Bondi: the impact of resolution on accretion and drag force modelling for supermassive black holes

NASA Astrophysics Data System (ADS)

Beckmann, R. S.; Slyz, A.; Devriendt, J.

2018-07-01

Whilst in galaxy-size simulations, supermassive black holes (SMBHs) are entirely handled by sub-grid algorithms, computational power now allows the accretion radius of such objects to be resolved in smaller scale simulations. In this paper, we investigate the impact of resolution on two commonly used SMBH sub-grid algorithms; the Bondi-Hoyle-Lyttleton (BHL) formula for accretion on to a point mass, and the related estimate of the drag force exerted on to a point mass by a gaseous medium. We find that when the accretion region around the black hole scales with resolution, and the BHL formula is evaluated using local mass-averaged quantities, the accretion algorithm smoothly transitions from the analytic BHL formula (at low resolution) to a supply-limited accretion scheme (at high resolution). However, when a similar procedure is employed to estimate the drag force, it can lead to significant errors in its magnitude, and/or apply this force in the wrong direction in highly resolved simulations. At high Mach numbers and for small accretors, we also find evidence of the advective-acoustic instability operating in the adiabatic case, and of an instability developing around the wake's stagnation point in the quasi-isothermal case. Moreover, at very high resolution, and Mach numbers above M_∞ ≥ 3, the flow behind the accretion bow shock becomes entirely dominated by these instabilities. As a result, accretion rates on to the black hole drop by about an order of magnitude in the adiabatic case, compared to the analytic BHL formula.

Bondi or not Bondi: the impact of resolution on accretion and drag force modelling for Supermassive Black Holes

NASA Astrophysics Data System (ADS)

Beckmann, R. S.; Slyz, A.; Devriendt, J.

2018-04-01

Whilst in galaxy-size simulations, supermassive black holes (SMBH) are entirely handled by sub-grid algorithms, computational power now allows the accretion radius of such objects to be resolved in smaller scale simulations. In this paper, we investigate the impact of resolution on two commonly used SMBH sub-grid algorithms; the Bondi-Hoyle-Lyttleton (BHL) formula for accretion onto a point mass, and the related estimate of the drag force exerted onto a point mass by a gaseous medium. We find that when the accretion region around the black hole scales with resolution, and the BHL formula is evaluated using local mass-averaged quantities, the accretion algorithm smoothly transitions from the analytic BHL formula (at low resolution) to a supply limited accretion (SLA) scheme (at high resolution). However, when a similar procedure is employed to estimate the drag force it can lead to significant errors in its magnitude, and/or apply this force in the wrong direction in highly resolved simulations. At high Mach numbers and for small accretors, we also find evidence of the advective-acoustic instability operating in the adiabatic case, and of an instability developing around the wake's stagnation point in the quasi-isothermal case. Moreover, at very high resolution, and Mach numbers above M_∞ ≥ 3, the flow behind the accretion bow shock becomes entirely dominated by these instabilities. As a result, accretion rates onto the black hole drop by about an order of magnitude in the adiabatic case, compared to the analytic BHL formula.

Un Détecteur de Neutrons pour la Spectrométrie de Masses Manquantes

NASA Astrophysics Data System (ADS)

Bollini, D.; Buhler-Broglin, A.; Dalpiaz, P.; Massam, T.; Navach, F.; Navarria, F. L.; Schneegans, M. A.; Zichichi, A.

A large (2 × 0.39 m3 plastic scintillator) neutron detector capable to measure with high accuracy the coordinates of the neutron interaction point as well as its time-of-flight is described. As a missing mass spectrometer, it allows to observe for example the η, meson with a mass resolution of ± 4.2 MeV. Nous décrivous un détectcur de neutrons de grand volume sensible (2 x 0,39 m3 de scintillatcur plastique) capable de mesurer avec précision les coordonnées du point d'interaction du neutron détecté ainsi que son temp-de-vol. Employé comme spectrométre de masses manquantes, it permet d'observer par exemple le méson η avec une resolution de ± 4,2 MeY.

