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At least 397 records · Page 22

Development and Implementation of Aseptic Operations for the MOMA-Mass Spectrometer

The ExoMars 2020 Rover is a life detection mission, and is classified as Planetary Protection (PP) Mission Category IVb, the first IVb mission since the Viking missions. Mars Organic Molecule Analyzer Mass Spectrometer (MOMA-MS) is a life detection instrument for the rover. To meet the stringent bioburden requirement of 0.03 spore/m2, the MS is subjected to Dry Heat Microbial Reduction (DHMR) to decrease the bioburden from a measured 88 spores/m2 to 0.009 spores/m2. After DHMR, exposure of the sample path must be kept to an absolute minimum and requires aseptic operations. Aseptic operations include determining the safe exposure time based on the surface area of exposure and particle fallout expected in the aseptic ISO class 5 workspace, preparing an aseptic ISO class 5 workspace, and using sterile garments and tools. During the exposure activity the environment is monitored with active and passive fallout for bioburden and real time airborne particle counts. Sterile tools are handled by a two person team so the operator touches only the tool and not the exterior surfaces of the sterilization pouch, and a sterile operating field is established as a safe place to organize tools or parts during the aseptic operations. In cases where aseptic operations are not feasible, localized DHMR is used after exposure. Any breach in the PP cleanliness can necessitate repeating instrument level DHMR, which not only has significant cost and schedule implications, but also is a risk to hardware that is not rated for repeated long exposures to high temperatures.

Aseptic processing↗

Measurement report: The Fifth International Workshop on Ice Nucleation phase 1 (FIN-01): intercomparison of single-particle mass spectrometers

Knowledge of the chemical composition and mixing state of aerosols at a single-particle level is critical for gaining insights into atmospheric processes. One common tool to make these measurements is single-particle mass spectrometry. There remains a need to compare the performance of different single-particle mass spectrometers (SPMSs). An intercomparison of SPMSs was conducted at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber at the Karlsruhe Institute of Technology (KIT) in November 2014, as part of the first phase of the Fifth International Workshop on Ice Nucleation (FIN-01). In this paper we compare size distributions and mass spectra of atmospherically relevant particle types measured by five SPMSs. These include different minerals, desert and soil dusts, soot, bioaerosol (Snomax; protein granule), secondary organic aerosol (SOA), and SOA-coated mineral particles. Most SPMSs reported similar vacuum aerodynamic diameter (d va ) within typical instrumental ranges from ~100–200 nm (lower limit) to ~2–3 µm (upper limit). In general, all SPMSs exhibited a wide dynamic range (up to ~10 3 ) and high signal-to-noise ratio (up to ~10 4 ) in mass spectra. Common spectral features with small diversities in mass spectra were found with high average Pearson's correlation coefficients, i.e., for average positive spectra r avg-pos =0.74 ± 0.12 and average negative spectra r avg-neg =0.67 ± 0.22. We found that instrument-specific detection efficiency (DE) was more dependent on particle size than particle type, and particle identification favored the use of bipolar, rather than monopolar, instruments. Particle classification from “blind experiments” showed that all instruments differentiated SOA, soot, and soil dust and detected subtle changes in the particle internal mixing but had difficulties differentiating among specific mineral types and dusts. This study helps to further understand the capabilities and limitations of the single-particle mass spectrometry technique in general and the specific performance of the instrument in characterizing atmospheric aerosol particles.

54 ENVIRONMENTAL SCIENCES↗

Preliminary investigation of an uncertainty budget for uranium isotope ratio analysis using a liquid sampling—atmospheric pressure glow discharge—orbitrap mass spectrometer system

The liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source has proven to be an effective analysis tool for making uranium isotope ratio measurements when coupled to high-resolution mass spectrometers, such as the Orbitrap. While previous studies have shown the capabilities of the LS-APGD for isotope ratio determination, a systematic evaluation of the measurement uncertainty of the technique has not been conducted. To this end, the International Standards Organizations (ISO) guidelines to the expression of uncertainty in measurement (GUM analysis) have been applied to generate an uncertainty budget. For this work, a preliminary assessment derived from the GUM analysis was performed. The uncertainty in the instrument blank determination has been identified as a primary factor contributing to measurement uncertainty for the LS-APGD-Orbitrap method. These findings for the specific test case of uranium isotopic analysis will be invaluable in applications across the breadth of isotope ratio mass spectrometry performed on this unique instrumental platform.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Development of a Low Power Gas Chromatograph-Mass Spectrometer for In-Situ Detection of Organics in Martian Soil

The Mars Organic Molecule Analyzer (MOMA) is a joint venture by NASA and the European Space Agency (ESA) to develop a sensitive, light-weight, low-power mass spectrometer for chemical analysis on Mars. MOMA is a key analytical instrument aboard the 2018 ExoMars rover mission seeking signs of past or present life. The current prototype was built to demonstrate operation of gas chromatography (OC) and laser desorption (LD) mass spectrometry under martian ambient conditions (5-7 Torr of CO2-rich atmosphere). Recent reports have discussed the MO MA concept, design and performance. Here, we update the current prototype performance, focusing specifically on the GCMS mode.

