Nano-Domain Analysis Via Massive Cluster Secondary Ion Mass Spectrometry in the Event-by-Event Mode

Secondary ion mass spectrometry (SIMS) is a surface analysis technique which characterizes species sputtered by an energetic particle beam. Bombardment with cluster projectiles offers the following notable advantages over bombardment with atomic ions or small clusters: enhanced emission of molecular ions, low damage cross-section, and reduced molecular fragmentation. Additionally, in the case of Au4004 and C60 impacts, desorption originates from nanometric volumes. These features make clusters useful probes to obtain molecular information from both nano-objects and nano-domains. The "event-by-event bombardment/detection mode" probes nano-objects one-at-a-time, while collecting and storing the corresponding secondary ion (SI) information. Presented here are the first experiments where free-standing nano-objects were bombarded with keV projectiles of atomic to nanoparticle size. The objects are aluminum nano-whiskers, 2 nm in diameter and ~250 nm in length. Au4004 has a diameter of ~2 nm, comparable to the nominal diameter of the nanowhiskers. There are notable differences in the SI response from sample volumes too small for full projectile energy deposition. The whisker spectra are dominated by small clusters?the most abundant species being AlO- and AlO2-. Bulk samples have larger yields for AlO2- than for AlO-, while this trend is reversed in whisker samples. Bulk samples give similar abundances of large SI clusters, while whisker samples give an order of magnitude lower yield of these SIs. Effective yields were calculated in order to determine quantitative differences between the nano-objects and bulk samples. The characterization of individual nano-objects from a mixture is demonstrated with negatively charged polymer spheres that are attracted to and retained by the nano-whiskers. The spheres are monodisperse polystyrene nanoparticles (30nm diameter). Our results show that the event-by-event mode can provide information on the nature, size, relative location, and abundance of nano-objects in the field of view. This study presents the first evidence of quantitative molecular information originating from nano-object mixtures. Biologically relevant systems (solid-supported lipid bilayers) were also characterized using Au5 , Au4004 and C60 . Organization-dependent SI emission was observed for phosphocholine bilayers. Lipid domain formation was also investigated in bilayers formed from cholesterol and a mixed lipid system. Trends in the correlation coefficient suggest that cholesterol segregates from the surrounding lipid environment during raft formation

Operational Parameters, Considerations, and Design Decisions for Resource-Constrained Ion Trap Mass Spectrometers

Mass spectrometers are increasingly finding applications in new and unique areas, often in situations where key operational resources (i.e. power, weight and size) are limited. One such example is the Mars Organic Molecule Analyzer (MOMA). This instrument is a joint venture between NASA and the European Space Agency (ESA) to develop an ion trap mass spectrometer for chemical analysis on Mars. The constraints on such an instrument are significant as are the performance requirements. While the ideal operating parameters for an ion trap are generally well characterized, methods to maintain analytical performance with limited power and system weight need to be investigated and tested. Methods Experiments have been performed on two custom ion trap mass spectrometers developed as prototypes for the MOMA instrument. This hardware consists of quadrupole ion trap electrodes that are 70% the size of common commercial instrumentation. The trapping RF voltage is created with a custom tank circuit that can be tuned over a range of RF frequencies and is driven using laboratory supplies and amplifiers. The entire instrument is controlled with custom Lab VIEW software that allows a high degree of flexibility in the definition of the scan function defining the ion trap experiment. Ions are typically generated via an internal electron ionization source, however, a laser desorption source is also in development for analysis of larger intact molecules. Preliminary Data The main goals in this work have been to reduce the power required to generate the radio frequency trapping field used in an ion trap mass spectrometer. Generally minimizing the power will also reduce the volume and mass of the electronics to support the instrument. In order to achieve optimum performance, commercial instruments typically utilize RF frequencies in the 1 MHz range. Without much concern for power usage, they simply generate the voltage required to access the mass range of interest. In order to reduce the required RF voltage (and power), operation of the ion trap at lower RF frequencies has been investigated. Surprisingly, the performance of the instrument has only been slightly degraded at RF frequencies all the way down to 500 kHz. Mass resolution is relatively stable to this point and depending on the resonant ejection point used, the peak intensity is also quite stable. To date only masses up to m/z 200 have been fully investigated, however, additional studies are planned to verify the performance with higher mass ions. The lower frequency and voltage should reduce the pseudo potential well depth, eventually affecting the trapping efficiency of the instrument -- effect that could manifest itself in significantly limiting the mass range of trapped ions. Other methods to reduce the RF power while maintaining analytical performance are also under investigation. This includes ion ejection at lower q(sub z) values to access a given mass with a lower RF voltage. The loss of mass resolution at lower q(sub eject) points has been measured and current work is underway to leverage scan speed and the use of non-linear resonances in order to counter this trend. The overall trap performance under this range of operating conditions will be presented with a goal of identifying what trade-offs are acceptable

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

Evaluation of Pulse Counting for the Mars Organic Mass Analyzer (MOMA) Ion Trap Detection Scheme