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

PubMed

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

Mass separation of deuterium and helium with conventional quadrupole mass spectrometer by using varied ionization energy

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

Yu, Yaowei; Hu, Jiansheng, E-mail: hujs@ipp.ac.cn; Wan, Zhao

2016-03-15

Deuterium pressure in deuterium-helium mixture gas is successfully measured by a common quadrupole mass spectrometer (model: RGA200) with a resolution of ∼0.5 atomic mass unit (AMU), by using varied ionization energy together with new developed software and dedicated calibration for RGA200. The new software is developed by using MATLAB with the new functions: electron energy (EE) scanning, deuterium partial pressure measurement, and automatic data saving. RGA200 with new software is calibrated in pure deuterium and pure helium 1.0 × 10{sup −6}–5.0 × 10{sup −2} Pa, and the relation between pressure and ion current of AMU4 under EE = 25 eVmore » and EE = 70 eV is obtained. From the calibration result and RGA200 scanning with varied ionization energy in deuterium and helium mixture gas, both deuterium partial pressures (P{sub D{sub 2}}) and helium partial pressure (P{sub He}) could be obtained. The result shows that deuterium partial pressure could be measured if P{sub D{sub 2}} > 10{sup −6} Pa (limited by ultimate pressure of calibration vessel), and helium pressure could be measured only if P{sub He}/P{sub D{sub 2}} > 0.45, and the measurement error is evaluated as 15%. This method is successfully employed in EAST 2015 summer campaign to monitor deuterium outgassing/desorption during helium discharge cleaning.« less

Characterization of goat colostrum oligosaccharides by nano-liquid chromatography on chip quadrupole time-of-flight mass spectrometry and hydrophilic interaction liquid chromatography-quadrupole mass spectrometry

PubMed Central

Martín-Ortiz, A.; Salcedo, J.; Barile, D.; Bunyatratchata, A.; Moreno, F.J.; Martin-García, I.; Clemente, A.; Sanz, M.L.; Ruiz-Matute, A.I.

2016-01-01

A detailed qualitative and quantitative characterization of goat colostrum oligosaccharides (GCO) has been carried out for the first time. Defatted and deproteinized colostrum samples, previously treated by size exclusion chromatography (SEC) to remove lactose, were analyzed by nanoflow liquid chromatography-quadrupole-time of flight mass spectrometry (Nano-LC-Chip-Q-TOF MS). Up to 78 oligosaccharides containing hexose, hexosamine, fucose, N-acetylneuraminic acid or N-glycolylneuraminic acid monomeric units were identified in the samples, some of them detected for the first time in goat colostra. As a second step, a hydrophilic interaction liquid chromatography coupled to mass spectrometry (HILIC-MS) methodology was developed for the separation and quantitation of the main GCO, both acidic and neutral carbohydrates. Among other experimental chromatographic conditions, mobile phase additives and column temperature were evaluated in terms of retention time, resolution, peak width and symmetry of target carbohydrates. Narrow peaks (wh: 0.2–0.6 min) and good symmetry (As: 0.8–1.4) were obtained for GCO using an acetonitrile:water gradient with 0.1% ammonium hydroxide at 40 °C. These conditions were selected to quantify the main oligosaccharides in goat colostrum samples. Values ranging from 140 to 315 mg L−1 for neutral oligosaccharides and from 83 to 251 mg L−1 for acidic oligosaccharides were found. The combination of both techniques resulted to be useful to achieve a comprehensive characterization of GCO. PMID:26427327

Assessment of benzophenone-4 reactivity with free chlorine by liquid chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Negreira, N; Rodríguez, I; Rodil, R; Cela, R