Pinnick, Veronica↗

Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign

The concentration, size, and composition of non-refractory submicron aerosol (NR-PM(sub l)) was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS. During the campaign the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA) species dominate the NR-PM(sub l) mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA) and biomass burning (BB) are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 microg/cubic m (STP) ppm(exp -1). This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006) and Kleinman et al. (2008). The stability of the OA/CO while O/C increases with photochemical age implies a net loss of carbon from the OA. BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major regional source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city likely due to evaporation. BB does not appear to be a strong source of nitrate despite its high emissions of nitrogen oxides, presumably due to low ammonia emissions. NR-chloride often correlates with HCN indicating a fire source, although other sources likely contribute as well. This is the first aircraft study of the regional evolution of aerosol chemistry from a tropical megacity.

DeCarlo, P. F.↗

Modeling and measurement of the performance of a branched conduit sampling system in a mass spectrometer leak detector

In the leak testing of a large engineering system, one may distinguish three stages, namely leakage measurement by an overall enclosure, leak location, and leakage measurement by a local enclosure. Sniffer probes attached to helium mass spectrometer leak detectors are normally designed for leak location, a qualitative inspection technique intended to pinpoint where a leak is but not to quantify its rate of discharge. The main conclusion of the present effort is that local leakage measurement by a leak detector with a sniffer probe is feasible provided one has: (1) quantitative data on the performance of the mass separator cell (a device interior to the unit where the stream of fluid in the sample line branches); and (2) a means of stabilizing the mass transfer boundary layer that is created near a local leak site when a sniffer probe is placed in its immediate vicinity. Theoretical models of the mass separator cell are provided and measurements of the machine-specific parameters in the formulas are presented. A theoretical model of a porous probe end for stabilizing the mass transfer boundary is also presented.

Russell, John M.↗

Fast and deep phosphoproteome analysis with the Orbitrap Astral mass spectrometer

Owing to its roles in cellular signal transduction, protein phosphorylation plays critical roles in myriad cell processes. That said, detecting and quantifying protein phosphorylation has remained a challenge. We describe the use of a novel mass spectrometer (Orbitrap Astral) coupled with data-independent acquisition (DIA) to achieve rapid and deep analysis of human and mouse phosphoproteomes. With this method, we map approximately 30,000 unique human phosphorylation sites within a half-hour of data collection. The technology is benchmarked to other state-of-the-art MS platforms using both synthetic peptide standards and with EGF-stimulated HeLa cells. We apply this approach to generate a phosphoproteome multi-tissue atlas of the mouse. Altogether, we detect 81,120 unique phosphorylation sites within 12 hours of measurement. With this unique dataset, we examine the sequence, structural, and kinase specificity context of protein phosphorylation. Finally, we highlight the discovery potential of this resource with multiple examples of phosphorylation events relevant to mitochondrial and brain biology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Sensitivity in Targeted Single-Cell Proteomics by Coupling a Dual Ion Funnel Interface with Triple Quadrupole Mass Spectrometer

Single-cell proteomics (SCP) has emerged as a powerful approach for understanding cellular heterogeneity and biological processes at unprecedented resolution. However, the extremely limited protein content of individual cells (femtogram to picogram levels) pushes current mass spectrometry instrumentation to its sensitivity limits, creating a critical analytical bottleneck. While selected reaction monitoring (SRM) using triple quadrupole (QqQ) instruments 1 offers advantages in sensitivity and reproducibility for targeted proteomics quantification, SRM still struggles with sensitivity for quantification of moderate- or low-abundance proteins from single-cell sample amounts. Here, we report the development and systematic evaluation of a dual ion funnel interface designed to address the sensitivity limitation by significantly enhancing ion transmission efficiency in commercial QqQ mass spectrometers. The dual ion funnel interface, composed of a curved S-funnel followed by a conventional ion funnel, improves ion transmission efficiency while reducing chemical noise through selective ion focusing. The performance of the dual ion funnel interface was systematically compared to standard interface on a TSQ Vantage platform across samples with different levels of complexity. The dual funnel interface demonstrated to provide up to 25-fold improvement in sensitivity across a wide range of protein concentrations in different biological matrices (low complex mouse macrophage and high complex human cells). Critically, enhanced sensitivity was accompanied by increased analytical reproducibility with lower coefficient of variations. Most importantly, the dual funnel interface enabled reliable quantification of low-abundance proteins that were barely detectable or not detected by the standard interface, extending analysis to single-cell equivalent amounts while maintaining excellent reproducibility. These results demonstrate that the dual funnel interface addresses the critical bottleneck in quantitative targeted proteomics, providing a technological foundation for ultrasensitive targeted SCP that requires both high sensitivity and robust quantitative performance.