The Mars Organic Mass Analyzer is being developed at Goddard Space Flight Center to identify organics and possible biological compounds on Mars. In the process of characterizing mass spectrometer size, weight, and power consumption, the use of pulse counting was considered for ion detection. Pulse counting has advantages over analog-mode amplification of the electron multiplier signal. Some advantages are reduced size of electronic components, low power consumption, ability to remotely characterize detector performance, and avoidance of analog circuit noise. The use of pulse counting as a detection method with ion trap instruments is relatively rare. However, with the recent development of high performance electrical components, this detection method is quite suitable and can demonstrate significant advantages over analog methods. Methods A prototype quadrupole ion trap mass spectrometer with an internal electron ionization source was used as a test setup to develop and evaluate the pulse-counting method. The anode signal from the electron multiplier was preamplified. The an1plified signal was fed into a fast comparator for pulse-level discrimination. The output of the comparator was fed directly into a Xilinx FPGA development board. Verilog HDL software was written to bin the counts at user-selectable intervals. This system was able to count pulses at rates in the GHz range. The stored ion count nun1ber per bin was transferred to custom ion trap control software. Pulse-counting mass spectra were compared with mass spectra obtained using the standard analog-mode ion detection. Prelin1inary Data Preliminary mass spectra have been obtained for both analog mode and pulse-counting mode under several sets of instrument operating conditions. Comparison of the spectra revealed better peak shapes for pulse-counting mode. Noise levels are as good as, or better than, analog-mode detection noise levels. To artificially force ion pile-up conditions, the ion trap was overfilled and ions were ejected at very high scan rates. Pile-up of ions was not significant for the ion trap under investigation even though the ions are ejected in so-called 'ion-micro packets'. It was found that pulse counting mode had higher dynamic range than analog mode, and that the first amplification stage in analog mode can distort mass peaks. The inherent speed of the pulse counting method also proved to be beneficial to ion trap operation and ion ejection characterization. Very high scan rates were possible with pulse counting since the digital circuitry response time is so much smaller than with the analog method. Careful investigation of the pulse-counting data also allowed observation of the applied resonant ejection frequency during mass analysis. Ejection of ion micro packets could be clearly observed in the binned data. A second oscillation frequency, much lower than the secular frequency, was also observed. Such an effect was earlier attributed to the oscillation of the total plasma cloud in the ion trap. While the components used to implement pulse counting are quite advanced, due to their prevalence in consumer electronics, the cost of this detection system is no more than that of an analog mode system. Total pulse-counting detection system electronics cost is under $25

In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds

Performance of the Linear Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer (MOMA) Investigation on the 2018 Exomars Rover

The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from degradation derived from cosmic radiation and/or oxidative chemical reactions. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. The MOMA investigation is led by the Max Planck Institute for Solar System Research (MPS) with the mass spectrometer subsystem provided by NASA GSFC. MOMA's linear ion trap mass spectrometer (ITMS) is designed to analyze molecular composition of: (i) gas evolved from pyrolyzed powder samples and separated in a gas chromatograph; and, (ii) ions directly desorbed from crushed solid samples at Mars ambient pressure, as enabled by a pulsed UV laser system, fast-actuating aperture valve and capillary ion inlet. Breadboard ITMS and associated electronics have been advanced to high end-to-end fidelity in preparation for flight hardware delivery to Germany in 2015

Mars Organic Molecule Analyzer (MOMA) Laser Desorption/Ionization Source Design and Performance Characterization

The Mars Organic Molecule Analyzer (MOMA), a dual-source, ion trap-based instrument capable of both pyrolysis-gas chromatography mass spectrometry (pyr/GC-MS) and laser desorption/ionization mass spectrometry (LDI-MS), is the core astrobiology investigation on the ExoMars rover. The MOMA instrument will be the first spaceflight mass analyzer to exploit the LDI technique to detect refractory organic compounds and characterize host mineralogy; this mode of analysis will be conducted at Mars ambient conditions. In order to achieve high performance in the Martian environment while keeping the instrument compact and low power, a number of innovative designs and components have been implemented for MOMA. These include a miniaturized linear ion trap (LIT), a fast actuating aperture valve with ion inlet tube, and a Microelectromechanical System (MEMS) Pirani sensor. Advanced analytical capabilities like Stored Waveform Inverse Fourier Transform (SWIFT) for selected ion ejection and tandem mass spectrometry (MS/MS) are realized in LDI-MS mode, and enable the isolation and enhancement of specific mass ranges and structural analysis, respectively. We report here the technical details of these instrument components as well as system-level analytical capabilities, and we review the applications of this technology to Mars and other high-priority targets of planetary exploration

How TMAH Thermochemolysis can improve the detection of trace organic matter on Mars using the MOMA-Pyr-GC-MS experiment aboard the ExoMars-2020

International audienceThe Mars Organic Molecule Ana-lyzer (MOMA) experiment aboard the future ExoMars2020mission will be the continuation of the search for the organic composition of the Mars surface. The mainadvantage of Exomars is that the sample will be ex-tracted as deep as 2 meters belowthemartian surfaceand is expected to be preserved fromtheeffects of ra-diation and oxidation onorganic materials. To analyze the wide range of potential organic composition (vola-tile and non volatilecompounds) of the martian soil,the MOMA instrument utilizes bothUV laser desorp-tion / ionization (LDI) andpyrolysis gas chromatog-raphy ion trap mass spectrometry (pyr-GC-ITMS). In order to analyse refractory organic compounds,and charactize the enantiomeric ratio for the chiral species,the sample can be submittedto a derivatization pro-cess, consisting of the reaction of the sample compo-nents with specific reactantsselected for MOMA