2012-09-19

The stability of the UV filter benzophenone-4 (BP-4) in free chlorine-containing water was investigated, for the first time, by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QqTOF-MS). High mass accuracy and resolution capabilities of this hybrid mass spectrometer were used for the reliable assignation of empirical formulae and chemical structures of BP-4 derivatives. Time-course profiles of the parent compound and its by-products were simultaneously recorded by direct injection of sample aliquots, after quenching the excess of chlorine, in the LC-QqTOF-MS system. At neutral pHs, in excess of chlorine, BP-4 showed a limited stability fitting a pseudo-first-order degradation kinetics. A noticeable reduction in the half-lives of BP-4 was observed when increasing the sample pH between 6 and 8 units and also in presence of bromide traces. The reaction pathway of this UV filter involved a first electrophilic substitution of hydrogen per chlorine (or bromide) in the phenolic ring, followed by oxidation of the carbonyl moiety to an ester group, which induced a further electrophilic substitution in the same aromatic ring. Above reactions were also noticed when mixing a BP-4 containing personal care product with chlorinated tap water and in chlorinated swimming pool and sewage water, previously spiked with a BP-4 standard. Copyright © 2012 Elsevier B.V. All rights reserved.

Comprehensive characterisation of flame retardants in textile furnishings by ambient high resolution mass spectrometry, gas chromatography-mass spectrometry and environmental forensic microscopy.

PubMed

Ionas, Alin C; Ballesteros Gómez, Ana; Uchida, Natsuyo; Suzuki, Go; Kajiwara, Natsuko; Takata, Kyoko; Takigami, Hidetaka; Leonards, Pim E G; Covaci, Adrian

2015-10-01

The presence and levels of flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and organophosphate flame retardants (PFRs), was determined in textile home furnishings, such as carpets and curtains from stores in Belgium. A comprehensive characterisation of FRs in textile was done by ambient high resolution mass spectrometry (qualitative screening), gas chromatography-mass spectrometry (GC-MS) (quantitation), and environmental forensic microscopy (surface distribution). Ambient ionisation coupled to a time-of-flight (TOF) high resolution mass spectrometer (direct probe-TOF-MS) was investigated for the rapid screening of FRs. Direct probe-TOF-MS proved to be useful for a first screening step of textiles to detect FRs below the levels required to impart flame retardancy and to reduce, in this way, the number of samples for further quantitative analysis. Samples were analysed by GC-MS to confirm the results obtained by ambient mass spectrometry and to obtain quantitative information. The levels of PBDEs and PFRs were typically too low to impart flame retardancy. Only high levels of BDE-209 (11-18% by weight) were discovered and investigated in localised hotspots by employing forensic microscopy techniques. Most of the samples were made of polymeric materials known to be inherently flame retarded to some extent, so it is likely that other alternative and halogen-free FR treatments/solutions are preferred for the textiles on the Belgian market. Copyright © 2015 Elsevier Inc. All rights reserved.

Vacuum compatible sample positioning device for matrix assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry imaging

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

Aizikov, Konstantin; Lin, Tzu-Yung; Department of Electrical and Computer Engineering, Boston University, Boston, Massachusetts 02215

The high mass accuracy and resolving power of Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS) make them ideal mass detectors for mass spectrometry imaging (MSI), promising to provide unmatched molecular resolution capabilities. The intrinsic low tolerance of FT-ICR MS to RF interference, however, along with typically vertical positioning of the sample, and MSI acquisition speed requirements present numerous engineering challenges in creating robotics capable of achieving the spatial resolution to match. This work discusses a two-dimensional positioning stage designed to address these issues. The stage is capable of operating in {approx}1 x 10{sup -8} mbar vacuum. The rangemore » of motion is set to 100 mm x 100 mm to accommodate large samples, while the positioning accuracy is demonstrated to be less than 0.4 micron in both directions under vertical load over the entire range. This device was integrated into three different matrix assisted laser desorption/ionization (MALDI) FT-ICR instruments and showed no detectable RF noise. The ''oversampling'' MALDI-MSI experiments, under which the sample is completely ablated at each position, followed by the target movement of the distance smaller than the laser beam, conducted on the custom-built 7T FT-ICR MS demonstrate the stability and positional accuracy of the stage robotics which delivers high spatial resolution mass spectral images at a fraction of the laser spot diameter.« less

A model of forest floor carbon mass for United States forest types

Treesearch

James E. Smith; Linda S. Heath

2002-01-01

Includes a large set of published values of forest floor mass and develop large-scale estimates of carbon mass according to region and forest type. Estimates of average forest floor carbon mass per hectare of forest applied to a 1997 summary forest inventory, sum to 4.5 Gt carbon stored in forests of the 48 contiguous United States.