Min, Sehong↗

Empirical model of global thermospheric temperature and composition based on data from the OGO-6 quadrupole mass spectrometer

An empirical global model for magnetically quiet conditions has been derived from longitudinally averaged N2, O, and He densities by means of an expansion in spherical harmonics. The data were obtained by the OGO-6 neutral mass spectrometer and cover the altitude range 400 to 600 km for the period 27 June 1969 to 13 May 1971. The accuracy of the analytical description is of the order of the experimental error for He and O and about three times experimental error for N2, thus providing a reasonable overall representation of the satellite observations. Two model schemes are used: one representing densities extrapolated to 450 km and one representing densities extrapolated to 120 km with exospheric temperatures inferred from N2 densities. Using the best fit model parameters the global thermospheric structure is presented in the form of a number of contour plots.

Hedin, A. E.↗

Wind tunnel mass spectrometer design study

The sampling probe to measure the free stream gas composition in a hypersonic wind tunnel is described. Using a free expansion of the continuum flow, a series of sampling inlet-pumping stages is evaluated. Mass analysis is carried out with a quadrupole mass spectrometer employing a crossed electron beam, molecular beam ion source, and an off-axis electron multiplier. The spatial distribution of the sampled molecular flux and the pumping requirements are evaluated for varying inlet conditions of gas density and flow velocity. The signal-to-noise ratio of the molecular beam formed by this series of coaxial inlets is also determined. The signal-to-noise ratio of the unscattered flux is sufficiently high that an unambiguous determination of the beam composition and of the free stream gas properties can be made. The magnitude of the detected signal is sufficiently high that measurement of trace constituents two orders of magnitude below the primary beam signal can be made.

Hueser, J. E.↗

In-Situ Studies of the Lunar Water Cycle Using a CLPS-Delivered Ion-Trap Mass Spectrometer (PITMS)

Characterize the lunar exosphere from the surface after descent and landing, and throughout the lunar day, to understand the release and movement of volatile species. Leverage the PROSPECT program and develop the ITMS as a standalone mass spectrometer suitable for commercial lunar landers. PITMS will consist of a PROSPECT-derived ITMS sensor and front-end electronics, newly developed controller and power supply boards, and a GSFC wrapper. Lander-friendly: low resource (<2 kg, 4-8 W), simple interfaces, passive, landing site agnostic.

Cohen, Barbara A.↗

Ion Mass Spectrometer for Sporadic-E Rocket Experiments

NASA grant NAG5-5086 provided funding for the William B. Hanson Center for Space Sciences at the University of Texas at Dallas (UTD) to design, fabricate, calibrate, and ultimately fly two ion mass spectrometer instruments on a pair of sounding rocket payloads. Drs. R.A. Heelis and G.D. Earle from UTD were co-investigators on the project. The principal investigator for both rocket experiments was Dr. Robert Pfaff of the Goddard Space Flight Center. The overall project title was "Rocket/Radar Investigation of Lower Ionospheric Electrodynamics Associated with Intense Mid-Latitude Sporadic-E Layers". This report describes the overall objectives of the project, summarizes the instrument design and flight experiment details, and presents representative data obtained during the flights.

Heelis, R. A.↗

Determination of nitrogen monoxide in high purity nitrogen gas with an atmospheric pressure ionization mass spectrometer

An atmospheric pressure ionization mass spectrometric (API-MS) method was studied for the determination of residual NO in high purity N2 gas. The API-MS is very sensitive to NO, but the presence of O2 interferes with the NO measurement. Nitrogen gas in cylinders as sample gas was mixed with NO standard gas and/or O2 standard gas, and then introduced into the API-MS. The calibration curves of NO and O2 has linearity in the region of 0 - 2 ppm, but the slopes changed with every cylinder. The effect of O2 on NO+ peak was additive and proportional to O2 concentration in the range of 0 - 0.5 ppm. The increase in NO+ intensity due to O2 was (0.07 - 0.13)%/O2, 1 ppm. Determination of NO and O2 was carried out by the standard addition method to eliminate the influence of variation of slopes. The interference due to O2 was estimated from the product of the O2 concentration and the ratio of slope A to Slope B. Slope A is the change in the NO+ intensity with the O2 concentration. Slope B is the intensity with O2 concentration.