Linear electric field mass spectrometry

DOEpatents

McComas, D.J.; Nordholt, J.E.

1992-12-01

A mass spectrometer and methods for mass spectrometry are described. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field. 8 figs.

The Dissemination of Mass in the United States: Results and Implications of Recent BIPM Calibrations of US National Prototype Kilograms

PubMed Central

Kubarych, Zeina J; Abbott, Patrick J

2014-01-01

The National Institute of Standards and Technology (NIST) is responsible for the dissemination of the unit of mass within the United States of America through the national prototype kilogram K20 and its check standard K4. These platinum-iridium artifacts have been in use since 1889 and are periodically sent to the International Bureau of Weights and Measures (BIPM) for recalibration. The following is a brief description of the roles of the national prototype kilograms in the dissemination of mass in the United States of America, and the implications for NIST mass calibration customers of the most recent recalibrations of K20 and K4. PMID:26601023

High-Resolution Ambient MS Imaging of Negative Ions in Positive Ion Mode: Using Dicationic Reagents with the Single-Probe

NASA Astrophysics Data System (ADS)

Rao, Wei; Pan, Ning; Tian, Xiang; Yang, Zhibo

2016-01-01

We have used the Single-probe, a miniaturized sampling device utilizing in-situ surface microextraction for ambient mass spectrometry (MS) analysis, for the high resolution MS imaging (MSI) of negatively charged species in the positive ionization mode. Two dicationic compounds, 1,5-pentanediyl-bis(1-butylpyrrolidinium) difluoride [C5(bpyr)2F2] and 1,3-propanediyl-bis(tripropylphosphonium) difluoride [C3(triprp)2F2], were added into the sampling solvent to form 1+ charged adducts with the negatively charged species extracted from tissues. We were able to detect 526 and 322 negatively charged species this way using [C5(bpyr)2F2] and [C3(triprp)2F2], respectively, including oleic acid, arachidonic acid, and several species of phosphatidic acid, phosphoethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, and others. In conjunction with the identification of the non-adduct cations, we have tentatively identified a total number of 1200 and 828 metabolites from mouse brain sections using [C5(bpyr)2F2] and [C3(triprp)2F2], respectively, through high mass accuracy measurements (mass error <5 ppm); MS/MS analyses were also performed to verify the identity of selected species. In addition to the high mass accuracy measurement, we were able to generate high spatial resolution (~17 μm) MS images of mouse brain sections. Our study demonstrated that utilization of dicationic compounds in the surface microextraction with the Single-probe device can perform high mass and spatial resolution ambient MSI measurements of broader types of compounds in tissues. Other reagents can be potentially used with the Single-probe device for a variety of reactive MSI studies to enable the analysis of species that are previously intractable.

Structural Characterization of a Thrombin-Aptamer Complex by High Resolution Native Top-Down Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Jiang; Loo, Rachel R. Ogorzalek; Loo, Joseph A.

2017-09-01

Native mass spectrometry (MS) with electrospray ionization (ESI) has evolved as an invaluable tool for the characterization of intact native proteins and non-covalently bound protein complexes. Here we report the structural characterization by high resolution native top-down MS of human thrombin and its complex with the Bock thrombin binding aptamer (TBA), a 15-nucleotide DNA with high specificity and affinity for thrombin. Accurate mass measurements revealed that the predominant form of native human α-thrombin contains a glycosylation mass of 2205 Da, corresponding to a sialylated symmetric biantennary oligosaccharide structure without fucosylation. Native MS showed that thrombin and TBA predominantly form a 1:1 complex under near physiological conditions (pH 6.8, 200 mM NH4OAc), but the binding stoichiometry is influenced by the solution ionic strength. In 20 mM ammonium acetate solution, up to two TBAs were bound to thrombin, whereas increasing the solution ionic strength destabilized the thrombin-TBA complex and 1 M NH4OAc nearly completely dissociated the complex. This observation is consistent with the mediation of thrombin-aptamer binding through electrostatic interactions and it is further consistent with the human thrombin structure that contains two anion binding sites on the surface. Electron capture dissociation (ECD) top-down MS of the thrombin-TBA complex performed with a high resolution 15 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer showed the primary binding site to be at exosite I located near the N-terminal sequence of the heavy chain, consistent with crystallographic data. High resolution native top-down MS is complementary to traditional structural biology methods for structurally characterizing native proteins and protein-DNA complexes. [Figure not available: see fulltext.