Kato, K.↗

Miniaturized GC/MS instrumentation for in situ measurements: micro gas chromatography coupled with miniature quadrupole array and paul ion trap mass spectrometers

Miniaturized chemical instrumentation is needed for in situ measurements in planetary exploration and other spaceflight applications where factors such as reduction in payload requirements and enhanced robustness are important. In response to this need, we are 'continuing to develop miniaturized GC/MS instrumentation which combines chemical separations by gas chromatography (GC) with mass spectrometry (MS) to provide positive identification of chemical compounds in complex mixtures of gases, such as those found in the International Space Station's cabin atmosphere. Our design approach utilizes micro gas chromatography components coupled with either a miniature quadrupole mass spectrometer array (QMSA) or compact, high-resolution Paul ion trap.

GC/MC miniature mass spectrometry MEMS↗

Computer-controlled mass spectrometer for on-line gas analysis

System detects gases in combustion chambers and records their levels of concentration. Simplified data recording and reduction process permits analysis rate of 9 msec per peak and recording of probe position, pressures, temperatures, and mass spectrometer data on same tape. System is applicable to air pollution control.

Hafner, F. W.↗

Molecular beam facility for studying mass spectrometer performance

An apparatus which produces neutral gas beams in the velocity range from thermal to 6 km/s makes possible studies simulating the motion of instruments through tenuous atmospheres. Use of the apparatus in studying the response of an open-source mass spectrometer is examined. Experiments performed include responses when the instrument is in a normal mode of operation, when the ion source potentials are adjusted to reject striking gas particles, when the beam is restricted so that portions of the ion source are struck, and when the beam strikes at angles other than normal incidence. Results indicate specular radiation of particles out of the source and stagnation ratios close to unity for normal operation. Retarding potential studies dropped the sensitivity by a factor of about 10, and as angles of attack are varied, the effect was found to depend upon beam velocity and the way the ions are initially accelerated.

Ballenthin, J. O.↗

A Fully Redundant On-Line Mass Spectrometer System Used to Monitor Cryogenic Fuel Leaks on the Space Shuttle

An on-line gas monitoring system was developed to replace the older systems used to monitor for cryogenic leaks on the Space Shuttles before launch. The system uses a mass spectrometer to monitor multiple locations in the process, which allows the system to monitor all gas constituents of interest in a nearly simultaneous manner. The system is fully redundant and meets all requirements for ground support equipment (GSE). This includes ruggedness to withstand launch on the Mobile Launcher Platform (MLP), ease of operation, and minimal operator intervention. The system can be fully automated so that an operator is notified when an unusual situation or fault is detected. User inputs are through personal computer using mouse and keyboard commands. The graphical user interface is very intuitive and easy to operate. The system has successfully supported four launches to date. It is currently being permanently installed as the primary system monitoring the Space Shuttles during ground processing and launch operations. Time and cost savings will be substantial over the current systems when it is fully implemented in the field. Tests were performed to demonstrate the performance of the system. Low limits-of-detection coupled with small drift make the system a major enhancement over the current systems. Though this system is currently optimized for detecting cryogenic leaks, many other gas constituents could be monitored using the Hazardous Gas Detection System (HGDS) 2000.

Griffin, Timothy P.↗

A Fully Redundant On-Line Mass Spectrometer System Used to Monitor Cryogenic Fuel Leaks on the Space Shuttle

An on-line gas monitoring system was developed to replace the older systems used to monitor for cryogenic leaks on the Space Shuttles before launch. The system uses a mass spectrometer to monitor multiple locations in the process, which allows the system to monitor all gas constituents of interest in a nearly simultaneous manner. The system is fully redundant and meets all requirements for ground support equipment (GSE). This includes ruggedness to withstand launch on the Mobile Launcher Platform (MLP), ease of operation, and minimal operator intervention. The system can be fully automated so that an operator is notified when an unusual situation or fault is detected. User inputs are through personal computer using mouse and keyboard commands. The graphical user for detecting cryogenic leaks, many other gas constituents could be monitored using the Hazardous Gas Detection System (HGDS) 2000.

Griffin, Timothy P.↗