Quantification of marine aerosol subgrid variability and its correlation with clouds based on high-resolution regional modeling: Quantifying Aerosol Subgrid Variability

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

Lin, Guangxing; Qian, Yun; Yan, Huiping

One limitation of most global climate models (GCMs) is that with the horizontal resolutions they typically employ, they cannot resolve the subgrid variability (SGV) of clouds and aerosols, adding extra uncertainties to the aerosol radiative forcing estimation. To inform the development of an aerosol subgrid variability parameterization, here we analyze the aerosol SGV over the southern Pacific Ocean simulated by the high-resolution Weather Research and Forecasting model coupled to Chemistry. We find that within a typical GCM grid, the aerosol mass subgrid standard deviation is 15% of the grid-box mean mass near the surface on a 1 month mean basis.more » The fraction can increase to 50% in the free troposphere. The relationships between the sea-salt mass concentration, meteorological variables, and sea-salt emission rate are investigated in both the clear and cloudy portion. Under clear-sky conditions, marine aerosol subgrid standard deviation is highly correlated with the standard deviations of vertical velocity, cloud water mixing ratio, and sea-salt emission rates near the surface. It is also strongly connected to the grid box mean aerosol in the free troposphere (between 2 km and 4 km). In the cloudy area, interstitial sea-salt aerosol mass concentrations are smaller, but higher correlation is found between the subgrid standard deviations of aerosol mass and vertical velocity. Additionally, we find that decreasing the model grid resolution can reduce the marine aerosol SGV but strengthen the correlations between the aerosol SGV and the total water mixing ratio (sum of water vapor, cloud liquid, and cloud ice mixing ratios).« less

High-Resolution Submillimeter and Near-Infrared Studies of the Transition Disk Around Sz 91

NASA Technical Reports Server (NTRS)

Tsukagoshi, Takashi; Momose, Munetake; Abe, Lyu; Akiyama, Eiji; Brandner, Wolfgang; Brandt, Timothy D.; Carson, Joseph; Currie, Thayne; Egner, Sebastian E.; Goto, Miwa;

(Un)targeted Scanning of Locks of Hair for Drugs of Abuse by Direct Analysis in Real Time-High-Resolution Mass Spectrometry.

PubMed

Duvivier, Wilco F; van Putten, Marc R; van Beek, Teris A; Nielen, Michel W F

2016-02-16

Forensic hair evidence can be used to obtain retrospective timelines of drug use by analysis of hair segments. However, this is a laborious and time-consuming process, and mass spectrometric (MS) imaging techniques, which show great potential for single-hair targeted analysis, are less useful due to differences in hair growth rate between individual hairs. As an alternative, a fast untargeted analysis method was developed that uses direct analysis in real time-high-resolution mass spectrometry (DART-HRMS) to longitudinally scan intact locks of hair without extensive sample preparation or segmentation. The hair scan method was validated for cocaine against an accredited liquid chromatography/tandem mass spectrometry (LC/MS/MS) method. The detection limit for cocaine in hair was found to comply with the cutoff value of 0.5 ng/mg recommended by the Society of Hair Testing; that is, the DART hair scan method is amenable to forensic cases. Under DART conditions, no significant thermal degradation of cocaine occurred. The standard DART spot size of 5.1 ± 1.1 mm could be improved to 3.3 ± 1.0 mm, corresponding to approximately 10 days of hair growth, by using a high spatial resolution exit cone. By use of data-dependent product ion scans, multiple drugs of abuse could be detected in a single drug user hair scan with confirmation of identity by both exact mass and MS/HRMS fragmentation patterns. Furthermore, full-scan high-resolution data were retrospectively interrogated versus a list of more than 100 compounds and revealed additional hits and temporal profiles in good correlation with reported drug use.